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Journal of Chromatography A
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Short communication

A simple and rapid method for the determination of lead dioxide in

minium by headspace gas chromatographic technique
Wei-Qi Xie a,b,∗, Yi-Xian Gong a,∗, Shi-Wen Huang b, Kong-Xian Yu c
a
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, Guangdong, China
b
School of Materials Science and Engineering, South China University of Technology, Guangzhou, Guangdong, China
c
Health Supervision Bureau of Liaoning Province, Shenyang, Liaoning, China

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

Article history: This paper demonstrated a simple and rapid approach for the determination of lead dioxide in minium
Received 31 July 2019 using a headspace gas chromatographic (GC) technique. This new approach was based on the mea-
Revised 13 December 2019
surement of carbon dioxide from the redox reaction between lead dioxide and oxalic acid in a sealed
Accepted 27 December 2019
headspace vial. The obtained results indicated that the new approach had good measurement accuracy
Available online xxx
(relative errors ≤8.71%) and precision (RSD ≤2.86%). Moreover, the limit of quantification (LOQ) and limit
Keywords: of detection (LOD) for this new approach were respectively 0.34% and 0.10%, and the recoveries ranged
Lead dioxide from 97.9 to 101.7%. The new approach is low-cost and reliable, which has potential for use in the analysis
Headspace GC of lead dioxide in minium and related products.
Minium
Redox reaction © 2020 Elsevier B.V. All rights reserved.

1. Introduction is the time-consuming procedure, which leads to low efficiency

Minium, also known as red lead, is a bright orange-red chem-
ical compound containing lead dioxide (PbO2 ) and lead monox-
ide (PbO) [1–3]. It is one of the earliest artificially prepared pig-
ments and has been widely applied in the decoration of wall, panel
paintings and manuscripts in the medieval times [4,5]. Currently,
minium is an important industrial raw material in the manufacture
of batteries, glass, and ceramics [6,7]. It is also applied in the pro-
tective coating for anticorrosive pigments and the oxidant for dyes
and some organic synthesis [8,9]. PbO2 is the main effective com-
ponents in minium, which can significantly affect the properties
(i.e., oxidation and anticorrosion properties) of minium in related
applications [10]. If the PbO2 content in minium is known in the
production process, a good control strategy can be made during
the minium production and application. Hence, a simple approach
that can measure PbO2 content in minium is of great significance
for the production and quality control of minium products.
Currently, several analytical approaches have been developed
for measuring PbO2 content in minium, e.g., titration method [11],
inductively coupled plasma optical emission spectrometry (ICP-
OES) method [12], X-ray diffraction (XRD) method [13,14], and
electrolytic method [15]. The main shortcoming of titration method
∗
Corresponding authors.
E-mail addresses: mswqxie@mail.scut.edu.cn (W.-Q.
msgyx@mail.scut.edu.cn (Y.-X. Gong).
in the batch sample determination. In the ICP-OES, XRD and elec-
trolytic method, the main shortcomings are the measurement ac-
curacy and precision in the PbO2 determination, especially when
measuring the minium samples with complex matrices. The impact
of other existing substances on the PbO2 measurement is difficult
to eliminate.
Headspace gas chromatography (HS-GC) is an efficient tech-
nique that can avoid the interference from other species in sam-
ple [16]. In this technique, the sample conditioning (e.g., heated
to a desired temperature) can be performed automatically in a
headspace oven [17]. In addition, by detecting volatile substances
generated from nonvolatile substances through some chemical re-
actions (i.e., reactions that can produce volatile products), HS-GC
is also capable of measuring some nonvolatile substances [18,19].
In headspace system, the headspace vial can be applied as a mi-
croreactor for some reactions and the volatile products from re-
actions can be collected and analyzed using HS-GC system. In a
previous paper [20], we investigated a simple approach for quanti-
fying trichloroacetic acid in urine samples by HS-GC. The principle
of the method is analyzing the chloroform generated from the self-
decomposition of trichloroacetic acid in sealed vial. According to
report in reference [21], under a proper acid condition, the PbO2 in
minium can be converted into CO2 via the redox reaction of PbO2
with oxalic acid (H2 C2 O4 ), which can be denoted as follows,
Xie),
2H2C2 O4 (aq ) + P bO2 (s ) → P bC2 O4 (s ) + 2C O2 (g) + 2H2 O(l ) (1)

https://doi.org/10.1016/j.chroma.2019.460832
0021-9673/© 2020 Elsevier B.V. All rights reserved.

