Journal of Electroanalytical Chemistry 463 (1999) 16 – 23

Voltammetric determination of the iodide ion with a quinine

copper(II) complex modified carbon paste electrode

Jeong-Sik Yeom, Mi-Sook Won, Yoon-Bo Shim *

Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National Uni6ersity, Pusan 609 -735, South Korea

Received 30 June 1998; received in revised form 20 October 1998

Abstract

A Cu(Qui)(NO3)2 modified-carbon paste electrode (where Qui is quinine) was constructed by incorporating Cu(Qui)(NO3)2 into
a carbon-paste composed of graphite powder and Nujol. The modification with Cu(Qui)(NO3)2 resulted in a deposit of iodide ions
on the electrode surface through a ligand exchange reaction. This exchange reaction was completed within 20 ms in a
CHCl3 +CH3OH solution. The rate constant, k 0, of the ion exchange reaction was determined to be 27 s − 1 by the stopped flow
spectroscopic method. The anodic peak of the pre-deposited iodide ion on the electrode surface was observed at +0.54 V in a
cyclic voltammogram. Various experimental parameters such as pH, deposition time, temperature, and electrode composition were
optimized to analyze the iodide ion employing linear sweep and differential pulse voltammetry. With the exception of thiosulfate
ions, inorganic anions did not interfere with the determination of the iodide ion. Using linear sweep voltammetry, a calibration
curve was attained over the concentration ranges of the iodide ion from 1.0 × 10 − 4 – 2.5×10 − 6 M at the deposition time of 10
min, with the detection limit determined as 1.0 ×10 − 6 M. Using differential pulse voltammetry, the logarithmic linear response
range for the iodide ion was between 10 − 6 and 10 − 8 M, and the detection limit was 1.0 ×10 − 8 M. This method was evaluated
by analyzing the iodide ion content in a commercial disinfectant. © 1999 Elsevier Science S.A. All rights reserved.

Keywords: Quinine copper complex; Analysis of the iodide ion; Carbon paste electrode

1. Introduction step, so that interference by the host electroactive spe-

Chemically modified electrodes (CMEs) are very use-
ful for environmental, clinical, and bio-technical analy-
ses. They are designed to provide desired selective sites
toward analytes. Several books [1,2] and review articles
[3 – 6] have introduced techniques of adopting CMEs.
Voltammetry often employs CMEs to determine selec-
tively an analyte preconcentrated via chemical reactions
[1 – 8]. Compared to conventional voltammetric tech-
niques, voltammetry with CMEs provides a versatile
preconcentration range with little interference. Another
advantage of using CMEs is exchanging the sample
solution with a blank electrolyte before the stripping
* Corresponding author. Fax: +82-51-5167421; e-mail: yb-
shim@hyowon.cc.pusan.ac.kr.
cies may be bypassed effectively. Of these CMEs, car-
bon paste electrodes (CPEs) have been used
occasionally to determine metal ions by employing the
stripping method, because they have some unique ad-
vantages. CPEs can be prepared readily and regener-
ated easily to a new electrode surface. Thus, there are a
number of reports using modified CPEs for the analyses
of heavy metal ions [9–13]. Anions have been deter-
mined mostly by potentiometric methods with metal
complex-containing electrodes [14–19]. However, there
are only a few reports on the analysis of anions employ-
ing voltammetry. Of these anions, the iodide ion is well
known as it has been used traditionally in photography
and in medicine. Until now, a few studies on the
voltammetric determination of iodide using cathodic
[20,21] and anodic stripping voltammetry [22] have

