Journal of Industrial and Engineering Chemistry 19 (2013) 215–219

Contents lists available at SciVerse ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Design and operating parameters affecting an electrochlorination system

Jusol Choi, Soojin Shim, Jeyong Yoon *
World Class University (WCU) Program of Chemical Convergence for Energy & Environment (C2E2), School of Chemical and Biological Engineering, College of Engineering, Institute of
Chemical Process (ICP), Seoul National University (SNU), 599 Gwanak-ro, Gwanak-gu, Seoul 151-744, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: Electrolysis of aqueous sodium chloride has been widely used in the chloro-alkali process, and its
Received 17 May 2012 operating parameters are well-known. This electrochemical mechanism can be applied to both on-site
Accepted 4 August 2012 chlorine production for disinfecting water in small-scale drinking water treatment plants and as a
Available online 10 August 2012
portable chlorine generator for emergency use or for campers. However, the design information and
operating parameters affecting the current efficiency and power consumption of small-scale
Keywords: electrochlorination systems are limited even though these systems have become popular. We investigate
Drinking water
the significant design and operating parameters affecting current efficiency and power consumption in
Disinfection
an electrochlorination system. IrO2 electrodes, NaCl concentration, current density, a separator, and
Electrochlorination
IrO2 temperature control were selected as the design and operating parameters in the two-electrode batch
Current efficiency system. The results show that the most important parameter affecting current efficiency and power
Power consumption consumption of chlorine generation was NaCl concentration. At low NaCl concentrations (1000 mg/L),
the type of anode, current density, and the separator considerably affected current efficiency and power
consumption to generate chlorine, whereas at high NaCl concentrations (>35,000 mg/L), anode type
became insignificant, with current efficiency >90% and power consumption of 4–6 Wh/g.
ß 2012 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction
Chlorine is one of the most important chemicals in drinking
water treatment plants to supply pathogen-free drinking water.
Safety problems are considerable, as chlorine required for
disinfection is transported in the gas phase by truck and stored
in a tank [1,2]. To resolve these chlorine gas safety issues, on-site
chlorine generation systems are necessary and can be achieved
using an electrochemical system that has many advantages,
including process versatility, energy effectiveness, and environ-
mental compatibility [3]. Hence, an electrochemical chlorine
generation system, electrochlorination system, would be consid-
ered as an alternative process.
An electrochlorination system consists of electrodes, an
electrolyte, and a circuit, and anodes are a significant factor for
chlorine generation. According to the property of anodic materials,
anodes are divided into active and nonactive electrodes; IrO2 and
RuO2 are the former and boron-doped diamond (BDD) is the latter
[4–6]. Among various electrodes such as IrO2, RuO2, and BDD, the
* Corresponding author at: 599 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic
of Korea. Tel.: +82 2 880 8927; fax: +82 2 876 8911.
E-mail address: jeyong@snu.ac.kr (J. Yoon).
IrO2 electrode has better efficiency than the others to produce
chlorine in the presence of NaCl [7]. Furthermore, the chlorine
solution generated in an electrochemical system is slightly more
efficient for inactivating microorganisms than free chlorine under
certain pH conditions [8].
In an electrochlorination system, chloride ions are oxidized to
form chlorine on the anode surface by two-electron transfer
(Eq. (1)), and then the chlorine exists as hypochlorous acid and/or
hypochlorite according to pH (Eqs. (2) and (3)) [9,10].
2Cl ! Cl2 þ 2e (1)
Cl2 þ H2 O ! HOCl þ Hþ þ Cl (2)
HOCl $ Hþ þ OCl (3)
Electrolysis of aqueous sodium chloride to produce several
chemicals such as chlorine, sodium hydroxide, and hydrogen in
chloro-alkali process has been widely employed by applying these
electrochemical reactions, and the design and operating param-
eters are well known [11]. However, concerns about electrolysis of
aqueous sodium chloride have been raised. First, the electrolysis of
aqueous sodium chloride can be applied to treat wastewater and
landfill leachate [12,13]. Furthermore, this has been increasingly
applied due to the safety issues of handling chlorine gas and

