J. Chem. & Cheml. Sci. Vol.

1 (4), 267-275 (2011)

Evaluation of Cationic and Anionic Polyelectrolytes as a

Coagulants Aid for Water Quality Improvement
J. K. KAPOOR1, SHAGUFTA JABIN2, H. S. BHATIA3 and NEHA KAPOOR1
1

Department of Chemistry, NIT, Kurukshetra. India

Department of Chemistry, Lingayas University, Faridabad. India
3
Department of Civil Engg., DTU, New Delhi. India
ABSTRACT
The water pollution control is one of the major thrust areas of
scientific research. The suspended particles which do not undergo
biological degradation need special attention. During the last few
decades several techniques have been used to remove the
suspension; whereas the use of Polyelectrolytes along with
inorganic coagulants is one of the most promising techniques.
Here, the use of polymers along with inorganic coagulants is
reviewed with emphasis on the type of polyelectrolytes i.e.
cationic and anionic, molecular mass and charge density,
mechanism of coagulation and flocculation and the kinetics aspect
of polymers.
Keywords: Polyelectrolytes, Water treatment, Coagulation and
Flocculation.

INTRODUCTION
The impurities present in
water are in the form of dissolved organic
matter1 or suspended material such as clays,
sand, silt, etc2,3. Dissolved organic
compounds (DOC) are those compounds
which will pass through a membrane having
pores of 0.45m size. DOC poses a problem
for the water treatment industry for a
number of reasons. Apart from the aesthetic
problems of colour, taste and odour, its
presence poses a health hazard4,5. It can also
block the pores of activated carbon filters,
hindering adsorption of trace organic

contaminants such as taste and odour.

Suspended matters are an important
component of all natural water. Particles can
range from 10m or more down to
submicron colloidal size. Such materials
need to be removed from water because it
supplies a surface on which microbes can be
adsorbed and protected from disinfection
chemicals by a coating of slime.
These impurities cannot be removed
alone by inorganic coagulants. Because most
essential drawbacks involve by using
inorganic coagulants are low efficiency, high
level of water mineralization and large
amount of sludge. So, a novel technology

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J. K. Kapoor, et al., J. Chem. & Cheml. Sci. Vol.1 (4), 267-275 (2011)

has been developed for the removal of

turbidity from water with the addition of
polyelectrolytes6,7. The polyelectrolytes in
combination with inorganic coagulants have
been utilized for coagulation and
flocculation methods for water purification
for at least four decades8. The above
combined complexes will be effective and
promising for the purification of water and
waste water. The polyelectrolytes used in
water treatment are water soluble and mainly
synthetic in nature9, although few natural
polyelectrolytes may be of interest. The
advantages over the usage of polyelectrolytes are lower coagulation dose
requirement, a small volume of sludge, a
smaller increase in the ionic load of treated
water and cost saving up to 25% to 30%10-13.
The aim of this paper is to review
the practicalities of polymers used for water
treatment with particular attention to the
polymer characteristics, types of polyelectrolytes used in water treatment,
mechanism of action and kinetic aspects.
Detail account of kinetic aspects has been
given in the appendix at the end.
Type of Polyelectrolytes Vs Polymer
Chain and Charge Density
The most important characteristics
of polymeric flocculants are molecular mass
and charge density. Molecular mass values
range from a few thousands up to tens of
millions. Conventionally polymers are
regarded as having low, medium and high
molecular mass. The range of molecular
mass are 105,105-106 and >106 for low,
medium and high molecular mass polymers
respectively. All polymers used as
flocculants in water treatment must be water

soluble. In aqueous solution, polymers adopt

a random coil configuration (Fig.1).
For very high molecular weight
polymers, the size of coil is typically in the
order of hundreds nanometer. If polymer
chain is fully stretched, then end to end
distance r

Fig.1 : A polymer chain in a random coil

configuration the end to end distance is r.

can be up to 10m or more. This is generally

unlikely arrangement. The random coil is the
most common configuration. The extent of
random coil depends upon the interaction
between polymer segments. If there is
appreciable repulsion between segments
then the coil expands. The most obvious
examples are those polyelectrolytes where
the segments are charged. In this case, the
polymer coil can be significantly expanded
and there can be important ionic strength
effects. At high ionic strength, the repulsion
between the charged segments is screened
by ions in solution and so the coil expansion
is not so great. As the salt concentration is
reduced, repulsion becomes more significant
and polymer coil adopt more expanded
configuration which can be seen in (Fig-2).