0022-0728/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 0 7 2 8 ( 9 8 ) 0 0 4 2 7 - 6
 J.-S. Yeom et al. / Journal of Electroanalytical Chemistry 463 (1999) 16–23
been reported. In addition, we have reported the study
for the anodic stripping voltammetric detection of io-
dide using a chinchonine modified carbon paste elec-
trode [23].
Quinine belongs to the quinoline alkaloids with anti-
malarial activity that forms complexes with certain
heavy metal ions. Utilizing the ligand exchange reac-
tion, we prepared the Cu-quinine complex,
Cu(Qui)(NO3)2, which could react selectively with an
iodide ion. This Cu-quinine complex-containing carbon
paste electrode led to the voltammetric determination
of iodide in an aqueous solution. The technique in-
volved the pre-deposition of iodide ions through an ion
exchange reaction between the complex and iodide ion
on the CPE surface, followed by voltammetry. In addi-
tion, we investigated the reaction mechanism between
the complex and iodide ions from the results of stopped
flow UV-vis. and UV-vis. spectroscopy. Experimental
parameters that affect the response of the electrode
processes, such as electrode composition, deposition
time, deposition temperature, and pH were optimized.
We investigated also the interference of other ions on
the analysis of the iodide ion.
2. Experimental
2.1. Reagents
Quinine and Nujol from Aldrich were used without
further purification. Other chemicals used in analytical
processes were purified analytical grade reagents. Iodide
solutions were prepared just before each measurement
by dilution of a 0.1 M stock solution. All aqueous
solutions were prepared in doubly distilled water ob-
tained from a Millipore Milli-Q water purification sys-
tem. The Cu(Qui)(NO3)2 complex was prepared by the
following procedure: a 0.01 M cupric nitrate solution
was added dropwise to a 50-ml ethanol solution of 0.01
M quinine for 1 h with stirring. The green precipitates
produced by this reaction were collected by filtration,
washed with cold ethanol, and then dried in vacuum at
40°C for 24 h. The precipitates were recrystallized in a
chloroform solution. These precipitates were stable in
air. The characterization of the complex was carried
out employing elemental analysis, ICP spectrometry,
and IR spectroscopy. The average values of the elemen-
tal analysis and ICP results were as follows: Calcu-
lated.: Cu, 12.41%; C, 46.92%; H, 4.69%; N, 10.94%; O,
25.04%. Found: Cu, 12.30%; C, 47.62%; H, 4.90%; N;
9.98%; O, 25.20%.
The Cu(Qui)I2 complex was prepared in order to
confirm the product of the ligand exchange reaction,
which was obtained in a reaction between 0.01 M
Cu(Qui)(NO3)2 complex and 0.02 M potassium iodide
in an acetone solution. After a 2-h digestion of the
17
colloidal product that was formed instantly by the
exchange reaction, the yellowish-green precipitate was
collected by filtration. The precipitates were washed
with cold acetone and dried in vacuum at 40°C for 1
day. The average values of the elemental analysis and
ICP results were as follows: Calculated.: Cu, 9.90%; C,
37.42%; H, 3.74%; N, 4.37%; O, 4.99%; I, 39.58%.
Found: Cu, 10.33%; C, 36.60%; H, 3.60%; N, 5.03%; O,
5.12%; I, 39.32%.
2.2. CPE preparation and analytical procedures
The unmodified CPEs were prepared as follows: 5 g
of reagent-grade graphite powder washed with ethanol
and dried under vacuum was mixed with 3 ml of Nujol.
To modify the CPEs, the graphite powder was mixed
with Cu(Qui)(NO3)2 complex in various composition
ratios, which were 0, 10, 20, 30, 40, 50 and 60% (w/w%)
of Cu(Qui)(NO3)2 complex to graphite powder. Both
unmodified and modified CPEs were packed into a 1-ml
disposable polyethylene syringe (5 mm I.D.) that had
been cut off at the end. Electrical contact to the paste
was established via a thin copper wire passed through
the syringe piston.
The fresh surfaces were obtained by polishing the
electrode on a clean paper until they showed a smooth
and shiny appearance after every measurement. To
activate fresh electrodes, the polished CPEs were pre-
conditioned by an exposure to a pH 7.0 phosphate
buffer solution containing a high concentration of
1.0× 10 − 3 M iodide for 3 min before measurement.
After the deposition at the activation step, the elec-
trodes were rinsed with deionized water, and repetitive
potential cycles between 0.0 and + 1.0 V were per-
formed to strip the deposited iodine into a 0.1 M KNO3
solution. The oxidation peak of the iodide ion disap-
peared completely after ten potential cycles in a blank
electrolyte solution. Three deposition/stripping cycles at
least provided highly sensitive and reproducible elec-
trode surfaces. When the activity of the CPE with the
iodide ion was poor, the carbon paste was forced out
by pressing the piston of the syringe and cutting off the
tip. The resulting new surface was preconditioned and
activated.
To record the voltammogram of the analyte, the CPE
deposited with iodide ions was taken off from the
deposition solution, washed thoroughly with distilled
water, and transferred to a separate cell containing only
blank electrolyte (0.1 M KNO3). The modified CPEs
were chemically stable in a blank electrolyte solution,
which showed no redox peaks over the measuring po-
