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DESALINATION

Desalination 247 (2009) 423429

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
Quantitative determination of polyethylene
glycol (PEG) is usually needed in membrane
technology, water environment [1] and chromatography. For example, in the preparation of
ultrafiltration membranes, determination of
molecular weight cut-off (MWCO) is usually
indispensable [2, 3]. PEG or protein with different molecular weight is often employed as the
standards [4, 5]. By measuring the concentrations
of the standards in the permeate and the feed, the
retention coefficient and MWCO of membranes
are obtained. As PEG is cheap and stable, it is
*Corresponding author.

widely employed especially in the separation of


linear polymers because the retention coefficient
of PEG is similar to that of the linear polymers.
To determine the PEG concentration, the Dragendorff reagent, widely used in the measurement
of alkaloid [6], is often employed. The reaction of
Dragendorff reagent with PEG generates an
orange-red complex, which is easily detected at
510 nm with UV-vis spectrophotometer [7, 8].
In the preparation of the calibration curve, PEG
standard solutions are mixed with the Dragendorff
reagent, and then the absorbance is measured with
UV-vis spectrophotometer. The absorbance of the
permeate and the feed solution are measured with
the same procedure and the concentrations are

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


doi:10.1016/j.desal.2008.09.004

424

Z. Jia, C. Tian / Desalination 247 (2009) 423429

read from the calibration curve. Nevertheless, in


the above procedures, Dragendorff reagent hydrolyzes seriously, resulting in nonlinear calibration
curve, poor accuracy and unsatisfied reproducibility. In this paper, the effects of acids and their concentrations 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 distilled 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 solution 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 distilled water to obtain the Dragendorff reagent.
2.2. Preparation of HAcNaAc 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 concentrations of 0, 5, 10, 15, 20, 25 and 30 mg L1
were added into 10-ml volumetric flasks. Then
1.0 ml of HAcNaAc buffer solution and 1.0 ml
of the Dragendorff reagent were added, respectively. Lastly, the mixed solution was diluted to
volume with distilled water. After 15 min, the
absorbance was determined with UV-vis spectrophotometer 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 goldenyellow precipitates settled down after a certain
time. These phenomena were attributed to the

Z. Jia, C. Tian / Desalination 247 (2009) 423429

1.4

a)

30 mg L1
25 mg L1
20 mg L1
15 mg L1
0 mg L1
10 mg L1
5 mg L1

Absorbance

Absorbance

1.2
1
A+B+HAc
Solution A

425

1.0
0.8
0.6
0.4

Solution B

0.2

0
300

400
500
Wavelength (nm)

600

300

Fig. 1. Absorption spectra of solution A, solution B and


the mixture.

400

500 600
700
Wavelength (nm)

800

900

0.75
b)

hydrolysis of BiI4 and the formation of black


BiI3 and orange BiOI precipitates [12].

BiI
4 ! BiI3 # I

Absorbance

0.70
0.65
0.60
0.55
0.50
0.45

BiI3 H2 O ! BiOI # 2HI


In the preparation of calibration curve, 5.0 ml
of standard PEG 10,000 solutions with concentrations of 0, 5, 10, 15, 20, 25 and 30 mg L1
were added into 10-ml volumetric flasks. Then
1.0 ml of HAcNaAc 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
PEGBiI4 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.

10
15
20
25
Concentration (mg L1)

30

Fig. 2. Results obtained according to the procedures in


the literature. (a) Absorption spectra of PEG 10,000 solutions 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 dissociation 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 precipitates were formed. When the mixture was diluted
with water to obtain the Dragendorff reagent, the

Z. Jia, C. Tian / Desalination 247 (2009) 423429

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 procedures, 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 corresponding 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 concentration of HAc solutions, the transparency of
the mixture increased, and the absorbance of
BiI4 at 465 nm and that of PEGBiI4 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.

HOCH2 CH2 On H H
H

! HOCH2 CH2 O n H
H

HOCH2 CH2 O n H Bil


4
H

! HOCH2 CH2 O n HBil


4

Absorbance

426

16.44 mol L1
12.98 mol L1
8.66 mol L1
6.06 mol L1
4.33 mol L1
2.16 mol L1
0 mol L1

400

500
Wavelength (nm)

600

Fig. 3. Effects of HAc concentration on the absorbance


spectra.

In the following experiments, in the preparation 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 apparent precipitation phenomena occurring in all
the samples. The samples with PEG concentrations 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 absorbanceconcentration
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 Dragendorff reagent, H2SO4 and HCl were also tried
in dissolving BiONO3 powder. It was found that
BiONO3 was almost insoluble in dilute H2SO4,
but soluble in HCl solutions with concentrations
equal to or larger than 1.0 mol L1. The stepwise
formation constants of Bi3+Cl complexes are

Z. Jia, C. Tian / Desalination 247 (2009) 423429


1.0

30 mg L
1
25 mg L
20 mg L1
15 mg L1
10 mg L1
5 mg L1
1
0 mg L

0.5

0.0
400

0.4

0.2

0.0
500
Wavelength (nm)

500

600

b)

0.4

0.4
Absorbance

Absorbance

600
Wavelength (nm)

b)

0.2

0.0
0

10

15

20

25

Concentration (mg L

10
15
20
25
Concentration (mg L1)

30

Fig. 5. Results obtained when HCl was employed in the


modified method. (a) Absorption spectra for PEG
10,000. (b) Calibration curve for PEG 10,000.

PEG 4000
PEG 6000
PEG 20000

c)

0.2

0.0

30

0.6

Absorbance

30 mg L1
25 mg L 1
20 mg L1
10 mg L1
5 mg L1

a)

Absorbance

Absorbance

0.6

a)

427

0.4

0.2

0.0
0

10

15

20

25

Concentration (mg L

30

35

Fig. 4. Results obtained when HAc was employed in the


modified method. (a) Absorption spectra for PEG
10,000 with different concentrations. (b) Calibration
curve for PEG 10,000. (c) Calibration curve for PEG
4000, 6000 and 20,000.

K1 = 2.44, K2 = 4.2, K3 = 5.0 and K4 = 5.6. It


seemed that the coordination of anions (e.g.,
Cl, Ac) with Bi3+ may be important in

dissolving BiONO3. In the preparation of


Dragendorff reagent, 0.800 g of BiONO3 was
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
a 50-ml brown volumetric flask and dissolved
with water to obtain solution B. Lastly, 5.0 ml
of solution A and 5.0 ml of solution B were
added into a 100-ml brown volumetric flask,
and diluted to volume with distilled water to
obtain Dragendorff reagent (pH 1.3).
In the preparation of the calibration curve,
HCl solution was also added to inhibit hydrolysis. To elucidate the effects of HCl concentration, 5.0 ml of 20 mg L1 PEG 10,000
standard solution was pipetted into 10-ml

428

Z. Jia, C. Tian / Desalination 247 (2009) 423429

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 precipitates 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 calibration 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 dissolution 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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