Analytica Chimica Acta 537 (2005) 293–298

Determination of free chlorine based on anodic voltammetry using

platinum, gold, and glassy carbon electrodes
Fumihiro Kodera, Minoru Umeda, Akifumi Yamada ∗
Department of Chemistry, Faculty of Engineering, Nagaoka University of Technology, 1603-1 Kamitomioka, Nagaoka, Niigata 940-2188, Japan

Received 4 February 2004; received in revised form 24 January 2005; accepted 24 January 2005
Available online 19 February 2005

Abstract

The oxidation of free chlorine on platinum, gold, and glassy carbon disk electrodes has been investigated by using anodic voltammetry to
determine the free-chlorine concentration. The voltammetric curves exhibited well-defined anodic peaks. The influences of pH, free-chlorine
concentration, and potential sweep rate on the electrode response were investigated. The results show that the measurement of the oxidation
peak current can be used as the basis for a simple, accurate, and rapid method for the determination of ClO− , within a concentration range of
4–400 mg Cl l−1 . The results of this method were in good agreement with those obtained by iodometric titration. Differential pulse voltammetry
has also been examined, resulting in an improved sensitivity at a concentration of 1.0 mg Cl l−1 .
© 2005 Elsevier B.V. All rights reserved.

Keywords: Anodic voltammetry; Free chlorine; Glassy carbon electrode; Platinum

1. Introduction that is capable of determining hypochlorite quantitatively,

Sodium hypochlorite is used for a number of purposes,
such as disinfection [1], bleaching [2], and as a powerful oxi-
dizing agent in various manufacturing processes [3]. In recent
years, there have been concerns about the environmental ef-
fects of such widespread use of hypochlorite, but alternative
oxidants have failed to compete effectively because sodium
hypochlorite is not only an efficient and inexpensive oxidant
but is also relatively easy to handle and store [4].
Sodium hypochlorite applied to water undergoes hydrol-
ysis to form free chlorine consisting of hypochlorous acid
(HOCl) and hypochlorite ion (ClO− ) [5]. Commercially,
sodium hypochlorite is available as an alkaline solution of ap-
proximately pH = 11, usually containing between 5 and 15%
(w/v) in the form of hypochlorite ion [6].
Several analytical methods, such as iodometric titration
and colorimetric methods, have been used to detect the free
chlorine [5]. However, there is not an ideal analytical method
∗ Corresponding author. Tel.: +81 258 47 9325; fax: +81 258 47 9300.
E-mail addresses: k fumi@agate.plala.or.jp (F. Kodera),
yamada@chem.nagaokaut.ac.jp (A. Yamada).
when we consider the advantages and disadvantages of each
method.
For the determination of free chlorine, the electroanalyti-
cal method [7–13] is very attractive because of its simplicity
due to the electroactivity of free chlorine. It measures current,
and most reagents are unnecessary. Therefore, it appears to
be the most suitable technique for on-line monitoring.
The electroanalytical method is currently based on the
following reduction reaction [13,14].
In basic region (pH > 8.5):
ClO− + H2 O + 2e− → Cl− + 2OH− , (1)
and in acidic region (pH < 5.5):
HOCl + 2e− → Cl− + OH− . (2)
Though this method is useful, the reaction is similar to the
reduction potential of the dissolved oxygen. Therefore, the
reduction of the dissolved oxygen should be considered. The
effect of trace amounts of metal ions should also be taken
into account.

0003-2670/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2005.01.053
294 F. Kodera et al. / Analytica Chimica Acta 537 (2005) 293–298

Here, we note the anodic reaction [14–20]. The overall
anodic reaction can be expressed as follows.
In basic region (pH > 8.5):
6ClO− + 3H2 O → 2ClO3 − + 4Cl− + 6H + + 3/2O2 + 6e− ,
(3)
sizes, 3 M Co), carefully sonicated in water, and then rinsed
with water. The polished electrode was then pretreated in an
electrolytic solution by a potential sweep in the conventional
manner [21,22].
2.4. Measurement procedure