tential ranges. In every measurement, a fresh electrolyte
solution replaced the used solution to avoid contamina-
tion of the dissolved trace iodide ion. The same elec-
trode surfaces could be reused up to five times after a
simple cycling of the potential from 0.0 V to + 1.0 V in
18 J.-S. Yeom et al. / Journal of Electroanalytical Chemistry 463 (1999) 16–23
a blank solution. The preconditioned CPE maintained
its sensitivity for over two months.
2.3. Apparatus
The voltammetric experiments were carried out using
a potentiostat/galvanostat M273 (Prinston Applied Re-
search) and an X– Y recorder (Kipp & Zonen). A
deposit solution for the deposition of iodide was con-
tained in a Teflon-covered 50-ml Pyrex cell, and an-
other cell contained a blank electrolyte solution for the
voltammetric measurement of the iodide ion. During
the deposition, the pre-deposit solution was well stirred
by a magnetic stirrer (about 600 rpm). All test solutions
were thermostated at 2590.1°C. A three-electrode sys-
tem, consisting of the CPE as working, platinum wire
auxiliary, and SCE reference electrodes, was used. A
stream of purified nitrogen gas was passed through the
test solutions to deaerate the solution in the measuring
cell. The potential scan rate was 100 mV s − 1 for cyclic
voltammetry (CV) and 5 mV s − 1 for differential pulse
voltammetry (DPV).
IR spectra and ICP – AES data were obtained with a
Polaris FT-IR spectrophotometer (Mattson) and an
inductively coupled plasma atomic emission spectrome-
ter (Thermo Jarrell Ash). UV-vis. spectra were recorded
on a PX-1 spectrophotometer (Ocean Optics) and a
stopped flow spectrophotometer (Otsuka Electronics).
A VARIO EL elemental analyzer (Elementa) per-
formed the elemental analysis.
3. Results and discussion
3.1. The exchange reaction of Cu(Qui )(NO3)2 with
iodide
The 1:1 composition ratio of a copper ion to a
quinine molecule in the complex was confirmed with
elemental analysis and ICP data. IR, UV-vis. spectra,
and the energy calculation of the possible structure of
the complex molecules showed that the copper ion
bonded to nitrogen and oxygen atoms in the quinine
molecules, which resulted in a Cu(Qui)(NO3)2 complex
that had a distorted tetrahedral structure. The antisym-
metric NC3 stretching [24] on the quinuclidine moiety
appeared at 1240 cm − 1 in the spectrum of quinine.
This band was reduced in intensity and shifted to 1250
cm − 1 in the spectrum of the Cu(Qui)(NO3)2 and
Cu(Qui)I2 complexes. The absorption band from C–N
vibration mode [25] was enhanced due to the complex
formation with a metal ion. This band appeared at
about 1370 cm − 1 for the Cu(Qui)(NO3)2 and Cu(Qui)I2
complexes. While the strong absorption band at 1385
cm − 1 appeared due to the stretching vibration of ni-
trate ions [24] in the spectrum of the Cu(Qui)(NO3)2
complex, this band did not appear in the spectra of
quinine and Cu(Qui)I2. The absorption band of the
–OH group appearing at 3205 cm − 1 in the quinine
molecule decreased in intensity and shifted to 3250
cm − 1 in the complex. These results show that the
copper ion coordinated with nitrogen and oxygen
atoms in the quinine molecule. In addition, the poten-
tial energy of three possible complex structures (Cu(II)
ion coordinated with a N atom on the quinuclidine and
an N atom on the quinoline moiety, an N atom on the
quinuclidine and an O atom of the hydroxide group, or
the O atom of the hydroxide group and an N atom on
quinoline) was calculated by the software Molecule
Modeling System, Hyperchem Release 3.0, supplied by
Hypercube. The result indicated that the complex
formed by combining with a nitrogen atom on the
quinuclidine and the oxygen atom of the hydroxyl
group (See Scheme 1) had the lowest value of 16.4 kJ
mol − 1. Thus, the structure of the complex was con-
firmed tentatively to be a distorted tetrahedral, which
was consistent with the previous result for similar
quinine metal complexes by Jeanmin et al. [26].
To characterize the ligand exchange reaction that
took place between nitrate ions in the Cu(Qui)(NO3)2
complex and iodide ions in a solution, the UV-vis.
spectrometric and stopped flow methods were carried
out for the ligand and complexes. Fig. 1(A) shows (a)
UV-vis. absorption spectra of the iodide ion, (b) the
Cu(Qui)(NO3)2 complex, and ((c)–(g)) their mixtures in
a CHCl3 solution. The spectra of the mixtures ((c)–(g))
were recorded for the CHCl3 solution containing vari-
ous mole ratios of KI to one mole of the
Cu(Qui)(NO3)2 complex (1.0× 10 − 5 M). The mole ra-
tios of iodide ions were 0.5, 1.0, 2.0, 3.0 and 4.0. The
band at 450 nm corresponding to the absorption of the
photons by the iodide substituted-complex increased
gradually until it reached a 1:2 mole ratio of the iodide
ion to the Cu(Qui)(NO3)2 complex. With Job’s (the
mole ratio) method [27], the intensity of the absorption
bands was constant at the 1:2 mole ratio. The result of
this method indicated that the Cu(Qui)(NO3)2 complex
turned into the iodide-substituted Cu(Qui)I2 complex,
which confirmed also the absorption band at 450 nm to
Scheme 1. Deposition mechanism through the ligand exchange reac-
tion.
 J.-S. Yeom et al. / Journal of Electroanalytical Chemistry 463 (1999) 16–23 19

