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Talanta 50 (2000) 1157 1162

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Potentiometric determination of hydrogen peroxide at


MnO2-doped carbon paste electrode
Xingwang Zheng *, Zhihui Guo
Department of Chemistry, Shaanxi Normal Uni6ersity, Xian 710062, Peoples Republic of China
Received 23 November 1998; received in revised form 20 May 1999; accepted 16 July 1999

Abstract
A novel hydrogen peroxide (H2O2) potentiometric sensor, made with a MnO2-doped carbon paste electrode (CPE),
is reported. Under optimum conditions, the electrode gives a Nernstian response for H2O2 in the concentration range
3.00 10 7 3.6310 4 mol/l, with a slope of 21 19.4 mV/pH2O2 and a detection limit of 1.2 10 7mol/l H2O2.
In addition, this sensor offers some analytical characteristics such as sensitivity, good reproducibility and a simple
preparation procedure. The effects of both the components of the electrode and other conditions on the potential
response of the sensor, as well as the possible response mechanism, are discussed. 2000 Elsevier Science B.V. All
rights reserved.
Keywords: Hydrogen peroxide; Manganese dioxide; Modified carbon paste electrode; Potentiometric sensor

1. Introduction
Chemically modified electrodes [1 3] as useful
analytical tools have been widely used in different
research fields since more analytical possibilities
[47] are offered by electrode manufacture. However, only a few analytical applications have employed chemically modified electrodes as
potentiometric sensors [8 13], and the modified
methods of the electrodes often involve covalent
attachment and polymeric films to the surface of
based electrodes [14 16], so the preparation of
these potentiometric sensors often suffers from
the complex preparation process of the based* Corresponding author. Tel.: +86-29-5235570.

electrodes and are time-consuming. Compared


with these methods, the fabrication of chemically
modified carbon paste electrodes (CPE) made
with liquid paraffin oil as the gluing material are
simple and cheap, these modified carbon paste
electrodes are often applied for this purpose and
many CPE-based potentiometric sensors have
been reported in the literature [1719], but these
CPE-based sensors often have poor stability and
poor reproducibility since the carbon powder on
the face of the CPE is easy to be omitted.
Recently, some CPE-based potentiometric sensors prepared with solid paraffin oil as the gluing
material have been reported [20,21], these new
types of CPE-based electrodes have presented
some advantages, such as good stability and
reproducibility.

0039-9140/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
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X. Zheng, Z. Guo / Talanta 50 (2000) 11571162

Hydrogen peroxide (H2O2) is a very important


intermediate in environmental and biological
reactions. The monitoring of H2O2 with a reliable, rapid and economic method is of great
significance for numerous processes. Several
analytical techniques have been employed for
its determination [22 24], including the manganese dioxide-modified CPE amperometric sensor [25], but most suffer from interference,
complex instrumentation and expensive reagents
[2628].
The potentiometric analytical method has
been found to be more suitable for determination
of many analytes since it possesses advantages
such as rapid, simple instrumentation and a
wide linear range. But until now, to the best
of our knowledge, a potentiometric method
for the determination of H2O2 has not been reported.
In this paper, by doping the CPE with MnO2
and using solid paraffin as gluing material, a new
CPE-based electrode was prepared and it was
found that this CPE-based electrode presented the
Nernstian response for H2O2. Based on this observation, a new potentiometric sensor for the determination of H2O2 was proposed and factors
which affected the analytical performance of this
sensor such as the components of paste and condition time were studied. At the same time, the
possible response mechanism of the sensor is discussed. This sensor has been used to detect H2O2
in rain water samples and it has some advantages
such as simple instrumentation, simple preparation procedures and good stability and
reproducibility.

2. Experimental

2.1. Reagents
All reagents were of analytical-reagent grade
or better and water doubly-distilled in a fusedsilica apparatus was used throughout the experiment. A stock solution of H2O2 (0.100 mol/l)
was prepared by diluting 5.5 ml of 30% v/v
H2O2 (Shanghai Chemical Reagents Plant) to
500 ml with water. The solution was standardized

by titration with potassium permanganate.


Test standard solutions were prepared daily by
appropriate dilution of the stock solution. A
0.10 mol/l NH4Cl solution was prepared by dissolving 5.5 g of NH4CL (Xian Chemical
Reagents Plant) in 1 l of water and a 0.10 mol/l
NH3 H2O solution was prepared by diluting
an appropriate volume of saturated NH3 solution (Xian Chemical Reagents Plant) in 1 l of
water.

2.2. Apparatus
The potentials were measured with a PHX215 ION-meter (Shanghai Second Analytical
Instrument Plant, China).The reference electrode was a saturated calomel electrode (SCE)
and the 0.10 mol/l NH3 NH4Cl buffer solution
(pH 8.50) was stirred with a Teflon-coated magnetic bar during measurement. The electrochemical cell used can be represented by
Cu MnO2-modified carbon paste sample solution
(0.10 mol/, pH 8.50, NH+
4 NH3 buffer solution) SCE.