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J. K. Kapoor, et al., J. Chem. & Cheml. Sci. Vol.1 (4), 267-275 (2011)

269

or high if the mol % of ionic groups are

10%-25%, 25%-50% and >50% respectively.
According to cationic and anionic charge
density, they are divided into cationic and
anionic polyelectrolytes.
Cationic Polyelectrolytes:

Fig.2 : Showing the expansion of a polyelectrolytes

chain with decrease of ionic strenth.

In case of polyelectrolytes, charge

density is also a very significant parameter.
Charge density can be expressed in terms of
mole percent of charge groups or as meq/g.
For example, we can calculate the charge
density from the molecular mass of
monomer units. In case of 100% cationic
polyelectrolytes such as poly allyl dimethyl
ammonium chloride, charge density follows
directly from the molecular wt of monomer
units (162), since one gram of polymer has
1/162 equivalent of charge. Hence, the
charge density is 6.2meq/g. Broadly charge
density values are regarded as low, medium

They are having cationic charge

density, and satisfy the cationic demand of
the negatively charged suspended particles
and initiate coagulation and flocculation
process. There are many variety of cationic
polymers available14,15. Usually they possess
quaternary ammonium groups that have a
positive charge and termed as a strong
positive electrolyte polymers16. Some of the
synthetic polyelectrolytes are polydiallyl
dimethyl ammonium chloride (PDADMAC),
Epichlorohydrine polymers and cationic
poly-acrilamides. PDADMAC is water
soluble and low to medium molecular mass
polymers whereas Epichlorohydrine polymers
form polymers with ammonia and primary
and secondary amines, in which the active
sites are quarternary ammonium group.
Cationic polyacrilamide is generally used in
water industry17,18. The cation content in the
cationic PAMS can be in the range of
10-80%.

Table 1: Formulation and charge density of some cationic polyelectrolytes

Mol. formula
C8H16NCl
C5H12ONCl
C8H16O2NCl
(C8H16O2NCl)0.5(C3H5ON)0.5
(C8H16O2NCl)0.5(C3H5ON)0.5
Chitosan

Charge density(mol%)
100
100
100
50
25
100

Charge density (meq/g)

6.2
7.3
5.2
3.8
2.5
5.2

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J. K. Kapoor, et al., J. Chem. & Cheml. Sci. Vol.1 (4), 267-275 (2011)

There are several naturally occurring

polymers that have inherent cationic
properties or modified to yield cationic
properties19, 20. The most prominent ones are
chitosan and starch. Starch is a polymer
composed of -D glucose units and can be
converted to cationic derivatives. Table-1
shows the formulation and charge density of
some of the cationic polyelectrolytes.
Anionic Polyelectrolytes
They are generally differentiated by
a functional group21. They are generally
manufactured by co polymerization of
acrilamide and acrylic acid. The most
commonly used anionic polyelectrolytes
contain weak acidic carboxyl groups .High

molecular weight carboxylic polymers

derived from PAM are extensively
employed as flocculating agents in the water
and other process industries.
Some
natural
anionic
polyelectrolytes are also available such as many
sulphated polysaccharides. The examples of
sulphated polysaccharides are heparin and
dextran sulphate. But as per literature
survey, their application is only medical
based. The natural polyelectrolyte which is
under discussion among the scientists for
water quality improvement is tannin 22.Some
of the important anionic polyelectrolytes are
listed in Table-2 in terms of charge density
as mol% and calculated on a theoretical
basis in meq/g of polymer.

Table 2: Formulation and charge density of some of the anionic polyelectrolytes

Mol. formula
C3H3O2Na
(C3H3O2Na)0.75(C3H5ON)0.25
(C3H3O2Na)0.50(C3H5ON)0.50
(C3H3O2Na)0.25(C3H5ON)0.75
(C3H3O2Na)0.1(C3H5ON)0.9

Charge Density (mol%)

100
75
50
25
10

Polymer bridging and Charge

neutralization
Mechanism of flocculation of
particles by polyelectrolytes can be
described under
two headings: Polymer
bridging and Charge neutralization which
includes electrostatic patch effects23. These
two effects are crucially important for
mechanism of flocculation.
Polymer adsorption: If there is some
affinity between polymer segment and a

Charge density(meq/g)
10.6
8.5
6.1
3.3
1.4

particle surface, then adsorption of polymer

chain may occur. Polyelectrolytes with a
charge opposite to that of surface adsorb
oppositely charged ionic groups. For
example, cationic polyelectrolytes adsorb
strongly on negative surface, whereas
anionic polyelectrolytes can adsorb on
negatively
charged
surfaces
despite
electrostatic repulsion. This can only occur
when there is sufficient concentration of
divalent metal ions. For example, Ca2+ can
act as bridge between anionic groups on the
polymer and negative sites on the surface.