The ligand exchange reaction of the Cu(Qui)(NO3)2

Fig. 1. UV-visible absorption spectra of Cu(Qui)(NO3)2 complex (A);
(a), iodide; (b), Cu(Qui)(NO3)2 complex; (c–g), mole ratio of iodide
for Cu(Qui)(NO3)2 complex was 0.5, 1.0, 2.0, 3.0, and 4.0, respec-
tively. The insert (Fig. 1(B)) shows a spectrum of the Cu(Qui)I2
complex in CHCl3.
complex with potassium iodide in the aqueous solution
can be described as the following reaction:
Cu(Qui)(NO3)2 + 2KI ? Cu(Qui)I2 + 2KNO3 (1)
The equilibrium constant (Keq) for this reaction is
described by the following equation:
Keq = [Cu(Qui)I2][NO3− ]2/[Cu(Qui)(NO3)2][I − ]2 (2)
When Cu(Qui)(NO3)2 and the Cu(Qui)I2 complexes
are in the solid state, the equilibrium constant will be
expressed by the following equation:
Keq : [NO3− ]2/[I − ]2 = ([NO3− ]/[I − ])2 (3)
To describe the Keq, the concentrations of NO3− and
−
I were determined by spectrometry [28] and titration
with potassium permanganate [29]. Before the spectro-
scopic measurement, the solution was treated with
toluene and a 3:1 diluted sulfuric acid. The concentra-
tion of the nitrate ion extracted toluene layer was
determined by measuring the absorbance at 284 nm in
UV-visible spectrophotometry, and the concentration
of the iodide ion was determined by iodometry. The
equilibrium constant (K) calculated from the above
result was 7.1. The stopped flow method determined the
reaction rate constant between the Cu(Qui)(NO3)2 com-