2.3. Construction of the sensor


A Teflon rod (11 mm o.d.) with a hole at one
end (7 mm diameter, 3.5 mm deep) for the carbon
paste filling served as the electrode body. Electrical contact was made with a copper wire through
the centre of the rode. Unmodified carbon paste
was prepared by adding 1.58 g of solid paraffin oil
to 5.00 g of spectral carbon powder. Modified
carbon paste was prepared by replacing corresponding amounts of the carbon powder (2.5, 5,
10, 15 and 20% m/m) with manganese dioxide and
then adding the solid paraffin oil.The mixtures
were homogenized carefully by heating on an
electric hot-plate and then the hot carbon paste
was packed into the hole of the electrode; after a
shorted cooling time, the carbon paste was
smoothed onto paper until it had a shiny appearance. Before using the modified paste for potentiometric measurements, the electrode was
preconditioned in 0.10 mol/l NH3 NH4Cl buffer
solution for 72 h until a steady potential response
was obtained.

X. Zheng, Z. Guo / Talanta 50 (2000) 11571162

2.4. EMF measurement and selecti6ities


The electrode potential was measured in 50 ml
of sample or standard hydrogen peroxide solutions (pH 8.50, 0.10 mol/l NH3 NH+
buffer)
4
with stirring at 28C, and potentiometric measurement of the steady-state response was carried out
in the usual manner. After each measurement, the
H2O2 sensor was washed free of residual H2O2
and pH buffer solution with water until a stable
blank potential was obtained. The selectivity coefficients of the electrode for H2O2 with respect to
other ions were quantified using the mixed solution method [29].

3. Results and discussion

3.1. Electrode response


A typical calibration curve of the electrode
response for 3.00 10 8 3.60 10 3 mol/l
H2O2 shows that the linear range of electrode
response is 3.0010 7 3.63 10 4 mol/l H2O2
and the electrode gives a near-Nernstian response
of 19.4 mV/pH2O2 and a detection limit of 1.20
10 7 mol/l H2O2. The calibration curve is presented in Fig. 1.

3.2. Choice of the modifier on the sensor


The composition of the electrode is an important aspect to be considered for the analytical

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performance of this sensor. The initial testing


showed that an unmodified carbon paste electrode
did not have any potential response to H2O2. In
order to improve the analytical characteristics of
the CPE electrode, different metal oxide microparticles of MnO2, NiO, Co2O3 and TiO2 were
employed as modifiers. Of these modified electrodes, the CPE modified with MnO2 showed a
stable Nernstian response to H2O2, the sensor
doped with Co2O3 gave an unstable potential
response to H2O2, and sensors prepared with
other modifiers did not show any Nernstian response to H2O2. Thus MnO2 was selected as the
modifier for preparing the H2O2 potentiometric
sensor.

3.3. Effect of the amount of MnO2 in CPE on


the response
The effect of the amount of MnO2 on the
potential response of the sensor for H2O2 was
investigated by altering the ratio of MnO2 to
graphite powder in the mixture.The results
showed that the potentiol response increased with
increasing amounts of MnO2 up to 4.0% and it
decreased above 7%. Thus, an electrode modified
with 4% MnO2 was employed in further work.

3.4. Effect of electrode conditioned time on the


response
The MnO2-doped carbon paste electrode gave a
stable response to H2O2 after conditioning for a
sufficient period of time in 0.10 mol/l NH4Cl
NH3aqueous buffer medium. The response of a
newly made electrode drops rapidly with time, but
becomes stable after conditioning for 72 h; Fig. 2
shows the response curves after different conditioning times. The response is also more rapid
(B 3 min) than that of a conventional electrode,
owing to the low resistance. Fig. 1 shows that the
response of this electrode conditioned for \72 h
is Nernstian.

3.5. Effect of pH on the response

Fig. 1. Typical calibration graph for the H2O2 sensor.

Based on the preliminary testing results, none


of the other acid or basic buffer solutions investi-

X. Zheng, Z. Guo / Talanta 50 (2000) 11571162

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Fig. 2. Effect of conditioning time of the sensor for 10.0


mmol/l H2O2 (pH 8.50, 0.10 mol/l NH+
4 NH3 solution).
Table 1
Interferences of various ions for the H2O2 sensor
Interfering ions
C2O2
4
Co2+
CO2
3
PO3
4
SO2
4
SO2
3
NO
2

7.2103
3.0102
2.4104
1.1102
1.6104
3.0104
2.5104

gated, such as H2SO4, HCl, NaOH, NaHCO3 and


N2B4O7 (their concentrations were 0.10 mol/l, respectively), proved to be better than 0.10 mol/l
NH+
4 NH3 buffer solution for H2O2 determination. So the NH+
4 NH3 buffer solution was chosen for controlling the pH values of sample
solutions.
The effect of pH values of sample solutions on
the potential readings of the H2O2 sensor was
Table 2
Results of examination of the sensor reproducibilitya
Number of repeats
for determination of
H2O2 response

1.00106 mol/l 1.00105 mol/l


H2O2
H2O2

1
2
3
4

183.2
182.6
182.5
183.1
a

Results are given in mV.

