DESALINATION

Desalination 247 (2009) 423–429

www.elsevier.com/locate/desal

Quantitative determination of polyethylene glycol with

modified Dragendorff reagent method
Zhiqian Jia*, Chunai Tian
Department of Chemistry, Beijing Normal University, Beijing 100875, PRC
Tel: +86-010-58210560; email: zhqjia@bnu.edu.cn

Received 5 January 2007; accepted 2 September 2008

Abstract
Quantitative determination of polyethylene glycol (PEG) is usually needed in membrane technology, water
environment and chromatography. The concentration of PEG is generally measured with the Dragendorff reagent.
But in the literature method, the hydrolysis of the Dragendorff reagent results in nonlinear calibration curve and
unsatisfied reproducibility. In this paper, a modified Dragendorff approach was provided to inhibit the hydrolysis
in the analysis. The effects of acids and its concentrations were studied. The results showed that, with the modified
method, the calibration curves for PEG 4000, 6000, 10,000 and 20,000 displayed good linearity.

Keywords: Polyethylene glycol; Dragendorff reagent; Ultrafiltration membrane; Molecular weight cut-off

1. Introduction widely employed especially in the separation of

linear polymers because the retention coefficient
Quantitative determination of polyethylene
of PEG is similar to that of the linear polymers.
glycol (PEG) is usually needed in membrane
To determine the PEG concentration, the Dra-
technology, water environment [1] and chroma-
gendorff reagent, widely used in the measurement
tography. For example, in the preparation of
of alkaloid [6], is often employed. The reaction of
ultrafiltration membranes, determination of
Dragendorff reagent with PEG generates an
molecular weight cut-off (MWCO) is usually
orange-red complex, which is easily detected at
indispensable [2, 3]. PEG or protein with differ-
510 nm with UV-vis spectrophotometer [7, 8].
ent molecular weight is often employed as the
In the preparation of the calibration curve, PEG
standards [4, 5]. By measuring the concentrations
standard solutions are mixed with the Dragendorff
of the standards in the permeate and the feed, the
reagent, and then the absorbance is measured with
retention coefficient and MWCO of membranes
UV-vis spectrophotometer. The absorbance of the
are obtained. As PEG is cheap and stable, it is
permeate and the feed solution are measured with
*Corresponding author. the same procedure and the concentrations are

0011-9164/09/$– See front matter Ó 2009 Published by Elsevier B.V.

doi:10.1016/j.desal.2008.09.004
424 Z. Jia, C. Tian / Desalination 247 (2009) 423–429
read from the calibration curve. Nevertheless, in
the above procedures, Dragendorff reagent hydro-
lyzes seriously, resulting in nonlinear calibration
curve, poor accuracy and unsatisfied reproducibil-
ity. In this paper, the effects of acids and their con-
centrations on the inhibition of the hydrolysis
were studied.
2. Experimental section [6, 7]
PEG (molecular weight of 4000, 6000,
10,000 and 20,000), Bismuth subnitrate
(BiONO3), glacial acetic acid (HAc), KI and
hydrochloric acid (HCl) were analytical pure
and provided by Beijing Reagents Factory. The
UV-vis absorbance was measured with UV-vis
spectrophotometer (Cintra 10e, Australia). The
pH of the solution was determined with pH
meter (Shanghai Jingke Instrument Co. Ltd.).
2.1. Preparation of Dragendorff reagent
A 0.800 g of BiONO3 and 10 ml of glacial
HAc were added into a 50-ml volumetric flask.
Then the mixture was diluted to volume with dis-
tilled water to obtain solution A. 20 g KI powder
was added into a 50-ml brown volumetric flask
and diluted to the mark with water to obtain sol-
ution B. Then 5 ml of solution A and 5 ml of
solution B were added into a 100-ml brown
volumetric flask and diluted to volume with dis-
tilled water to obtain the Dragendorff reagent.
2.2. Preparation of HAc–NaAc buffer
solution (pH 4.8)
A 590 ml of 0.2 mol L1 NaAc solution and
410 ml of 0.2 mol L1 HAc solution were added
into a 1000-ml volumetric flask and diluted to
the mark with distilled water.
2.3. Preparation of PEG standard solutions
Exactly 0, 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 ml of
1000 mg L1 PEG stock solution was pipetted
into 100-ml volumetric flasks, respectively and
diluted to the mark with distilled water to obtain
the PEG standard solutions with concentrations
of 0, 5, 10, 15, 20, 25 and 30 mg L1.
2.4. Preparation of calibration curve
A 5.0 ml of PEG standard solutions with con-
centrations of 0, 5, 10, 15, 20, 25 and 30 mg L1
were added into 10-ml volumetric flasks. Then
1.0 ml of HAc–NaAc buffer solution and 1.0 ml
of the Dragendorff reagent were added, respec-
tively. Lastly, the mixed solution was diluted to
volume with distilled water. After 15 min, the
absorbance was determined with UV-vis spectro-
photometer to obtain the calibration curves.
3. Results and discussions
According to the literature [6, 7], in the
preparation of Dragendorff reagent, 5.0 ml of
solution A (i.e., BiONO3 solution) was mixed
with 5.0 ml of solution B (i.e., KI solution),
and then diluted to 100 ml with water. Figure 1
shows that solution A has no absorption band
from 300 nm to 800 nm, and solution B only
shows absorbance below 340 nm. When solution
A was mixed with B, I reacts with Bi3+ and
forms BiI3 precipitates. As KI is in excess
in the mixture (the molar ratio of I to Bi3+
is 43.3), BiI3 reacts with I and forms [BiI4]
complex:
3I + Bi3+ ? BiI3
BiI3 + I ? BiI4
The stepwise formation constants of [BiI4]
are K1 = 3.63 and K4 = 14.95 [9]. The maximum
absorbance of [BiI4] is displayed at 465 nm
(Fig. 1) [10, 11].
When the mixed solution was diluted to
100 ml with water to obtain the Dragendorff
reagent, the mixture became turbid and golden-
yellow precipitates settled down after a certain
time. These phenomena were attributed to the
 Z. Jia, C. Tian / Desalination 247 (2009) 423–429 425