and in acidic region (pH < 5.5): A background voltammogram was measured in the elec-
− − +
6HOCl + 3H2 O → 2ClO3 + 4Cl + 12H + 3/2O2 + 6e . − trolytic aqueous solution, then each amount of the free-
chlorine solution was pipetted into the solution. The deter-
(4) mination of free-chlorine concentration was carried out by
using for the anodic reaction at 25 ± 1 ◦ C. The measurement
To the authors’ knowledge, no report regarding an analytical
was carried out after the addition of the free-chlorine solution
method utilizing this reaction has been published.
in 1 h to prevent the decomposition of free chlorine. All ex-
The present work presents an attempt to examine the use
periments were performed under a non-deaerated condition.
of anodic voltammetry for the quantitative determination of
free chlorine. This information is important for the evalu-
ation of the direct use of voltammetry in actual analytical
3. Results and discussion
situations. Furthermore, we have also examined the use of
differential pulse voltammetry (DPV) which is useful for the
3.1. Pt electrode activation
low concentration determination.
The application of large potential excursions to noble-
metal electrodes has long been known to result in repro-
2. Experimental
ducibly clean and reactive electrode surfaces. Virtually ev-
ery publication on voltammetric data for noble-metal elec-
2.1. Reagents
trodes briefly describes a protocol for an electrode pretreat-
ment applied to maintain electrode activity and ensure repro-
A standard free-chlorine solution was prepared by dilut-
ducible data. Most commonly, the pretreatment involves the
ing a sodium hypochlorite aqueous solution (Nakarai, Japan).
application of repeated cyclic potential scans or alternated
The concentration of the solution was determined by iodo-
positive and negative potential pulses. Such electrochemical
metric titration [5]. Sodium perchlorate (Merck, Germany)
treatments for maintaining the optimal activity of Pt elec-
was used as a supporting electrolyte. All reagents were of
trodes have been reported elsewhere [23–25]. In this study,
analytical grade and were used as received. Water was ob-
the surface of the working electrode was polished with pol-
tained from a Milli-Q Labo purification system (Millipore,
ishing films. The polished electrode was then pretreated in
Japan). The pH was measured with a conventional glass elec-
an electrolytic solution by repeating cyclic potential scans
trode system (HORIBA, F-12, Japan).
from the oxygen evolution potential to the hydrogen gener-
ation potential. The influence of the activation on the cyclic
2.2. Instrumentation voltammograms at the Pt electrode is shown in Fig. 1: (a) is

The electrochemical measurements were carried out

in a conventional three-electrode cell using a computer-
controlled electrochemical system (BAS100B/W, USA) or a
potentiostat (HA-301, Hokuto Denko, Japan), a function gen-
erator (HB-105, Hokuto Denko, Japan) and an X–Y recorder
(WX1100, Graphtec, Japan). A platinum (Pt) disk (1.6 mm
or 10 ␮m diameter, BAS, Japan) was used as a working elec-
trode, and a gold (Au) disk (1.6 mm diameter, BAS, Japan)
and a glassy carbon (GC) disk (1.0 mm diameter, BAS, Japan)
were used for comparison. A platinum wire was used as
a counter electrode, and an Ag/AgCl electrode (3 M NaCl,
BAS, Japan) was used as a reference electrode.

2.3. Pretreatment of electrodes

Fig. 1. Effect of pretreatment of Pt disk electrode on the cyclic voltammo-
The surface of the working electrode was polished with grams in 0.1 M NaClO4 : (a) before and (b) after the treatment with cyclic
polishing films (in a sequence of 3, 2, 1, 0.5 and 0.3 ␮m grain potential scans. Sweep rate: 50 mV s−1 .
 F. Kodera et al. / Analytica Chimica Acta 537 (2005) 293–298 295

function of free-chlorine concentration: (a) 140 mg Cl l−1 , (b)

70 mg Cl l−1 , and (c) blank. In Fig. 3, a well-defined anodic
peak is apparent at 1.1 V for each electrode.
Plots of the anodic peak current versus the concentration of
free chlorine at each electrode are in good agreement. This
implies the reaction non-electrocatalytically occurs. A lin-
ear relationship is observed over the concentration range of
4–400 mg Cl l−1 , with a linear regression coefficient (R2 ) of
more than 0.99.

