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International Journal of Polymer Analysis

and Characterization
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Origin of Color of Poly(N-vinyl

Pyrrolidone) Concentrated Aqueous
Solutions
a b d d a b c
Veronica Muşat , M. Popa & Natalia Gospodinova
a
Institut de Science des Matériaux de Mulhouse , Mulhouse, France
b
Université de Haute Alsace , Mulhouse, France
c
Ecole Nationale Superieure de Chimie de Mulhouse de l'Université
de Haute Alsace, Université de Haute Alsace , Mulhouse, France
d
Department of Natural and Synthetic Polymers, Faculty of
Chemical Engineering and Environmental Protection , “Gheorghe
Asachi” Technical University of Iasi , Iasi, Romania
Published online: 20 Oct 2011.

To cite this article: Veronica Muşat , M. Popa & Natalia Gospodinova (2011) Origin of Color of Poly(N-
vinyl Pyrrolidone) Concentrated Aqueous Solutions, International Journal of Polymer Analysis and
Characterization, 16:7, 442-448, DOI: 10.1080/1023666X.2011.598271

To link to this article: http://dx.doi.org/10.1080/1023666X.2011.598271

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 International Journal of Polymer Anal. Charact., 16: 442–448, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 1023-666X print=1563-5341 online
DOI: 10.1080/1023666X.2011.598271

ORIGIN OF COLOR OF POLY(N-VINYL PYRROLIDONE)

CONCENTRATED AQUEOUS SOLUTIONS

Veronica Muşat,1,2,4 M. Popa,4 and Natalia Gospodinova1,2,3

1
Institut de Science des Matériaux de Mulhouse, Mulhouse, France
2
Université de Haute Alsace, Mulhouse, France
3
Ecole Nationale Superieure de Chimie de Mulhouse de l’Université de Haute
Alsace, Université de Haute Alsace, Mulhouse, France
4
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Department of Natural and Synthetic Polymers, Faculty of Chemical

Engineering and Environmental Protection, ‘‘Gheorghe Asachi’’ Technical
University of Iasi, Iasi, Romania

A hypothesis about the origin of the well-known color of concentrated poly(N-vinyl pyrro-
lidone) aqueous solutions is proposed. We have shown that the aqueous solutions containing
strongly hydrated ions and/or polymer with higher molar mass are more colored while
the coloration of poly(N-vinyl pyrrolidone) solutions in D2O is negligible. It has been
assumed that Mie scattering light from aggregates formed by well-hydrated poly(N-vinyl
pyrrolidone) chains explains the color of its concentrated aqueous solutions.

Keywords: Mie light scattering; Poly(N-vinyl pyrrolidone) aqueous solutions

INTRODUCTION
Poly(N-vinyl pyrrolidone) (PVP) is a water-soluble polymer exhibiting excel-
lent biocompatibility and strong coordination ability, among other characteristics.
Despite important progress in understanding the structure and properties of aqueous
PVP solutions,[1–9] the origin of their obvious yellow to brown coloration has not
been elucidated up to now. We consider that knowledge of the origin of this phenom-
enon should contribute not only to better comprehension of the interactions of PVP
with water but also to extending the applications of this polymer. In the present
study, the relation between color appearance and polymer hydrophilicity is shown.
For this purpose, we have studied light absorption of the solutions of PVP with dif-
ferent molar masses in pure water and in D2O. Water-based solutions containing
ions with different hydration capacities were also tested. We have proposed that
Mie scattering light[10] occurring when the size of PVP aggregates is similar to the
wavelength of light is responsible for the color appearance. Aggregate formation

Submitted 16 May 2011; accepted 2 June 2011.

Correspondence: Natalia Gospodinova, Institut de Science des Matériaux de Mulhouse (LRC
7228), 15 rue Jean Starcky, BP 2488, 68057 Mulhouse Cedex, France. E-mail: ngospodinova@hotmail.fr,
natalia.gospodinova@uha.fr

442
 ORIGIN OF COLOR OF PVP AQUEOUS SOLUTIONS 443

is favored by the presence of highly hydrated ions. Moreover, a more intense color of
aqueous solutions of PVP of higher molar mass is found. This last fact is in agree-
ment with Zaslavsky et al.’s[1] finding of better hydrophilicity of high-molar-mass
PVPs than low-molar-mass PVPs.