1226-086X/$ – see front matter ß 2012 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2012.08.004
216 J. Choi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 215–219

producing chlorine. Additionally, a small-scale chlorine generator Table 1

Atomic percentages of the IrO2 electrodes.
for emergency use or for campers has been developed, and various
design and operating parameters affecting electrochemical chlo- Atomic percentage (%)
rine generation have been reported [14–16]. C O Ti Ir Ta Others
However, design and operating information for a small-scale
IrO2-A 15.6 62.4 16.2 5.1 – 0.7
electrochlorination system with respect to current efficiency and IrO2-B 17.4 37.3 35.6 0.9 – 8.8
power consumption are limited. Therefore, we investigate the IrO2-C 38.0 48.4 0.3 7.2 6.1 –
most important design and operating parameters affecting current
efficiency and power consumption during chlorine generation in
an electrochlorination system. In this study, IrO2 electrodes, NaCl to its facile procedure [17]. Iridium salts are dissolved in suitable
concentration, current density, the presence of a separator, and solvents, and then the solvent is coated by brushing or dipping
temperature control were selected as design and operating onto the substrate. After that, the coated substrate is calcinated.
parameters. Table 1 summarizes the surface atomic percentages of the IrO2
electrodes as analyzed by EDS. The results showed Ir atomic
percentages of 0.9–7.2%. A stainless steel plate with the same
2. Experimental
working area was used as the cathode. The anode and cathode
were placed parallel in the undivided and divided cells, and
2.1. Chemicals and analyses
the distances between them were 10 mm and 20 mm for the
undivided and divided cells, respectively.
All chemicals used in this study were reagent grade and used
without further purification. Sodium chloride was purchased from
2.3. Design and operating parameters and experimental procedures
Sigma–Aldrich Co. (St. Louis, MO, USA). The water used for cleaning
or dissolving solutes was distilled and deionized by a Millipore
Table 2 summarizes the details of the experimental conditions
purification system (Bedford, MA, USA). The total chlorine
used in this study. As shown in Table 2, IrO2 electrodes, NaCl
concentration was measured by the DPD (N,N-diethyl-p-pheny-
concentration, current density, the absence or presence of a
lenediamine) colorimetric method (DR/2010, HACH Co., Loveland,
separator, and with or without temperature control were selected
CO, USA) at 530 nm. The atomic percentages of the electrode
as the design and operating parameters. Experimental results at
surface were characterized by field emission scanning electron
various conditions were compared with the control condition
microscopy (JSM-6701F, JEOL Co., Tokyo, Japan) equipped with an
(entry 1) (IrO2-A, 167 mA/cm2, no temperature control, no
energy dispersive X-ray spectrometer (EDS).
separator, NaCl concentration of 1000 mg/L (about five-times
higher NaCl concentration than that of wastewater [18])). All
2.2. Electrochemical cells and apparatus
experiments were carried out at neutral pH without pH control.
Electrochlorination was conducted as follows. Prior to the
Fig. 1 shows the electrochemical cells employed in this study
experiments, the electrodes were sonicated (60 kHz and 500 W,
((a) and (b) show an undivided cell and a divided cell, respectively).
Powersonic 410, Whasin Tech Co., Seoul, Korea) and cleaned with
Constant current density was provided by a DC power supply
deionized water several times. Then, the anode and cathode were
(UDP-150I, Unicorn Tech Co., Seoul, Korea). The cylindrically
immersed in the divided or undivided cells containing a 150 mL
shaped undivided cell (Fig. 1(a)) has a volume of 150 mL. The
solution of a predetermined NaCl concentration. Low and high
divided cell (Fig. 1(b)) consists of a 50-mL cathode compartment
NaCl concentrations represented the salt concentration of waste-
and a 100-mL anodic compartment, and a Nafion 117 membrane
water treatment effluents (1000 mg/L), and a saturated salt
(DuPont, Wilmington, DE, USA) was placed between the compart-
concentration (350,000 mg/L), respectively. In the case of the
ments. Commercial IrO2 electrodes, IrO2-A (Samsung DSA Co.,
temperature control (20 8C) experiment, the cell was placed in a
Seoul, Korea), IrO2-B (Daejun Chemical Co., Seoul, Korea), and IrO2-
water bath (Model RW-2025G, JEIO TECH, Seoul, Korea). Other-
C (Dongsung Co., Seoul, Korea) with a working area of 6 cm2
wise, the experiments were carried out at room temperature
(2 cm  3 cm) were used as anodes. The thermal decomposition
without temperature control. Electrochlorination was performed
method is generally preferred over electrodeposition, and chemi-
for 10 min with predetermined constant current densities (33 mA/
cal vapor deposition in synthesizing commercial IrO2 electrode due
cm2, 67 mA/cm2, 100 mA/cm2, 133 mA/cm2 or 167 mA/cm2). All
experiments were performed in triplicate to examine reproduc-
ibility.