3.3. Effect of Ph

The concentration of free chlorine in water is dependent

on the pH, as follows:
HOCl = ClO− + H+ . (5)
Since the equilibrium constant of HOCl is assumed to be
2.9 × 10−8 mol l−1 at 25 ◦ C [26], HOCl is dominant in the
Fig. 2. Cyclic voltammograms at Pt disk electrode in 0.1 M NaClO4 as a
function of free-chlorine concentration: (a) 280 mg Cl l−1 , (b) 140 mg Cl l−1 , acidic region (pH < 5.5), while almost all the free chlorine is
(c) 70 mg Cl l−1 , and (d) blank. Sweep rate: 50 mV s−1 . present as ClO− at higher pH values (pH > 8.5). Moreover,
it is reported that ClO3 − is formed by the self-oxidation re-
before the activation, and (b) is after the activation. In Fig. 1, action when the pH of the solution is maintained as neutral
a clear improvement due to the repetition of cyclic potential (6) and (7) [16]:
scans is evident in the sensitivity of the voltammogram. In
2HOCl + ClO− → ClO3 − + 2H+ + 2Cl− . (6)
addition, the repeatability was also improved. For the Au and
GC electrodes, the same result is observed. However, high temperatures (60–110 ◦ C) are necessary for
reaction (6) to occur preferentially. In this study, the setting
3.2. Current–potential curve in free-chlorine-containing cell temperature is approximately 25 ◦ C. Therefore, reaction
solution (6) can be neglected. In general, the pH of water containing
sodium hypochlorite is in the range of 5–9. From reaction
To assess the voltammetric behavior, we applied cyclic (5), it is apparent that the hypochlorous acid coexists with
voltammetry to the free chlorine. Fig. 2 shows a cyclic hypochlorite ion in the solution. It has been reported that these
voltammogram obtained at the Pt disk electrode in 0.1 M chemical species are electrochemically oxidized by reactions
NaClO4 as a function of free-chlorine concentration: (a) (3) and (4). However, the reactions bring about H+ which
280 mg Cl l−1 , (b) 140 mg Cl l−1 , (c) 70 mg Cl l−1 , and (d) indicates strong pH dependence, therefore, the interpretation
blank. When the potential was swept from +0.6 to 1.2 V ver- of elementary process differs for each researcher [17–20].
sus Ag/AgCl, an anodic peak at +1.1 V was observed. These Therefore, we examined the reaction species in this anodic
results confirm that free chlorine can be electrochemically voltammetry method.
oxidized on the Pt electrode. The measurement was carried out at the Pt and GC
Table 1 lists the anodic peak current of cyclic voltam- disk electrodes. The pH was adjusted using perchloric acid
metry at different free-chlorine concentrations. The relative (HClO4 ) and sodium hydroxide (NaOH). The voltammo-
standard deviation (R.S.D.) was less than 2% for three-times grams obtained at the Pt electrode are shown in Fig. 4(a).
repetition. In Fig. 4(b), the plot of the peak current and the pH at the GC
We next examined Au and GC disk electrodes for com- electrode is shown. In Fig. 4(a), the peak current increases for
parison. Fig. 3 shows the cyclic voltammograms obtained at pH values above 6.5, and the rest potential shifts toward the
the Au (A) and GC (B) disk electrodes in 0.1 M NaClO4 as a negative direction. In Fig. 4(b), the peak current increases in
the same manner at the Pt electrode. The form of free chlorine
Table 1 in the bulk solution follows reaction (5), because reaction (6)
Repeatability test at different free-chlorine concentrations
can be disregarded as noted above. As a result, it is consid-
C (mg Cl l−1 ) Ip (␮A) R.S.D.a (%) ered that the species of the anodic reaction is hypochlorite
1 2 3 Mean σb ion. This finding agrees with the report of Yoshida et al. [18].
355 17.64 17.41 17.81 17.62 0.20 1.14
141 7.82 7.73 7.96 7.837 0.12 1.48 3.4. Electrode reaction mechanism
71 4.18 4.04 4.09 4.103 0.07 1.73
a Relative standard deviation. The effect of the sweep rate on the voltammetric response
b Standard deviation. to free-chlorine oxidation at the Pt disk electrode was exam-
296 F. Kodera et al. / Analytica Chimica Acta 537 (2005) 293–298
Fig. 3. Cyclic voltammograms at (A) Au and (B) GC disk electrodes in 0.1 M NaClO4 as a function of free-chlorine concentration: (a) 140 mg Cl l−1 , (b)
70 mg Cl l−1 , and (c) blank. Sweep rate: 50 mV s−1 .
ined. The voltammogram for the change of the sweep rate is
shown in Fig. 5, and the inset shows the anodic peak current
versus the square root of the sweep rate plots. It was found
that the peak current is linearly proportional to the square root
of the sweep rate, within the range 10–300 mV s−1 . A linear
regression statistical analysis (y = ax) yielded a correlation
Fig. 4. Effect of pH on the oxidation of free chlorine: (a) linear sweep voltam-
mograms of 50 mg Cl l−1 free chlorine in 0.1 M NaClO4 at Pt electrode; (b)
Ip vs. pH plots of the 200 mg Cl l−1 free chlorine in 0.1 M NaClO4 at GC
electrode. Sweep rate: 50 mV s−1 .
coefficient, R2 = 0.9997. The good linearity and the zero in-
tercept indicate the reaction takes place diffusion controlled.
A shift in the peak potential with an increase in sweep rate
was observed, which means the electrode reaction is not re-
versible [27]. Djordjević et al. reported that during the initial
step, a neutral radical is formed by the one-electron oxida-
tion of ClO− [17]. The radical reaction can be expressed as
follows:
ClO− → ClO• + e− . (7)
To estimate the number of electrons, n, transferred during
the electrode process, we performed measurements of the
stationary diffusion-controlled limiting current, Id , at the Pt
microelectrode as a function of free-chlorine solution, and
applied the following equation [28]:
Id = 4nFC∗ Da, (8)
where a is the radius of the disk electrode, F the Fara-
day constant, D the diffusion constant, and C* is the bulk
Fig. 5. Linear sweep voltammograms of 200 mg Cl l−1 free chlorine in
0.1 M NaClO4 for various sweep rates: (a) 10 mV s−1 , (b) 50 mV s−1 , (c)
100 mV s−1 , (d) 200 mV s−1 , and (e) 300 mV s−1 at Pt electrode. Insert
shows a plot of the anodic peak current vs. the square root of sweep rate.
 F. Kodera et al. / Analytica Chimica Acta 537 (2005) 293–298 297