be due to the iodide ion substituted-Cu(Qui)I2 complex

that was attained from Cu(Qui) (NO3)2 through the
ligand exchange reaction. Fig. 1(B) shows a UV-vis
absorption spectrum of the Cu(Qui)I2 complex. This
spectrum was identical with the spectra of the complex
substituted by the iodide ion shown in Fig. 1(A). In
addition, while the asymmetry stretching band of NO3−
appeared at 1385 cm − 1 in the IR spectrum of the
Cu(Qui)(NO3)2 complex, the band at 1385 cm − 1 disap-
peared in the spectrum of the Cu(Qui)I2 complex as
iodide ions were substituted, reconfirming the iodide
ion exchange with the nitrate ion in the Cu(Qui)(NO3)2
complex.
Fig. 2(A) shows the difference absorption spectra for
the reaction mixtures at different concentrations of the
iodide ion in 1:2 methanol+chloroform solutions, and
the 7.5 ×10 − 5 M Cu(Qui)(NO3)2 complex. The concen-
trations of the iodide ion were: (a) 2.5× 10 − 5 M; (b)
5.0× 10 − 5 M; (c) 7.5 ×10 − 5 M; (d) 1.0 × 10 − 4 M and
(e) 1.25 × 10 − 4 M. It shows that the intensity of bands
at 450 nm corresponding to those of the Cu(Qui)I2
complex increased as the concentration of the iodide
ion increased. Fig. 2(B) shows a calibration plot ob- Fig. 2. (A) Difference absorption spectra for reaction mixtures at the
tained from the data of Fig. 2(A). The linear response different concentrations for iodide ion with 7.5 × 10 − 5 M
range for the determination of the iodide ions using the Cu(Qui)(NO3)2 complex in a 1:2 methanol+chloroform solution. (B)
A calibration plot obtained from the spectra in (A). The concentra-
7.5 ×10 − 5 M Cu(Qui)(NO3)2 complex in 1:2 tions of the iodide ion in the reaction mixtures were (a) 2.5 × 10 − 5
methanol+chloroform solution was 2.5×10 − 5 to M; (b) 5.0× 10 − 5 M; (c) 7.5×10 − 5 M; (d) 1.0× 10 − 4 M and (e)
1.25× 10 − 4 M. 1.25 × 10 − 4 M.
20 J.-S. Yeom et al. / Journal of Electroanalytical Chemistry 463 (1999) 16–23
Fig. 3. Cyclic voltammograms of the carbon paste electrode; the plain
carbon paste electrodes (a and b) and CME (c and d). Electrodes
were exposed for 10 min to a 0.1 M KNO3 blank solution (a and c)
and a 1.0×10 − 5 M iodide ion solution (b and d) (pH 7.0).
plex and the iodide ion. This reaction was completed
within 20 ms, and the reaction rate constant, k 0, was 27
s − 1. The data indicate that the ligand exchange reac-
tion between the Cu(Qui)(NO3)2 complex and the io-
dide ion in CHCl3 +CH3OH was fast enough to use the
analysis of the iodide ion.
3.2. Electrochemical beha6ior of CPE and the
deposition of the iodide ions
The cyclic voltammograms were obtained for two
unmodified (Fig. 3(a and b)) and two complex modified
CPEs (Fig. 3(c and (d)). Fig. 3(a and c) are cyclic
voltammograms recorded for the blank phosphate
buffer solution and (b) and (d) are those obtained after
dipping the CPE into the buffer solution containing
1.0 ×10 − 5 M iodide ions. There were no redox peaks
in the CVs of the unmodified CPE (a) and the
Cu(Qui)(NO3)2 complex-modified CPE(c) over the po-
tential range from 0.0 to +1.0 V (vs. SCE). The only
difference between (a) and (c) was that the magnitude
of the background current of the CPE (c) was higher
than that of the unmodified CPE (a) due to the elevated
resistance. To test the responses of the CPEs for iodide
ions, the unmodified CPE and the modified CPE were
immersed and predeposited in a pH 7.0 buffer solution
containing the iodide ions. These were rinsed with
deionized water and transferred into a 0.1 M KNO3
solution after the dipping procedure. While the CV
recorded for (b) the unmodified CPE, showed no redox
peak, the one for (d), the modified CPEs interacting
with the iodide ions showed an anodic peak at +0.54
V. The height of the oxidation peak at + 0.54 V
increased gradually as the concentration of iodide ions
increased. This indicates that the oxidation peak is
related to the presence of iodide ions in a test solution.
Over 40 mV s − 1 for the scan rate, the peak currents
were directly proportional to the square root of the
scan rate, indicating that the oxidation process of an
iodide ion was diffusion controlled from the CPE sur-
face into the bulk solution. This implies that the thick-
ness of the diffusion layer is thicker than that of the
adsorption layer formed by the pre-deposition. Thus,
the infinite diffusion process is operative in the anodic
process at over 40 mV s − 1 for the scan rate. As shown
in the above results, the iodide ions exchanged fast with
NO3− ions on the Cu(Qui)(NO3)2 complex-modified