163.9
164.1
163.8
164.0

checked by recording the e.m.f. of a standard cell


Cu MnO2 chemically modified CPE 1.00 10 5
mol/l H2O2, NH+
4 NH3 buffer solution SCE and
varying the acidity by the addition of small volumes of HCl and/or ammonium solution (1.0
mol/l of each); the concentration of H2O2 was
1.00 10 5 mol/l. The results showed that while
the pH changed in the range 7.08.0, the potential response increased with increasing pH; this
results may be related to the enhancing of oxidizing ability of H2O2 when pH changed in this
range. For pH values in the range 8.09.0, the
response was almost constant; Above pH 9.0, the
potential response dropped, possibly because it is
difficult to oxidize MnO2 + to its higher oxidation
state when pH\ 9.0. So the potential response
dropped. Thus, pH 8.50 NH+
4 NH3 buffer solution was selected for the further experiments.

3.6. Selecti6ity of the electrode


The selectivity of the sensor was evaluated by
the mixed solution method. The results are presented in Table 1 and show that the sensor offered
a good selectivity for H2O2, and that many potentially interfering ionic species, excepting Co2 + and
PO34 , do not interfere in the determination of
H2O2.

3.7. The performance of the sensor


3.7.1. The response time
When the hydrogen peroxide concentration was
above 1.00 10 5 mol/l, the response time was
shorter than 3 min; when the H2O2 concentration
was 3.00 10 7 mol/l, the response time was 5
min.
3.7.2. The reproducibility of the sensor
The reproducibility of the sensor was examined
using the reference method [30]. The results are
shown in Table 2 and reveal that the sensor had a
good reproducibility for determination of H2O2.
3.7.3. The life time of the sensor
After the new sensor had been conditioned for
a given time, it showed a stable response for H2O2
when it was used continually for 20 days; the

X. Zheng, Z. Guo / Talanta 50 (2000) 11571162

response slope and linear range of the sensor for


H2O2 kept from any obvious various. The sensor
appeared the poor stability and long response
time after it was continually used over such a long
time as 30 days; at the same time, the response
linear range of the sensor for H2O2 was also poor.
But the sensor regained its good response performance after it was smoothed and conditioned
when it was first prepared.

3.8. Discussion on the possible response


mechanism of the sensor
When the sensor was conditioned in 0.10 mol/l
NH3 NH+
4 buffer solution, the e.m.f. increased
with time at first and then gave a constant response over a long time.While a few of H2O2
presented in the testing buffer solution, the response of this sensor was faster than that of blank
testing buffer solution. Based on those experimental phenomena and some of MnO2 chemically
properties, we proposed the possible response
mechanism of this sensor as follows. First, a few
of the solvated MnO2 was formed on the face of
the sensor when the sensor was inserted in the
testing solution. Second, H2O2 can oxidize MnO2
to produce MnO24 [31], so the sensor appeared
response for H2O2. Third, the response results
showed that the e.m.f. became more positive with
increasing H2O2 concentration and the sensor regained its blank e.m.f. response after it was again
inserted in the blank solution (not contained
H2O2). The possible reason is that the organic
materials which existed in parallin oil reduced the
Table 3
Analytical concentrations (mol/l) of H2O2 in rainwater samples
Sample

Concentration as deter- Concentration as demined by proposed


termined by CL
methoda
methodb

1
2
3
4

(2.5 9 0.3)106
(3.7 9 0.4)106
(0.8 90.4)106
(0.9 90.3)106
a
b

2.6106
3.6106
0.8106
0.9106

Mean of four determinations ( 9 R.S.D., %).


Mean of three replications.

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MnO24 to produce MnO2. So the possible response mechanism of this sensor is attributed to
the following procedures and reactions:
MnO2 (in CPE)+ H2O
MnO2H2O (in solventing film)

(1)

MnO2H2O MnO(OH)2 (in solventing film)


(2)
MnO(OH)2
MnO2 + + OH (in solventing film)
MnO

2+

+ H2O2 + OH

MnO24 + H2O (in solventing film)


2
4

MnO

(3)

+ R (in parallin) MnO2 + Ox

(4)
(5)

So the potentiometric response of this sensor


my be a mixture redox potentiol between the
MnO24 and MnO2 + ; at the same time, the ratio
of [MnO24 ]/[MnO2 + ] (in the solvent film) is adjusted by the concentration of H2O2 in buffer
solution, so the electrode gives the Nernstian response for the H2O2.

3.9. The sample analysis


The utility of this sensor was checked by using
it for the quantitative determination of H2O2 in
rainwater samples collected on different days (in
Xian, China) and comparing the results with that
of the chemiluminescence (CL) method [32]. The
results (shown in Table 3) clearly show that the
proposed method performs exceptionally well and
the results obtained are in agreement with the CL
method.
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