Please cite this article as: W.-Q. Xie, Y.-X. Gong and S.-W. Huang et al., A simple and rapid method for the determination of lead dioxide
in minium by headspace gas chromatographic technique, Journal of Chromatography A, https://doi.org/10.1016/j.chroma.2019.460832
JID: CHROMA
ARTICLE IN PRESS
2 W.-Q. Xie, Y.-X. Gong and S.-W. Huang et al. / Journal of Chromatography A xxx (xxxx) xxx
In Eq. (1), H2 C2 O4 acts as the reducing agent for convert-
ing lead(IV) to lead(II), and PbO2 acts as the oxidizing agent and
limiting reactant. Thus, the quantitative analysis of PbO2 may be
achieved by detecting the CO2 produced from the above reaction
using HS-GC system.
In this work, we proposed an alternative approach to analyze
PbO2 in minium with HS-GC system. The main contents were to
search for the optimal conditions (the dosage of H2 C2 O4 , pH value
of reaction system, condition of headspace equilibrium) for com-
pleting the redox reaction. The validation of the HS-GC approach
was also carried out.
2. Experimental section
2.1. Materials
H2 C2 O4 , sodium chloride (NaCl), sodium acetate (NaAc), Acetic
acid (HAc) and PbO2 were analytical-grade and bought from TCI
Development Co., Ltd., (Shanghai, China). The NaAc-HAc buffer
(1:1) was prepared by mixing 0.5 mol/L NaAc and 0.5 mol/L HAc
(pH = 6.0). The standard samples were prepared by mixing proper
weight (0–25.0 mg) of pure PbO2 with 1.0 mL of NaAc-HAc buffer
(1:1). Distilled water was used in this research. The minium sam-
ples were collected from factories and minium suppliers in south-
ern China.
2.2. Apparatus and conditions
The HS-GC detection was run by a fully-automated headspace
sampler (Thermo Scientific TriPlus 300, USA) and a GC system
(Agilent Technologies 7890A GC system, USA) equipped with a
thermal conductivity detector (TCD) and a GS-Q capillary column
(30 m × 0.32 mm, i.d., 1 μm phase thickness, Agilent J&W Sci-
entific, USA). The GC was operated at a temperature of 105 °C
with nitrogen (99.999%, Guangzhou Shengying Gas Co., Ltd., China)
carrier gas (flow rate = 2.7 mL/min). Conditions in headspace
sampler: equilibration temperature = 90 °C, pressurization pres-
sure = 0.10 Mpa, carrier gas pressure = 0.15 MPa, vial pressuriza-
tion time = 15 s, sample loop fill time = 10 s, and sample loop
volume = 3 mL.
2.3. Lead dioxide analysis by HS-GC
50.0 mg of dried minium was placed in a small beaker that
contains 2.0 mL of HNO3 solution (4.0 mol/L). The mixture was
then stirred for 20 min at room temperature. After that, the mix-
ture was filtered by vacuum filter and the filter residue (contain-
ing PbO2 ) was washed with distilled water (three times). The filter
residue was placed in headspace vial (20.0 mL, Thermo Scientific,
USA). 1.0 mL of NaAc-HAc buffer (1:1) and 1.0 mL of H2 C2 O4 so-
lution (0.4 mol/L) were then successively placed in the vial and
sealed with septum (PTFE/silicone, Thermo Scientific, USA) and
aluminum cap. After that, the sealed vial was measured using HS-
GC. The sample equilibration temperature and time were respec-
tively 90 °C and 30 min before the HS-GC measurement.
2.4. Lead dioxide analysis by titration [11]
A suitable weight of minium powder was triturated with 30 mL
of sodium acetate. And then, 50 ml of 0.1 mol/L sodium thiosul-
phate was added and the mixture was stirred until the red lead