2.4. Current efficiency and power consumption

Based on two-electron transfer (Eq. (1)) to form chlorine during

electrochlorination, current efficiency (Eq. (4)) was calculated
using Faraday’s law [19], and power consumption (Eq. (5)) was
calculated as follows:

Vol  DC  n  F
Current efficiency ð%Þ ¼  100% (4)
iapp  t

E  iapp  t 1
Power consumption ðWh=gÞ ¼  (5)
Vol  DC 71  3600
where iapp is the applied current (A), t is the elapsed time (s), Vol is
the solution volume (L), DC is the concentration difference in
Fig. 1. Schematic of the electrochemical cell employed in this study ((a) the chlorine (M), n is the number of electrons required, F is the Faraday
undivided cell and (b) the divided cell). constant (96,485 C mol1), and E is the average voltage (V) during
 J. Choi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 215–219 217

Table 2
Details of the experimental conditions.

Entry Design and operating parameters

Type of electrode NaCl concentration (mg/L) Current density (mA/cm2) Separator Temperature control

1 IrO2-A 1000 167 No No

2 10,000
3 35,000
4 Saturation (350,000)
5 1000 167 No Yes
6 Yes No
7 1000 133 No No
8 100
9 67
10 33

11 IrO2-B 1000 167 No No

12 Saturation (350,000)

13 IrO2-C 1000 167 No No

14 Saturation (350,000)

electrochlorination. The current efficiency (Eq. (4)) is the ratio of
the electrical charge consumed to the total electrical charge passed
during the electrochemical reaction. Power consumption (Wh/g) is
the total energy required for producing a unit of chlorine by
electrochlorination (Eq. (5)).
3. Results and discussion
power consumption is about 4.4 Wh/g [2] at NaCl concentration of
>35,000 mg/L. One explanation is that current densities for
chlorine on IrO2-coated electrodes are very high as compared to
exchange current densities for oxygen although oxygen evolution
is thermodynamically preferred [21]. Excess NaCl concentration
higher than 35,000 mg/L is not recommended in field operation to

3.1. Effect of the IrO2 electrodes

Fig. 2 shows current efficiency and power consumption at two

representative conditions of NaCl concentration (low NaCl
concentration [1000 mg/L], and high NaCl concentration [saturat-
ed NaCl concentration of 350,000 mg/L]) with the IrO2-A, IrO2-B,
and IrO2-C electrodes. As shown in Fig. 2(a), all current efficiencies
for the electrodes were low and varied (14–32%) at a low NaCl
concentration (1000 mg/L), showing extreme high power con-
sumption of 127–291 Wh/g, whereas at the high NaCl concentra-
tion, all current efficiencies were high (>94%), and consumed very
little power of 3–4 Wh/g (Fig. 2(b)).
One explanation for the different current efficiencies and power
consumption at low NaCl concentration can be found from the
different Ir contents on the electrode surface (Table 1), considering
a report that the active surface area of an electrode is proportional
to IrO2 loading [20]. That is, IrO2-B, which has a rather low Ir
content on the electrode surface (0.9%), compared to that of the
other electrodes (IrO2-A, IrO2-C), resulted in relatively low current
efficiency. However, at a high NaCl concentration (saturated salt
concentration), the difference in Ir content on the electrode surface
had no significant effect on current efficiency or power consump-
tion. Thereafter, all experiments were carried out using the IrO2-A
electrode.