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But in the absence of divalent cations, no

flocculation occurs, even at high ionic
strength.
Polymer bridging
An essential requirement for
bridging flocculation is that there should be
sufficient unoccupied surface on the particle
for attachment of segments of polymer
chains adsorbed on other particles24. The
adsorbed amount should not be too high,
otherwise the particle surfaces will become
so highly covered that there will be
insufficient adsorption sites available25.
Polymer bridging can be seen in figure-1
(a & b). If adsorbed amount is too low then,
polymer bridging will not be formed. This
leads to an idea of optimum dosage for
bridging flocculation. Typical optimum
dosages in practical systems are in the order
of 1mg polymer / g of suspended solids. It is
generally found that most effective polymers
for bridging are linear chain of high
molecular weight. Charge density has large
influence on bridging effectiveness. Very
strong flocs are formed by bridging but
broken flocs may not easily regrow.26

271

are the most effective flocculants.

Electrostatic interaction gives strong
adsorption in this system27. It has been found
that polyelectrolytes of high charge density
are more effective because for a given
dosages; they deliver more charges to the
particle surface. Since high charge density
polymers tend to adsorb in a rather flat
configuration and there is little opportunity
for bridging interactions. When high charge
density polyelectrolytes adsorb on negative
surfaces with low density of charged sites,
then electrostatic patch mechanism will
develop which can be seen in figure- 4.This
model was
independently suggested by
Gregory 28 in 1973.

Figure 4 : Electrostatic patch model for flocculation.

Figure 3 : (a) Bridging flocculation

(b) Destabilization of adsorbed chain

Charge neutralization
In most of the cases, suspended
particles are negatively charged thats why it
has been found that cationic polyelectrolytes

There is electrostatic attraction

between positive patches and negative areas,
which can give particle attachment and it
leads to flocculation29. Flocculation formed
by this way is not as strong as by bridging.
Re-flocculation after flocculation breakage
occurs more readily in electrostatic patch
than in polymer bridging. The summary of
mechanism of polyelectrolytes in terms of
different parameters has been tabulated in
Tab-3.

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J. K. Kapoor, et al., J. Chem. & Cheml. Sci. Vol.1 (4), 267-275 (2011)
Table-3: The summary of mechanism of polyelectrolytes

Serial
no
1.

Parameters
Molecular.
mass
Polyelectrolytes

2.

Charge density

3.

Bridging
of

Higher the mol. mass, more

effective is the bridging.

Electrostatic patch
mechanism
Mol. mass does not have
much effect

Polyelectrolytes of similar
charge to particle surface

Bridging more effective at

higher charge density due
to larger loop.
Destabilization by bridging
mechanism

Higher the charge density,

more effective will be
destabilization
Inoperative

4.

Polyelectrolytes of opposite
charge to particle surface

Destabilization by bridging
mechanism

5.

Nonionic polyelectrolytes

Destabilization by bridging
mechanism

6.

Ampholytic
Polyelectrolytes

Destabilization by bridging
mechanism possible

Destabilization by
electrostatic patch
mechanism possible
Destabilization by
electrostatic patch
mechanism inoperative
Destabilization by
electrostatic mechanism
possible

CONCLUSION AND DISCUSSION

There are various methods for
removing turbidity. Some stabilized chemical
coagulants were tried earlier under different
conditions for turbidity removal. But results
have shown that they are partially successful
in removing turbidity. So the present study
explores the advantages of use of
polyelectrolytes in water treatment. It is
being found that polyelectrolyte can do this
job in excellent way if proportioning is done
in optimum manner.
Work so far has revealed that high
charge density polymers with least polar
structure are most effective in removing
dissolved organic matter. Cationic charged

polyelectrolytes seems to be more effective

for the removal of suspended particles. In
fact cationic charged polyelectrolytes
facilitate
the
destabilization
and
agglomeration of suspended colloids by
neutralizing their surface charges, whereas if
polyelectrolytes are having similar charges
to the particle surface then destabilization
generally occurs by bridging mechanism. In
summary, it can be said about the bridging
that high molecular weight and linear
polymers are most effective and only a
limited adsorbed amount of polymer is
needed in bridging lest excess level can give
restabilization. The ionic strength also plays
an important part and presence of some
divalent metal ions can be very important for