disappeared. The mixture was stirred with a porosity thimble, and
the residue was washed with water. An excess of sodium thiosul-
phate was then triturated with the combined filtrate and rinsed
with 0.1 mol/L iodine. Blank test was carried out in the same
method.
Please cite this article as: W.-Q. Xie, Y.-X. Gong and S.-W. Huang et al., A simple and rapid method for the determination of lead dioxide
in minium by headspace gas chromatographic technique, Journal of Chromatography A, https://doi.org/10.1016/j.chroma.2019.460832
[m5G;January 8, 2020;9:55]
Fig. 1. Effect of the dosage of H2 C2 O4 .
2.5. Method calibration and validation
The calibrated curve for PbO2 content analysis was obtained
from a group of standard samples. The PbO2 standard samples
for was analyzed by the procedures of HS-GC approach men-
tioned above. The method precision was evaluated using the rel-
ative standard deviation (RSD,%) of those values. The accuracy of
the approach was assessed using the recovery test and compar-
ison test. The comparison test was conducted by comparing the
results of PbO2 obtained from the HS-GC and titration method
(seven minium samples). Triplicate measurements were conducted
for each sample.
3. Results and discussion
3.1. Optimization of reaction conditions
The minium sample was firstly treated with an excess of HNO3
solution to obtain PbO2 . After that, the obtained PbO2 (filter
residue) was used for HS-GC testing using the procedures in exper-
imental section (according to Eq. (1)). In Eq. (1), H2 C2 O4 acts as the
reductant agent and Pb(IV) is converted into Pb(II) under an acidic
medium. The effects of the reaction conditions (i.e., the dosage of
H2 C2 O4 , the reaction temperature and time, and pH value) on the
complete redox reaction (Eq. (1)) were discussed below.
In this work, 0.05 g of minium sample was used in each test-
ing throughout the research. According to the literature [21], it is
necessary to use an excess amount of H2 C2 O4 for completing the
reaction of PbO2 with H2 C2 O4 (PbO2 is the limiting reactant). Fig. 1
showed the effect of H2 C2 O4 dosage on the conversion of PbO2
to CO2 under the reaction conditions obtained from literature. It
was clear that the complete conversion of PbO2 to CO2 could be
achieved when 0.4 mmol of H2 C2 O4 was added, and thus 0.4 mmol
of H2 C2 O4 (1.0 mL of 0.4 mol/L H2 C2 O4 solution) was selected for
the following investigation.
Typically, a high temperature can improve the rate of chemi-
cal reactions [21]. Besides, in order to reduce the content of resid-
ual CO2 in reacting (liquid) phase and reduce the time needed
for the vapor-liquid equilibrium of generated CO2 , it is also better
to choose a high temperature. However, the temperature above or
near the boiling point of water also leads to a higher water vapor
in the headspace vial, which increases the risk of accidental rup-
ture of the headspace vial. Besides, according to the literature [21],
the redox reaction (Eq. (1)) should be treated in an acid condition.
Therefore, it is necessary to explore the appropriate reaction tem-
perature, time and pH value in this work. Fig. 2(a)–(e) showed the
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W.-Q. Xie, Y.-X. Gong and S.-W. Huang et al. / Journal of Chromatography A xxx (xxxx) xxx 3