1.4 a)
30 mg L⫺1
1.2 25 mg L⫺1
20 mg L⫺1
Absorbance

Absorbance
1.0 15 mg L⫺1
A+B+HAc
0 mg L⫺1
0.8 10 mg L⫺1
Solution A
5 mg L⫺1
0.6

Solution B 0.4

0 0.2
300 400 500 600
300 400 500 600 700 800 900
Wavelength (nm)
Wavelength (nm)
Fig. 1. Absorption spectra of solution A, solution B and
the mixture. 0.75
b)
0.70

Absorbance
0.65
hydrolysis of BiI4 and the formation of black
BiI3 and orange BiOI precipitates [12]. 0.60

0.55

BiI
4 ! BiI3 # þI
 0.50

0.45
BiI3 þ H2 O ! BiOI # þ2HI 0 5 10 15 20 25
Concentration (mg L⫺1)
30

Fig. 2. Results obtained according to the procedures in

In the preparation of calibration curve, 5.0 ml
of standard PEG 10,000 solutions with concen-
trations of 0, 5, 10, 15, 20, 25 and 30 mg L1
were added into 10-ml volumetric flasks. Then
1.0 ml of HAc–NaAc buffer solution, 1.0 ml of
Dragendorff reagent and water were added,
respectively. After 15 min, the absorbance was
determined with UV-vis spectrophotometer. In
these procedures, large amount of precipitates
were formed in the mixture. Figure 2a shows
that the absorption spectra of the solutions are
plat and there is no characteristic band of
PEG–BiI4 complex at 510 nm. The scattering
phenomena on the long wavelength areattributed
to the suspended precipitates. The relation
between the absorbance at 510 nm and the
concentrations of PEG isnot linear (Fig. 2b),
indicating that the reproducibility and accuracy
of the method arevery poor.
the literature. (a) Absorption spectra of PEG 10,000 sol-
utions with different concentrations. (b) The calibration
curve of PEG 10,000.
From the above results, it can be seen that, in
the preparation of Dragendorff reagent and
calibration curve, the hydrolysis of BiI4 should
be effectively inhibited. For the lack of solubility
data of BiI3 and BiOI, the proper pH value had to
be estimated empirically. In solution A, the HAc
concentration, C, was 3.494 mol L1. The disso-
ciation constant of HAc, Ka,HAC, is 104.76. Then
pH = [lg H+] = lg (Ka,HACC)1/2 = 2.11. When
solution A was mixed with solution B, the HAc
concentration decreased to 1.747 mol L1 and
the pH increased to 2.26. In this case no precipi-
tates were formed. When the mixture was diluted
with water to obtain the Dragendorff reagent, the
426 Z. Jia, C. Tian / Desalination 247 (2009) 423–429
HAc concentration declined to 0.174,7 mol L1
and the pH was 2.76. At this pH, large amounts
of precipitates were formed. So the pH value
should be lower than 2.76. In the modified proce-
dures, the mixture of 5.0 ml of solution A and
5.0 ml of solution B was diluted with 3.85
mol L1 HAc solution to 100 ml. In the modified
Dragendorff reagent, the HAc concentration was
3.669 mol L1 and the pH was 2.10. The modified
reagent appeared as orange-yellow transparent
solution with an absorption band at 465 nm, and