3.2. Effect of NaCl concentration and current density

Fig. 3 shows the change in current efficiency and power

consumption with a change in NaCl concentration. The results of
Fig. 2, which were obtained at two NaCl concentrations (1000 mg/L
and 350,000 mg/L), were included for comparison. When NaCl
concentration was increased from 1000 mg/L, current efficiency
increased rapidly and power consumption decreased significantly.
Note that at NaCl concentration of 1000 mg/L, the current
efficiency and the power consumption were about 32% and
131 Wh/g, respectively (Fig. 3). However, current efficiency
Fig. 2. Current efficiency and power consumption using three commercial IrO2-A,
stagnated at 90% and power consumption at 4–6 Wh/g when IrO2-B, and IrO2-C electrodes at two NaCl concentrations: (a) 1000 mg/L and (b)
the NaCl concentration exceeded 35,000 mg/L, supporting previ- saturated NaCl concentration (350,000 mg/L) (i = 167 mA/cm2, no separator and
ous studies stating that current efficiency is about 90% [21] and temperature control, reaction time = 10 min).
218 J. Choi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 215–219
Fig. 3. Current efficiency and power consumption as a function of NaCl
concentration (electrode: IrO2-A, i = 167 mA/cm2, [NaCl]0 = 1000 mg/L,
10,000 mg/L, 35,000 mg/L, and a saturated concentration (350,000 mg/L), no
separator and temperature control, reaction time = 10 min).
Fig. 4. Current efficiency and power consumption as a function of current density
(electrode: IrO2-A, i = 33, 67, 100, 133, and 167 mA/cm2, [NaCl]0 = 1000 mg/L, no
separator and temperature control, reaction time = 10 min).
enhance current efficiency. Fig. 4 shows the changes in current
efficiency and power consumption with respect to current density.
Note that this experiment was performed under the low NaCl
concentration condition (1000 mg/L). As shown in Fig. 4, current
efficiency decreased slightly from 40% to 32%, whereas power
consumption increased significantly from 28 Wh/g to 131 Wh/g as
current density increased from 33 mA/cm2 to 167 mA/cm2. The
diminished current efficiency with the increase in current density
can be explained by the highly competitive reaction such as oxygen
evolution under high current density conditions [22,23].
3.3. Effect of temperature control and the separator
Fig. 5 shows the changes in current efficiency and power
consumption in the presence or absence of the separator and
whether temperature control was used during electrolysis as
compared with the control condition. As shown in Fig. 5, the
presence of temperature control had no significant effect on
current efficiency (30–32%), which was consistent with previous
studies [15,16]. In contrast, the presence of the separator had a
slight negative effect on current efficiency, decreasing it by about
8%. Additionally, power consumption increased by 158 Wh/g in the
presence of the separator compared to that under the control
condition. The increase in power consumption in the presence of
Fig. 5. Current efficiency and power consumption affected by the presence of a
separator and temperature control (electrode: IrO2-A, i = 167 mA/cm2,
[NaCl]0 = 1000 mg/L, control (no separator and temperature control),
temperature control (+no separator): separator (+no temperature control),
reaction time = 10 min).
the separator can be explained by an increase in total resistance
consisting of solution, circuit, and separator resistance [11].
Thus, the most important design and operating parameter
affecting current density and power consumption was NaCl
concentration. As a result, NaCl concentration should be consid-
ered first when operating an electrochlorination system efficiently.