Fig. 2. Effect of temperature and time on PbO2 conversion at different pH values ((a) 4.0, (b) 5.0, (c) 6.0, (d) 7.0, and (e) 8.0).

effect of time and temperature (70, 80 and 90 °C) on the conver-
sion of PbO2 to CO2 at different pH values (4.0, 5.0, 6.0, 7.0 and
8.0, pH value was adjusted by NaAc-HAc buffer (1:1)). As can be
found in each figure (Fig. 2(a)–(e)), the redox reaction was greatly
affected by the temperature, and the reaction rate and the rate
of vapor-liquid equilibrium increase with the increase of reaction
temperature until it reached 90 °C. The reason for the results may
be that higher temperature can both enhance the rate of the redox
reaction and vapor-liquid equilibrium. Thus 90 °C was selected as
the optimal reaction temperature in this work. In addition, Fig. 3
showed the effect of pH value on the reaction under the temper-
ature of 90 °C, which can been seen that the optimal pH value in

Please cite this article as: W.-Q. Xie, Y.-X. Gong and S.-W. Huang et al., A simple and rapid method for the determination of lead dioxide
in minium by headspace gas chromatographic technique, Journal of Chromatography A, https://doi.org/10.1016/j.chroma.2019.460832
JID: CHROMA
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Table 1
Method repeatability.

Replica PbO2 content,%

no. Sample 1 Sample 2 Sample 3

1 34.09 27.86 16.25

2 34.34 26.63 16.71
3 34.81 27.57 17.13
4 35.47 26.94 16.08
RSD,% 1.75 2.07 2.86

In the present research, appropriate acidity (pH = 6.0) was se-

Fig. 3. Effect of pH value on PbO2 conversion at 90 °C.
lected for meeting the requirement of the redox reaction. However,
in an acidic medium, some other compounds (e.g., lead carbon-
ate) in minium might also react with hydrogen ion and produce
CO2 , and the possible interference that may affect PbO2 estima-
tion should be investigated. Actually the effect of lead carbonate
on PbO2 estimation can be minimized by conducting a blank test
(sample that contains no H2 C2 O4 solution). Besides, the CO2 in the
headspace air also has the possibility of interfering with the lead
dioxide analysis, and the interference can be minimized by purging
the headspace vial with nitrogen before testing.

3.3. Method calibration and validation

In this work, a set of standard PbO2 samples prepared in the

Fig. 4. Chromatogram of a minium sample from the HS-GC analysis.
the redox reaction was 6.0, which was due to that a suitable acid-
ity is helpful to dissolve minium sample and promote the redox
reaction (i.e., suitable acidity plays a catalytic role for the redox
reaction) [21]. When the reaction time was under 25 min, the re-
action was incomplete and the CO2 yield was nearly 97% under
the optimal conditions (90 °C and pH value of 6.0). Therefore, it is
needed to extend the reaction time for improving the conversion
rate, and 30 min is sufficient for completing the reaction (GC sig-
nal no longer increased) under the above optimal conditions (90 °C
and pH value of 6.0). Thus, it was reasonable to select 6 as the
optimal pH value, and 90 °C and 30 min as the optimal reaction
temperature and time, respectively.
3.2. Chromatographic separation
In the redox reaction, CO2 is the volatile product that needs
analysis. There is a significant amount of air in the tested
headspace vial, and thus it is particularly important to separate
the substances from air in the GC analysis. Fig. 4 showed a chro-
matogram of CO2 and other substances (oxygen (O2 ) and water va-
por (H2 O)) from air, it proved that the given GC conditions were
appropriate for separating CO2 from O2 and H2 O in the air.
experimental section (as standard curve) were used to calibrate the
present approach. By adding standard PbO2 samples to headspace
vials and performing the procedures of the present method, the
standard curve was obtained,
 