electrode surface. Then, the iodide ions exchanged into
the complex of Cu(Qui)I2 on the surface of the CPE
were oxidized at + 0.54 V to iodine. The clean surface
of the CPE was stable chemically for repetitive cycling
for about a few hours unless it was exposed to an
extremely high potential or temperature. The activity of
CPEs with regard to the iodide ion lasted over two
months.
3.3. Application to the analysis of iodide
The CPEs made in various content ratios of the
Cu(Qui)(NO3)2 complex to carbon powder (10, 20, 30,
40, 50 and 60% w/w) were tested. To deposit the test
ions on the electrode, each modified CPE was dipped
into a pH 7.0 buffer solution containing 1.0 ×10 − 5 M
iodide ion for 10 min. After this step, the electrode-cap-
tured test ions were rinsed with deionized water, and
the cyclic voltammograms were recorded in a 0.1 M
KNO3 blank electrolyte solution. At all the composi-
tion ratios of the Cu(Qui)(NO3)2 complex to the carbon
powder, the iodide ions responded to the
Cu(Qui)(NO3)2 complex-modified CPE. The maximum
peak current in the voltammogram was obtained at 40
(% w/w) of the Cu(Qui)(NO3)2 complex (Fig. 4(A)). At
higher compositions than 40%, the peak current de-
creased. This might be due to the resistance of the
CPEs being higher than that of 40% composition of the
complex.
The peak current change according to the deposition
time in a 1.0 ×10 − 5 M iodide solution (pH 7.0) is
shown in Fig. 4(B). Anodic currents increased rapidly
as the deposition time increased from 0 to 10 min, while
the increase slowed down after 10 min. The interaction
sites between the iodide ion and the active sites of the
electrode surface should be saturated after 10 min.
When the deposition time was longer than 20 min, the
removal of iodide ions deposited on the electrode was
not completed. This indicates that the iodide ion de-
 J.-S. Yeom et al. / Journal of Electroanalytical Chemistry 463 (1999) 16–23
posited during a long period had penetrated into the
electrode surface and combined strongly with the
modifier. Therefore, in all subsequent work, an accu-
mulation time of 10 min was used.
Fig. 4(C) shows the variation of the oxidation peak
current in CV as a function of the deposition tempera-
ture. The CPE (40% w/w) was dipped into a 1.0× 10 − 5
M iodide solution for 10 min at all temperatures. As
the temperatures of the preconcentration solution in-
creased from 15 to 35°C, the anodic current of the
iodide ion increased. The maximum peak current was
obtained at 35°C. At temperatures over 35°C, the peak
current decreased, which may be due to the dissolution
of electrode surfaces at higher temperatures. Thus, the
experiment was run at 25°C during all the deposition
steps.
The peak current changed also according to the pH
of the deposition solutions (see Fig. 4(D)). Here, the
chemical deposition was done under the same condi-
tions (1.0 × 10 − 5 M of the iodide ion containing solu-
tion for 10 min at 25°C). At pHB5.0 and \10.0, the
oxidation peaks were smaller than those obtained in the
pH range 5.0–10.0. This may be due to the enhanced
signal-to-noise in a pH range that iodide and/or the
copper complex exist as a neutral species. The response
was most sensitive for the iodide ion at pH 7.0. There-
fore, all subsequent experiments were taken in a phos-
Fig. 4. The effect of (A) the electrode composition; (B) the deposition
time, (C) the deposition temperature and (D) pH of the deposition
solution on the peak current of the Cu(Qui)(NO3)2 -modified elec-
trode. The concentration of iodide ion was 1.0 ×10 − 5 M. (deposition
time: 10 min, deposition temp.: 25°C, pH: 7.0, scan rate: 100 mV s − 1)
21
Fig. 5. A calibration plot (B) and differential pulse voltammograms
(A) for iodide ion with 40% Cu(Qui)(NO3)2 complex-modified elec-
trodes following 30 min stirring in iodide ion solutions. The concen-
trations of solutions: (a) 1.0 ×10 − 6 M; (b) 5.0×10 − 7 M; (c)
1.0 ×10 − 7 M; (d) 5.0 ×10 − 8 M and (e) 2.5 × 10 − 8 M. (pH: 7.0,
scan rate: 5 mV s − 1, pulse height: 0.025 V, pulse width: 0.05 s,
condition voltage: +0.2 V, condition time: 1 min, condition temp:
25°C.)
phate buffer solution of pH 7.0. In summary, the
optimum conditions for the analysis of iodide ions were
attained as follows: deposition solution of pH 7.0;
composition of CPE of 40% (w/w); deposition time of
10 min; and deposition temperature of 25°C. In the CV,
the scan rate was fixed at 100 mV s − 1 with consider-
ation of the sensitivity, although the current increased