Then, determining the anode type, current density, and the
presence of a separator would become considerably important
when electrochlorination is operated at a low NaCl concentration
(1000 mg/L). However, under a high NaCl concentration
(>35,000 mg/L), the type of anode and current density (33–
167 mA/cm2) would appear to be insignificant.
4. Conclusions
We report important design and operating parameters (type of
electrodes, NaCl concentration, current density, separator, and
temperature control) affecting current efficiency and power
consumption in an electrochlorination system. The most critical
parameter affecting current efficiency and power consumption
was NaCl concentration. Current efficiency increased by 62% and
power consumption decreased by 127 Wh/g as NaCl concentration
increased from 1000 to 350,000 mg/L. The type of anode, current
density, and the presence of a separator considerably affected
current efficiency and power consumption for chlorine generation
at a low NaCl concentration (1000 mg/L). In contrast, the type of
anode became insignificant at a high NaCl concentration
(>35,000 mg/L), revealing a current efficiency > 90% and power
consumption of 4–6 Wh/g.
Acknowledgment
This research was supported by WCU (World Class University)
program through the National Research Foundation of Korea
funded by the Ministry of Education, Science and Technology (R31-
10013).
References
[1] K.P. Cantor, C.F. Lynch, M.E. Hildesheim, M. Dosemeci, J. Lubin, M. Alavanja, G.
Craun, Epidemiology 9 (1998) 21.
[2] G.C. White, The Handbook of Chlorination and Alternative Disinfectants, J. Wiley,
New York, 1999.
 J. Choi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 215–219
[3] K. Rajeshwar, J.G. Ibanez, G.M. Swain, Journal of Applied Electrochemistry 24
(1994) 1077.
[4] B. Marselli, J. Garcia-Gomez, P.A. Michaud, M.A. Rodrigo, C. Comninellis, Journal of
the Electrochemical Society 150 (2003) D79.
[5] C. Comninellis, Electrochimica Acta 39 (1994) 1857.
[6] P.A. Michaud, M. Panizza, L. Ouattara, T. Diaco, G. Foti, C. Comninellis, Journal of
Applied Electrochemistry 33 (2003) 151.
[7] J. Jeong, C. Kim, J. Yoon, Water Research 43 (2009) 895.
[8] H. Son, M. Cho, H. Chung, S. Choi, J. Yoon, Journal of Industrial and Engineering
Chemistry 10 (2004) 705.
[9] L.R. Czarnetzki, L.J.J. Janssen, Journal of Applied Electrochemistry 22 (1992) 315.
[10] L. Szpyrkowicz, J. Naumczykt, F. Zilio-Grandi, Toxicological and Environmental
Chemistry 44 (1994) 189.
[11] D. Pletcher, F. Walsh, Industrial Electrochemistry, Chapman and Hall, London,
1990.
[12] E. Turro, A. Giannis, R. Cossu, E. Gidarakos, D. Mantzavinos, A. Katsaounis, Journal
of Hazardous Materials 190 (2011) 460.
219
[13] L.-C. Chiang, J.-E. Chang, T.-C. Wen, Water Research 29 (1995) 671.
[14] O. Scialdone, S. Randazzo, A. Galia, G. Silvestri, Water Research 43 (2009) 2260.
[15] A. Khelifa, S. Moulay, F. Hannane, S. Benslimene, M. Hecini, Desalination 160
(2004) 91.
[16] A. Kraft, M. Stadelmann, M. Blaschke, D. Kreysig, B. Sandt, F. Schröder, J. Rennau,
Journal of Applied Electrochemistry 29 (1999) 859.
[17] C. Comninellis, G. Chen, Electrochemistry for the Environment, Springer Verlag,
New York, London, 2009.
[18] V.L. Snoeyink, D. Jenkins, Water Chemistry, J. Wiley, New York, 1980.
[19] A. Bard, L. Faulkner, Electrochemical Methods: Fundamentals and Applications, J.
Wiley, New York, 2001.
[20] R.F. Savinell, R.L. Zeller III, J.A. Adams, Journal of the Electrochemical Society 137
(1990) 489.
[21] J.E. Bennett, International Journal of Hydrogen Energy 5 (1980) 401.
[22] M. Badruzzaman, J. Oppenheimer, S. Adham, M. Kumar, Journal of Membrane
Science 326 (2009) 392.
[23] M. Bergmann, A. Koparal, Journal of Applied Electrochemistry 35 (2005) 1321.