A = 0.36(±0.02 ) + 139.5( ± 0.52 ) × N n = 7, R2 = 0.999
(2)
where A and N represent the GC signal of headspace CO2 and the
PbO2 amount (in mmol) added in the headspace vial, respectively.
The PbO2 in minium was calculated by
NM
C= × 100% (3)
2m
where C represents the PbO2 content (%) in minium samples. M, m,
2 are the molar mass (g/mol) of PbO2 , the weight (mg) of minium
sample, and the mole ratio of CO2 to PbO2 .
The limit of quantification (LOQ) and limit of detection (LOD)
for the this new approach were respectively calculated using
Eqs. (4) and (5),
10|a|
LOQ = (4)
s
3|a|
LOD = (5)
s
where s, a and a represent the slope, the intercept and the un-
certainty of the intercept in both Eqs. (4) and (5), respectively. The
LOQ for CO2 in this approach is 1.43 μmol (corresponds to 0.34%
for PbO2 content), and LOD for CO2 in this approach is 0.43 μmol
(corresponds to 0.10% for PbO2 content).
The repeatability of the proposed technique was investigated by
quadruplicate tests on three minium samples from the different
sources. As listed in Table 1, the relative standard deviation (RSD)
of the proposed technique was within 2.86%.
The method accuracy was examined using a recovery test, i.e.,
spiking different amount (known) of PbO2 into the real minium
samples and check their actual contents measured by the HS-GC
method. Table 2 showed the results from the recovery test, and il-
lustrated that the recoveries of PbO2 by this method are ranged
from 97.9 to 101.7%, which further proved that the complete con-
version of PbO2 to CO2 was achieved in the redox reaction and the

Please cite this article as: W.-Q. Xie, Y.-X. Gong and S.-W. Huang et al., A simple and rapid method for the determination of lead dioxide
in minium by headspace gas chromatographic technique, Journal of Chromatography A, https://doi.org/10.1016/j.chroma.2019.460832
JID: CHROMA
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Table 2 CRediT authorship contribution statement

Recovery test.

Sample PbO2 content,% Wei-Qi Xie: Conceptualization, Writing - original draft, Method-
ID Added (n = 3) Measured (n = 3) Recovery,% ology, Software. Yi-Xian Gong: Data curation, Writing - original
1 5.26 ± 0.03 5.18 ± 0.16 98.48 draft, Supervision, Validation. Shi-Wen Huang: Writing - review &
2 11.20 ± 0.01 10.96 ± 0.31 97.86 editing. Kong-Xian Yu: Validation, Supervision.
3 16.64 ± 0.02 16.87 ± 0.45 101.38
4 8.64 ± 0.01 8.57 ± 0.24 99.19
Acknowledgements
5 20.08 ± 0.05 20.43 ± 0.53 101.74

The authors acknowledge the financial and technical support

from the State Key Laboratory of Pulp and Paper Engineering,
South China University of Technology, China.

References

Fig. 5. The correlation between the results from titration method and HS-GC
method.
new approach was reliable for PbO2 estimation in minium sam-
ples. The results also proved that the complete conversion of PbO2
to CO2 was confirmed.
The PbO2 of 12 minium samples were also tested by both titra-
tion approach and this new approach, and the correlation between
the results from titration approach and new approach was shown
in Fig. 5. As seen from Fig. 5 that there is an excellent correlation
(R2 = 0.997) between these two methods, which further proved
that the complete conversion of PbO2 to CO2 (The CO2 yield was
nearly 100%) was achieved in the HS-GC approach. Moreover, un-
like the titration technique, the HS-GC can not only perform an au-
tomated headspace equilibration (the reaction in this case) at pre-
cisely controlled temperature and time but also in a batch sample
testing manner, a high-throughput test can be realized if the batch
sample analysis is required.
4. Conclusions
In this paper, we have proposed an automated and rapid ap-
proach for the PbO2 analysis in minium samples based on HS-GC
technique. This approach has not only a high measurement preci-
sion but also the accuracy when compared with those measured by
a reference method. It is also low-cost and reliable, aim at provid-
ing a valuable tool for the assessment of PbO2 content in minium
related products.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
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Please cite this article as: W.-Q. Xie, Y.-X. Gong and S.-W. Huang et al., A simple and rapid method for the determination of lead dioxide
in minium by headspace gas chromatographic technique, Journal of Chromatography A, https://doi.org/10.1016/j.chroma.2019.460832