Fig. 6. Stationary voltammograms at Pt microelectrode (ϕ = 10 ␮m) in 0.1 M

NaClO4 as a function of free-chlorine concentration: (a) 300 mg Cl l−1 , (b)
200 mg Cl l−1 , and (c) 100 mg Cl l−1 . Sweep rate: 50 mV s−1 , pH = 8.5.

concentration of the electroactive species. It is assumed

that D = 1.10 × 10−5 cm2 s−1 , as reported by Czarnetzki and
Janssen [20]. The stationary voltammograms obtained at
the 10 ␮m-diameter electrode in 0.1 M NaClO4 as a func-
tion of the free-chlorine concentration are shown in Fig. 6:
(a) 300 mg Cl l−1 , (b) 200 mg Cl l−1 , (c) 100 mg Cl l−1 . The
dashed line represents the background-corrected voltammo- Fig. 7. (a) Linear sweep and (b) differential pulse voltammograms at Pt
gram. We attempted to evaluate the number of electrons on electrode in 0.1 M NaClO4 as a function of free-chlorine concentration:
the basis of the background-corrected limiting current. By
using the dissociation constant, the ratio of ClO− :HOCl is
calculated to be 90:10 at pH = 8.5. Even when the electrode
reaction brings about H+ , the pH in the diffusion layer of
the microelectrode is equal to that of the bulk solution. Since
ClO− is the reactant, by putting the ratio and the diffusion
constant, one can obtain the number of electron by using Eq.
(8) and Id observed in Fig. 6, resulting in n = 0.90–0.92. Con-
sequently, chloroxyl radicals, as indicated by reaction (7), are
formed by the exclusive oxidation of hypochlorite ions.
3.5. Comparison between the electrochemical method
and iodometric titration
The anodic voltammetry method with a Pt electrode was
applied for the determination of the free-chlorine concentra-
tion in three standard samples. The analytical results obtained
are compared with those obtained by iodometric titration [4].
Table 2 shows the anodic voltammetry results for the three
samples. The results are in good agreement with those ob-
tained by iodometric titration.
Table 2
Comparison of results for various free-chlorine concentrations obtained by
the anodic voltammetry method with a Pt electrode and iodometric titration
Anodic voltammetrya (mg Cl l−1 ) Iodometric titration (mg Cl l−1 )
6.4 7.3
87.3 90.8
259.4 263.7
a Mean value over three replicate analyses.
(a) E = 50 mV, E = 10 mV, tp = 50 ms, tm1,2 = 20 ms, τ = 2 s; (b) sweep rate:
50 mV s−1 .
3.6. Use of DPV method
Next we compared the linear sweep voltammetry method
with the DPV method. In general, pulse voltammetry renders
the residual current small and the sensitivity high. The free-
chlorine concentration utilized for the disinfection of drink-
ing water is very low. For example, in Japan, the concentration
at the end points of domestic water supply systems is regu-
lated to be in the range of 0.1–1.0 mg l−1 . Fig. 7(a) and (b)
respectively shows the conventional linear sweep voltammo-
grams, and the differential pulse voltammograms. By com-
paring the voltammograms, the DPV method clearly shows
the anodic peak current, and the residual current is dimin-
ished. The low concentration of free chlorine which could
not be detected by the linear sweep voltammetry method was
measured by the DPV method. As a result, the oxidation
peak current was observed at the free-chlorine concentration
of less than 4.0 mg Cl l−1 . The detection limit of the DPV
method under this wave form parameter was 1.0 mg Cl l−1 .
On the basis of this finding, it is considered to be possible
to measure low free-chlorine concentrations by applying the
pulse method.
4. Conclusions
A novel approach to the determination of free-chlorine
concentration has been developed which involves anodic
298 F. Kodera et al. / Analytica Chimica Acta 537 (2005) 293–298
voltammetry based on platinum, gold, and glassy carbon disk
electrodes. These electrodes exhibit a clear voltammetric re-
sponse to ClO− . A good linear relationship was obtained
between oxidation peak current and concentration, and the
repeatability was also found to be good. Thus, it is apparent
that this method can be adapted for application in a monitor-
ing instrument for high free-chlorine concentrations in dis-
infection, bleaching, and various manufacturing processes.
Moreover, by employing the DPV method, the detecting limit
was enhanced to 1.0 mg Cl l−1 .
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