EXPERIMENTAL SECTION
Materials
PVP with weight-average molar mass of 2.500 and 10.000 (Polyscience, Inc.,
USA), D2O, HCl, and HClO4 acids, NaCl, and LiCl (Sigma Aldrich) were all of
reagent quality and were used as purchased.

Solution Preparation
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PVP solutions of 20, 40, and 60 wt.% were prepared by dissolving polymer
powder at ambient temperature in pure water (Millipore), D2O, and acid or salt
aqueous solutions.

Characterization
UV-VIS absorption spectra of PVP solutions were recorded with a Lambda 35
spectrometer.

RESULTS AND DISCUSSIONS

In order to quantitatively compare color intensity of PVP concentrated solu-
tions we monitored the light absorption of PVP solutions in pure water, in D2O,
and in aqueous solutions of HCl, NaCl, LiCl, and HClO4. The choice of the medium
is governed by its hydration capacity: while in D2O the formation of hydrogen bonds
is practically absent, the presence of different ions in water alters the PVP chains’

Figure 1. Absorbance at 440 nm of PVP solutions in pure water.

 444 V. MUŞAT ET AL.
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Figure 2. Absorbance at 440 nm of 60 wt.% aqueous PVP solutions containing NaCl.

hydration. The absorbance corresponding to maximal light absorption or the spectra

in the visible range of PVP solutions in the above-mentioned media are presented in
Figures 1–5.
The PVP solutions in pure water are characterized by light absorption with a
maximum situated at about 440 nm, explaining their yellow color. As can be seen
from Figure 1, the color intensity and even its dependence on polymer concentration
is affected by the molar mass of PVP. While for the PVP with lower molar mass the
yellow color of solutions becomes more intense with increase of polymer concen-
tration, the more intense color of higher-molar-mass PVP solutions corresponds
to polymer concentration of 40 wt.%. Moreover, the 60 wt.% solution of PVP
2.500 is more strongly colored than the solution of PVP 10.000 at the same polymer
concentration.

Figure 3. Absorbance at 440 nm of 60 wt.% PVP solutions in pure water and 5 M solutions of HCl, HClO4,
and LiCl.
 ORIGIN OF COLOR OF PVP AQUEOUS SOLUTIONS 445
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Figure 4. Light absorption spectra of 60 wt.% solutions of PVP 2.500 in D2O and H2O.

We found that in 5 M NaCl solution, the yellow color of PVP 10.000 is more
intense than that in pure water (Figure 2). In contrast, under the same conditions,
polymer precipitation is observed for lower-molar-mass PVP.
Color intensity of the PVP solutions in 5 M HCl, HClO4, and LiCl is also
strongly affected by the molar mass of the polymer. Stronger coloration of the
higher-molar-mass PVP solutions in HCl and HClO4 than that in pure water solu-
tions was recorded (Figure 3). Moreover, these solutions have an orange color. In
contrast, a less pronounced yellow color of the acid or salt solutions of PVP with
lower molar mass than those in pure water was found.
A non-negligible coloration of the PVP solutions in D2O (independent of
molar mass of polymer) seems to be the most important observation of this study
(Figures 4 and 5).

Figure 5. Light absorption spectra of 60% PVP solutions of PVP 10.000 in D2O and H2O.
 446 V. MUŞAT ET AL.