kept stable for several months.
In the preparation of the calibration curve, to
inhibit the hydrolysis, the mixture of PEG and
Dragendorff reagent should also be diluted
with HAc solution. To elucidate the effects of
HAc concentration, 5.0-ml aliquots of standard
20 mg L1 PEG 10,000 solution was pipetted
into 10-ml volumetric flasks. Then 3.0 ml of
HAc solutions with concentrations of 0, 2.16,
4.33, 6.06, 8.66, 12.98 and 16.44 mol L1
were added, respectively. Lastly, 1.0 ml of
modified Dragendorff reagent was added, and
the mixture was diluted to volume with the cor-
responding HAc solution. The pH values of the
mixtures were 2.60, 2.40, 2.22, 2.16, 2.09, 2.01
and 1.95, respectively. With the increasing con-
centration of HAc solutions, the transparency of
the mixture increased, and the absorbance of
BiI4 at 465 nm and that of PEG–BiI4 at
510 nm increased (Fig. 3). The reason was that
high acidity favors the inhibition of hydrolysis
of Bi3+ and the formation of BiI4 and PEG–
BiI4 complex.
HOðCH2 CH2 OÞn H þ Hþ
Hþ
! HOðCH2 CH2 O Þn H
Hþ
HOðCH2 CH2 O Þn H þ Bil
4 but soluble in HCl solutions with concentrations
Hþ
! HOðCH2 CH2 O Þn HBil
4 formation constants of Bi3+–Cl complexes are
2
16.44 mol L⫺1
12.98 mol L⫺1
8.66 mol L⫺1
6.06 mol L⫺1
Absorbance
4.33 mol L⫺1
2.16 mol L⫺1
1 0 mol L⫺1
0
400 500 600
Wavelength (nm)
Fig. 3. Effects of HAc concentration on the absorbance
spectra.
In the following experiments, in the prepara-
tion of the calibration curves, 3.0 ml of 8.66
mol L1 HAc solution was used in the analysis.
That was, 5.0 ml of PEG standard solutions
(0, 5, 10, 15, 20, 25 and 30 mg L1) were pipetted
into 10-ml volumetric flasks, respectively. Then
3.0 ml of 8.66 mol L1 HAc solution and 1.0
ml of modified Dragendorff reagent were added.
Lastly the mixture was diluted to volume with
8.66 mol L1 HAc solution. The final pH value
was 2.09. It was found that there were not appa-
rent precipitation phenomena occurring in all
the samples. The samples with PEG concentra-
tions of 0 mg L1 and 5 mg L1 displayed yellow
solutions, whereas those with PEG concentrations
from 10 mg L1 to 30 mg L1 were orange.
Figure 4a and b shows that the absorbance at
510 nm increases with the concentrations of
PEG 10,000 and the absorbance–concentration
relation is linear. Figure 4c shows that, for PEG
4000, 6000 and 20,000, the calibration curves
also display good linearity.
Instead of HAc, in the preparation of the Dra-
gendorff reagent, H2SO4 and HCl were also tried
in dissolving BiONO3 powder. It was found that
BiONO3 was almost insoluble in dilute H2SO4,
equal to or larger than 1.0 mol L1. The stepwise
 Z. Jia, C. Tian / Desalination 247 (2009) 423–429 427

1.0 0.6
⫺1
a) 30 mg L a) 30 mg L⫺1
25 mg L
⫺1
25 mg L ⫺1
20 mg L⫺1 20 mg L⫺1
15 mg L⫺1 10 mg L⫺1
Absorbance