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J. K. Kapoor, et al., J. Chem. & Cheml. Sci. Vol.1 (4), 267-275 (2011)

bridging, although it does not have much

effect in electrostatic patch mechanism.
Work so far revealed that with many
advantages that polyelectrolytes have in
water
treatment,
their
usage
is
recommended, although more quantitative
research is necessary on this aspect.
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APPENDIX
Turbidity removal mechanism:/ Kinetic
aspects:
When polyelectrolytes are added in
the suspended particles, several processes
are initiated which have been discussed
below.
Mixing: It is an essential process in which
polymer is distributed evenly through out the
suspension. The process of mixing is
generally achieved rapidly otherwise excess
concentration will give non uniform
adsorption and some particles may re estabilize as a result of adsorbing excess
amount of polyelectrolytes. Poor mixing is
generally responsible for residual haze in
water after polymer flocculation and
sedimentation. For proper mixing, a high
degree of turbulence is desired, although
some scission of polymer chains may occur
under this condition. The rapid mixing
generally has major effects on the
flocculation process. Mixing effect is
generally more important for more
concentrated suspension.
Adsorption: The attachment of polymer
chain to particles happens at a rate which
generally depends upon the concentration. If
particle concentration is increased, the

optimum polymer dosage will also increase

proportionally. For low molecular weight
polymers adsorption depend mainly on
diffusion, but with high molecular weight
flocculants shear induced collisions between
polymer molecules and particles become
more important. The rate of polymer
adsorption depends upon mixing condition.
For low turbidity waters, the time required
for adsorption of polymers can be of the
order of minutes, whereas for high turbidity
water, adsorption time can be less than 1
second.
Rearrangement of adsorbed chain
A polymer chain adsorbed on a
particle is needed to be arranged. A polymer
chain reaches its equilibrium adsorbed
configuration with characteristic distribution
of loops, trains and tails. The time required
for rearrangement of adsorbed chains
depends upon a number of factors, although
a little information is available in the
literature about rearrangement of adsorbed
chain. For high molecular weight polymers,
time of several seconds may be needed,
during which time adsorbed polymer has a
more extended configuration than in the
final equilibrium arrangement; thats why it
readily forms bridging contacts. Pelssers29 et
al developed a kinetic model in term of
active and inactive adsorbed polymer chains,
in which active polymer chain is having
extended configuration whereas inactive one
is flattened on the surface. If low molecular
weight polymer is pre-adsorbed on particles
to give around 50% coverage, then
flocculation by a high molecular weight
polymer is much improved. This may be
possible because a second polymer adopts a

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J. K. Kapoor, et al., J. Chem. & Cheml. Sci. Vol.1 (4), 267-275 (2011)

more extended adsorbed configuration, since

the pre-adsorbed configuration polymer
makes many surface sites unavailable to the
second polymer 30.
Flocculation
When particles have acquired
enough adsorbed polymer to become
destabilized then collision results in
attachment, either by bridging or by
electrostatic mechanism. For high solid
concentration, flocculation rates may
become very high. All flocculation process
is carried out under some form of applied
shear in the stirred tank or in the flow
through reactor. In case of high mol weight
polymers, adsorption time may be
considerably longer than particle collision

275

times, so that adsorption may be the rate

determining steps.
The particle collision time relative
to the re-conformation time also needs to be
considered. If the former is quite short then
particles are likely to collide before the
adsorbed polymer has achieved its
equilibrium configuration and so is more
extended from the particle surface. It
generally occurs in more concentrated
suspension. Bridging interaction most likely
gives the possibility of non-equilibrium
flocculation.
In
case
of
cationic
polyelectrolytes and negative particles,
bridging may occur in non-equilibrium
phase but electrostatic patch flocculation
would be more likely when the adsorbed
chains are in a flatter configuration.

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