Based on these results we suppose that the appearance of color in concentrated

PVP solution is a result of Mie light scattering, commonly observed in colloidal sys-
tems in which particle size is similar to the wavelength of light. Due to PVP’s
capacity to establish hydrogen bonds with water, the intercalation of water mole-
cules between polymer chains is likely to be responsible for the formation of aggre-
gates with a size similar to light wavelength. But the capacity of PVP to be hydrated
has to be dependent on the presence of ions in water. With increasing aggregate size,
the scattered light becomes red-shifted.
It is well known that the introduction of anions and cations leads to appreci-
able variation of the neutral species solubility in water.[11–13] Although the exact
mechanism of this process still remains unclear, the ability of ions to perturb
inherent water structuring seems to be responsible for the alteration of the neutral
species hydration. The ability of ions to disturb water structuring was assumed to
depend on ion hydration. This last grows with increase of charge=ionic radius ratio.
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The Hofmeister series provides a qualitative ranking of anion and cation

hydration[14]:
Strongly hydrated anions Weakly hydrated anions

SO2
2

4 > HPO4 > F > Cl > Br > I > NO3 > ClO4

NðCH3 Þþ þ þ þ þ þ þ þ
4 < NH4 < Cs < Rb < K < Na < Li < H < Ca
2þ
< Mg2þ < Al3þ

Weakly hydrated cations Strongly hydrated cations

Many studies have been devoted to the influence of the nature of ions added to
water on PVP solubility.[6–9] By means of h temperatures measurements it was shown
that the decreasing of anion or cation charge=ionic radius ratio leads to a salting out
(precipitation) of polymer.[7] As has been found recently, the cloud points of
pyrrolidone-based polymer aqueous solutions containing different anions are also
in agreement with anion position in the Hofmeister series.[9]
The influence of molar mass of PVP on the partition coefficient, defined as the
ratio of the PVP concentration in the octanol phase to that in the aqueous phase, has
been studied by. Zaslavsky et al.[1] Based on these results it was shown that PVP with
higher molar mass is more hydrophilic.
Assuming the more hydrophilic character of higher-molar-mass PVP, it is logi-
cal to suppose that it forms aggregates more easily that lower-molar-mass PVP. This
fact can explain the more intense color of aqueous solutions at 20 and 40 wt.%
(Figure 1). However, at a higher polymer concentration, the aggregate size becomes,
probably, more important than the light wavelength, which leads to a decrease of
color intensity. In contrast, for less hydrophilic PVP (molar mass 2.500) the increase
of polymer concentration seems to be responsible for continuous increase in number
of aggregates with sizes similar to the wavelength of light.
Adding NaCl to 60 wt.% solution of more hydrophilic PVP with molar mass of
10.000 leads to relatively slow variation of yellow color intensity relative to solutions
in pure water, in contrast to less hydrophilic lower-molar-mass PVP (Figure 2).
This latter solution becomes substantially less colored with increase of Cl

ion concentration, and finally in 5 M NaCl solution a salting-out is observed. Such
 ORIGIN OF COLOR OF PVP AQUEOUS SOLUTIONS 447

influence of Cl
ions is in agreement with their relatively modest hydration, which
disfavors the PVP hydration. As can be expected, less hydrophilic lower-molar-mass
polymer is more sensitive to Cl
ion presence.
Replacing the Naþ ions by more hydrated Liþ and especially by Hþ ions pro-
motes substantially the coloration of the aqueous solutions for both molar masses.
Much more intense color observed for higher-molar-mass PVP (Figure 3) is in
agreement with the above presented statements.
Finally, substantially lower coloration of concentrated PVP solution in D2O
(Figures 4 and 5) than those in water confirms our idea about the origin of the color
of aqueous PVP solutions.
Based on the above presented results we assume that the formation of aggre-
gates with sizes similar to the wavelength of light results in the Mie scattering light
effect, which is responsible for the color of aqueous PVP solutions. The aggregate
formation seems to be promoted by PVP hydration, which is more pronounced
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for higher-molar-mass polymer and in the presence of highly hydrated ions.

CONCLUSIONS
The origin of the color of PVP concentrated aqueous solutions is proposed.
The PVP chains’ hydration seems to be responsible for aggregate formation. When
their size is similar to the wavelength of light, the Mie light scattering occurs. The
hydration of PVP is influenced by molar mass of the polymer as well as by the
presence of ions in water. Increasing both the molar mass of PVP and the hydration
of ions present in aqueous solution favors aggregate formation and hence increases
the probability of color appearance.

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