as the scan rate increased.
Various ions were examined to investigate the inter-
ference in determination of iodide ions. Cl − , Br − ,
SCN − , CN − , C2O24 − , ClO4− , S2O23 − , NO2− , SO24 − and
S2 − ions present by ten-fold excess in the test solutions
did not interfere with the determination of the iodide
ions. The influences of thiosulfate ion had some nega-
tive effect on the magnitude of the oxidation peak
current. The shape and peak potential of CVs recorded
in the presence of interfering ions was the same as those
CVs without foreign ions, except that the peak heights
become smaller than those in the absence of foreign
ions. After immersing for 10 min the modified CPE into
a pH 7.0 phosphate buffer solution containing 1.0×
10 − 5 M iodide and thiosulfate ions, anodic voltam-
mograms for the ions were recorded in a blank
electrolyte solution. The oxidation peak height of io-
dide was reduced in the presence of the equimolar
thiosulfate ion to about 10% of the one in the absence
of thiosulfate ions. This may have occurred because of
22 J.-S. Yeom et al. / Journal of Electroanalytical Chemistry 463 (1999) 16–23
Table 1
Data for the calibration plot derived from the iodide solution
Sample Concentration S.D./%
Certified/ppb Observed/ppb
Iodide 55 51 93.1
a competitive reaction between iodide and thiosulfate
ions on the active sites of the copper complex. This
indicates that thiosulfate ions hindered the reaction
between iodide and the Cu(Qui)(NO3)2 complex.
At the analysis condition optimized from the cyclic
voltammetric results, we obtained the calibration plot
for the analysis of the iodide ion (not shown) and
determined the detection limit. The detection limit was
taken as the concentration that the magnitude of the
analytical signal was twice that of the one recorded for
the background. Here, the least square analysis of the
result was described by the equation of I/mA =197.8+
35.1(log ([I − ]/mol l − 1)), and the correlation coefficient
was 0.993 (not shown). The detection limit was 1.0×
10 − 6 M. Based on the CV experiment, DPV was under-
taken to obtain the calibration plot in a lower
concentration. Fig. 5(A) shows differential pulse
voltammograms of the standard iodide ion solution
(pH 7.0) with a 40% CPE. The deposition time and the
scan rate were 10 min and 5 mV s − 1, respectively. Fig.
5(B) shows the calibration plot obtained from the data
of Fig. 5(A) yielding a logarithmic response. The linear
response ranges for the determination of iodide ions
were in the order of 10 − 6 – 10 − 8 M, using DPV. Least
square analysis from the data of Fig. 5(B) provided the
equation I/mA =3.69+0.47(log ([I − ]/mol l − 1)) and the
correlation coefficient was 0.998. Based on the signal-
to-background characteristics of the response, the de-
tection limit of the iodide ions was ca. 1.0× 10 − 8 M by
dipping the CPE into the test solution for 20 min. The
relative standard deviation was93.5% for five determi-
nations in 2.5×10 − 8 M iodide ions.
To demonstrate the suitability of this analytical
method for actual samples using the modified CPEs, we
examined the concentration dependency and performed
a precision test. The sample was diluted to the concen-
tration of 1.0× 10 − 7 M before measurement. The cer-
tified iodide concentration in this sample was about 6%.
Table 1 shows the analytical results of iodide in this
disinfectant by using DPV, where the average concen-
tration of three analyses is given.
4. Conclusions
The iodide ion was deposited chemically through the
ligand exchange reaction onto the surface of the carbon
paste electrode modified with the Cu(Qui)(NO3)2 com-
plex. The oxidation peak potential of iodide ions, which
exchanged with nitrate ions in the Cu(Qui)(NO3)2 com-
plex, was + 0.54 V. The optimum conditions for the
analysis of iodide were investigated using cyclic voltam-
metry. The optimum conditions for the determination
of iodide were as follows: deposition solution of pH 7.0;
composition of CPE of 40% (w/w); deposition time of
10 min; and deposition temperature of 25°C. The detec-
tion limit adopted from differential pulse voltammetry
was 1.0 × 10 − 8 M for iodide, and the relative standard
deviation was 9 3.5% for 2.5 ×10 − 8 M iodide ion. The
oxidation current of the iodide ions was reduced by ca.
10% in the presence of thiosulfate ion.
Acknowledgements
This research was supported by Grant 96-0501-05-
01-3 from the Korean Science and Engineering
Foundation.
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