Polyelectrolyte solutions

Polyelectrolyte refers to the polymer chain having

ionic charges on the repeating units

Related Los:-
Prior viewing: Single chain conformation- Ideal Chain, Overlap concentration
Future viewing: Polyelectrolyte solution properties
Course Name: Polymeric Materials
Level(UG/PG): PG

Author: Manish Gupta, MTech student, IIT Madras

Mentor: Dr. Abhijit P. Deshpande
 Learning objectives
1
 After interacting with this Learning Object, the
learner will be able to:
2
 Differentiate behaviour of polyelectrolyte and neutral
polymer in solutions.
 Explain the effect of dielectric medium and ionic strength of
3 solvent on polymer conformation.

5
 Definitions and Keywords
1
1. Polyelectrolyte: It is a polymer with ionic/charged group on its
repeating units.
2
2. Theta solvent: It is a solvent in which polymer coils act like an ideal
chain.

3. Counterion: It is an ion ( anion or cation) which moves freely when ionic

3 group of the repeating unit dissociates.

4. Dielectric constant: It is the ratio of the permittivity of a substance to

the permittivity of free space. Ionic group dissociate easily in high
dielectric constant solvent.
4

5
 Master Layout
1 This animation consists of three parts:
Part 1: Neutral polymer and polyelectrolyte
Part 2: Effect of dielectric medium
Part 3: Effect of ionic strength of the solvent
2

4
Neutral Polymer Charged polymer /
Polyelectrolyte

5
 Part 1: Step 1

1 Neutral polymer and Polyelectrolyte

Negative Anion
ball
1.1
Cation

3
Positive
ball
Neutral Polymer Charged polymer /
4 Polyelectrolyte
Poly vinyl alcohol
Polystyrene Polyacrylic acid
Polyethylene Sodium polystyrene sulfonate
Polypropylene Natural polymers like DNA, RNA
and proteins
5 Nylon and many more
 Part 1: Step 2

1 Neutral polymer and Polyelectrolyte examples

1.1 Neutral polymer Polyelectrolyte
Anion is SO-3
Figure 2
2 Figure 1

Cation is Na+

3
Polystyrene Sodium polystyrene sulfonate
4
No ionic group Ionic group SO-3 Na+

Image sources:
5 pslc.ws/macrog/styrene.html
http://en.wikipedia.org/wiki/Sodium_polystyrene_sulfonate
 Part 1: Step 3

1 Neutral polymer and Polyelectrolyte

1.1
Anion
Cation

3
Neutral Polymer Charged polymer /
4 Polyelectrolyte
Poly vinyl alcohol
Polystyrene Polyacrylic acid
Polyethylene Sodium polystyrene sulfonate
Polypropylene Natural polymers like DNA, RNA
and protein
5 Nylon and many more
 Part 1: step 1,2 and 3:
1
Action Description of the action
As shown in 1. Matter of slide 5 should appear as
animation follows:
2. Red curve is to be shown initially
followed by ‘neutral polymer’ caption.
3. Then green curve should appear .
2 4. All the positive and negative balls
should appear simultaneously on the
green curve and as a legend
5. ‘Charged polymer/polyelectrolyte’
caption should appear finally.
3
6. For slide no 6:
7. Heading ( in red color) ‘Neutral polymer’
should appear first followed by Figure 1
and then caption ( polystyrene) should
appear. Finally ‘ No ionic group’ should
appear.
8. Heading ( in red color) ‘Polyelectrolyte’
should appear first followed by Figure 2
and then caption (sodium polystyrene
4 sulfonate) should appear. Finally ‘ionic
group SO-3 Na+ ’ should appear.
9. Then negative ball and positive ball
should appear with caption.
10. Then slide no 7 should come as it is
without animation. Entire content of the
slide should come up together.
5
Audio Narration
1. Let us observe the difference
between neutral polymer and
polyelectrolyte
2. Neutral polymer is composed of
repeating units having no charge
3.
or ionizable group on it.
On the other hand, polyelectrolyte
or charged polymer has ionizable
group on the repeating units.
4. To explain you the difference
between neutral and charge
polymer in a better way, lets us
take the case of neutral
polystyrene and charged
polystyrene as an example.
5. In neutral polystyrene which has
no ionic group attached to the
monomer where as sulfonated
sodium polystyrene sulfonate has
sodium sulfonic salt as ionic group
on the repeating units.
6. This ionic group has two parts,
that is anion as sulfonate ion and
cation as sodium ion which is also
called counterion.
 Part 1: Step 4

1 Conformations of polymer in dilute solution

Neutral polymer
1.1 in Conformation of neutral
poor solvent polymer chain in solvent
depends upon solvent-
polymer interactions.

2 Monomer-monomer interaction > solvent-polymer interaction

3 Ro
Ro ~ bN0.33

Ro is the end to end

distance of a polymer
chain
4 In poor solvent, solvent-
polymer interaction is very low b is the size of the
which results in collapse of monomer
chain molecule as shown
above. N is the number of
monomer in a chain
5
 Part 1: step 4
Action Description of the action Audio Narration
1 As shown in 1. All the figures should appear sequentially. 1. Now, let us discuss the
animation 2. Red lines/curves, picture as a whole conformation of both neutral
should wiggle. polymer and polyelectrolyte in
dilute solution regime in different
types of solvents. In dilute
solution, polymers exist as an
individual chain.
2 2. Conformation of polymer chain in
solvent depends upon short ranged
interaction like solvent–polymer
interaction, monomer-monomer
interaction, excluded volume

3
interaction and long ranged
electrostatic interaction, in case
of polyelectrolyte.
3. Consider neutral polymer solution
in poor solvent. Polymer chain
collapse into dense coils due to
strong monomer-monomer
interaction than solvent-polymer
interaction. As a result end to end
4 distance varies as N raise to 0.33.