0.4
5 mg L⫺1

Absorbance
10 mg L⫺1
0.5 5 mg L⫺1
⫺1
0 mg L
0.2

0.0 0.0
400 500 600 500 600
Wavelength (nm) Wavelength (nm)

b)
b)
0.4 0.4
Absorbance

0.2 Absorbance 0.2

0.0
0 5 10 15 20 25 30 0.0
⫺1 0 5 10 15 20 25 30
Concentration (mg L )
Concentration (mg L⫺1)
0.6 Fig. 5. Results obtained when HCl was employed in the
c) PEG 4000
PEG 6000
modified method. (a) Absorption spectra for PEG
PEG 20000 10,000. (b) Calibration curve for PEG 10,000.
Absorbance

0.4
dissolving BiONO3. In the preparation of
Dragendorff reagent, 0.800 g of BiONO3 was
0.2 added into a 50-ml volumetric flask, then 1.0
mol L1 HCl was added to the mark to obtain
solution A. 20 g of KI powder was added into
0.0 a 50-ml brown volumetric flask and dissolved
0 5 10 15 20 25 30 35
⫺1
with water to obtain solution B. Lastly, 5.0 ml
Concentration (mg L )
of solution A and 5.0 ml of solution B were
Fig. 4. Results obtained when HAc was employed in the added into a 100-ml brown volumetric flask,
modified method. (a) Absorption spectra for PEG and diluted to volume with distilled water to
10,000 with different concentrations. (b) Calibration
curve for PEG 10,000. (c) Calibration curve for PEG
obtain Dragendorff reagent (pH 1.3).
4000, 6000 and 20,000. In the preparation of the calibration curve,
HCl solution was also added to inhibit hydro-
K1 = 2.44, K2 = 4.2, K3 = 5.0 and K4 = 5.6. It lysis. To elucidate the effects of HCl concen-
seemed that the coordination of anions (e.g., tration, 5.0 ml of 20 mg L1 PEG 10,000
Cl, Ac) with Bi3+ may be important in standard solution was pipetted into 10-ml
428 Z. Jia, C. Tian / Desalination 247 (2009) 423–429
volumetric flasks. Then 3.0 ml of HCl solutions
with concentrations of 0, 0.013, 0.025, 0.038,
0.050, and 0.075 mol L1 were added. After
mixing, 1.0 ml of Dragendorff reagent was
added. Lastly the mixture was diluted to volume
with the corresponding HCl solution. The pH
values of the mixture were 2.3, 2.0, 1.82, 1.70,
1.60 and 1.46, respectively. It was found that
for 0 and 0.013 mol L1 HCl solutions, large
amount of precipitates were formed. For 0.050,
and 0.075 mol L1 HCl solutions, no precipi-
tates were formed. In the following experiments,
0.050 mol L1 HCl solution was used in the
analysis. Figure 5 shows that the calibration
curves are in good linearity. Similar linear cali-
bration curves were also obtained for PEG
4000, 6000 and 20,000. It seemed that HAc
and HCl were suitable for the inhibition of
hydrolysis, whereas H2SO4 and HNO3 were
not suitable because of the unsatisfied dissolu-
tion ability or oxidizing property.
4. Conclusions
The Dragendorff reagent method for the
measurement of PEG concentration was
modified to inhibit the hydrolysis of Bi3+. It
seemed that HAc and HCl were suitable in the
acidification. When HAc was employed, in the
preparation of Dragendorff reagent, 5.0 ml of
solution A and 5.0 ml of solution B were diluted
to 100 ml with 3.85 mol L1 HAc solution. In the
preparation of the calibration curves, 3.0 ml of
8.66 mol L1 HAc solution was added to the
mixture of PEG and Dragendorff reagent.
When HCl was employed, in the preparation
of Dragendorff reagent, 0.800 g of BiONO3 was
dissolved with 1.0 mol L1 HCl. Then, 5.0 ml of
solution A and 5.0 ml of solution B were diluted
to 100 ml with distilled water. In preparing the
calibration curves, 3.0 ml of 0.050 mol L1
HCl solution was added to the mixture of PEG
and Dragendorff reagent. The results showed
that, with the modified methods, the calibration
curves of PEG 4000, 6000, 10,000 and 20,000
were in good linearity. As the Dragendorff
reagent is widely used in the determination of
PEG concentration, the modified methods
seem to be helpful and interesting.
Acknowledgments
The authors gratefully acknowledge the
supports from the National Natural Science
Foundation of China (No. 20676016), the Youth
Foundation of Beijing Normal University (BNU,
No. 107189) and the Analytical Foundation of
BNU.
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