5
 Part 1: Step 5

1 Conformations of polymer in dilute solution

1.1
Neutral polymers in theta solvent

Monomer-monomer interaction = solvent-polymer interaction

2
Ro ~ bN0.5

3 Ro
Ro is the end to end
distance of a polymer
chain

b is the size of the

monomer
4 N is the number of
In theta solvent, polymer chain
has random walk conformation monomer in a chain
which in turn is a consequence of
zero excluded volume effect. In
other words, polymer acts like
5 ideal chain.
 Part 1, Step 5:
Action Description of the action Audio Narration
1 As shown in 1. All the figures should appear sequentially. 1. Whereas in theta solvent, end to
animation 2. Red lines/curves, picture as a whole end distance of the same polymer
should wiggle. chain is little larger than that in
poor solvent. This is because
monomer–monomer interaction is
just equal to solvent-polymer
interaction. In fact, polymer chain
2 behaves like ideal chain because
chain takes random walk
conformation due to zero
excluded volume effect.

3
4

5
 Part 1: Step 6

1 Conformations of polymer in dilute solution

Neutral polymer in good solvent
1.1

Monomer-monomer interaction > solvent-polymer interaction

Ro ~ bN0.588

3 Ro
Ro is the end to end
distance of a polymer
chain

b is the size of the

4 monomer
In good solvent, polymer chain
has self avoiding walk N is the number of
conformation which in turn due to monomer in a chain
excluded volume effect.

5
 Part 1: Step 7

1 Conformations
Neutral polymers in
of polymer in dilute solution
1.1

Ro ~ bN0.33
2 Ro
Poor solvent
Increasing
size

3 Ro
Ro ~ bN0.5

Theta solvent
4
Ro ~ bN0.588

5 Good solvent
Ro
 Part 1, Step 6 and 7:
Action Description of the action Audio Narration
1 As shown in 1. All the figures should appear sequentially. 1. In good solvent, excluded volume
animation 2. All the red lines/curves, picture as a keep the chain apart which make
whole should wiggle. them to adopt self avoiding walk
conformation. Therefore, end to
end distance of the polymer chain
is higher compare to that in poor
and theta solvent.
2 2. In conclusion, end to end distance
of the chain is the smallest in poor
solvent where as it is the largest
in good solvent.

3
4

5
 Part 1: Step 8

1 Conformations of polymer in dilute solution

1.1
Dilute polyelectrolyte solution with no
salt
Counterions Polyanion
2

3
4
Ro ~ bN

Polyelectrolyte, in dilute solution with no added salt, conformation

becomes rod like due to the electrostatic repulsion between
5 charges along the backbone.
 Part 1,Step 8:

Action Description of the action Audio Narration

1 As shown in 1. All the figures should appear sequentially. 1. Conformation of polyelectrolyte
animation 2. Green curve along with negative and chain in dilute solution with no
positive ball should wiggle as a whole. added salt is rod like. This is
because of the dissociation of the
ionic groups on the monomers,
which leads to charges on the
backbone and results in
2 electrostatic repulsion. This
electrostatic interaction stretches
the chain apart.

3
4

5
 Master Layout
1 This animation consists of three parts:
Part 1: Neutral polymer and polyelectrolyte
Part 2: Effect of dielectric medium
Part 3: Effect of ionic strength of the solvent
2

5
Part 2: Step 1

1 Effect of dielectric medium

Electrostatic interactions
between charges is inversely
proportional to dielectric
constant of the solvent
2
Low dielectric medium

High dielectric medium

3
Lower the dielectric medium is,
higher the counterions
condensation takes place.
4

5 Very high dielectric medium

 Part 2,Step 1:

Action Description of the action Audio Narration

1 As shown in 1. Green curve along with negative and 1. Conformation of polyelectrolyte
animation positive ball should wiggle as a whole. chain in dilute solution depends
on factors like dielectric
constant and ionic strength of the
solvent. Let us first discuss the
effect of dielectric medium. We
know from the fundamentals of
2 physics, that any dielectric
medium between two charges,
decreases the electrostatic force
between them.
2. Therefore, conformation of

3
polyelectrolyte depends strongly
on the dielectric constant of the
solvent.
3. In low dielectric medium solutions
not all ionic groups dissociates. As
a result, there is less charge on
the backbone which results in
conformation same as that of
neutral polymer.
4 4. As dielectric constant increases,
electrostatic attraction between
cation and anion of ionic groups
decreases leading to more and
more negative charge on the
backbone which leads to repulsion
along the backbone. As a result,
5 chains stretches themselves and
conformation become rod like.
 Interactivity option 1:Overall view
1

5 Increasing dielectric constant of solvent

Interactivity option 1 : Step 1

Figure 1 a

Increasing dielectric constant of solvent

Interactivity option 1 : Step 2

Figure 1 b

Increasing dielectric constant of solvent

Interactivity option 1 : Step 3

Figure 1 c

Increasing dielectric constant of solvent

Interactivity Instruction to Boundary Instructions for the animator Results and Output
type the learner limits

As 1. As green controller
Drag By dragging the shown in on the horizontal bar
along the green button over figure is dragged, figure
red the dielectric 1a, 1b and 1c should
bar(whic constant range appear. The
h acts bar, you can see appearance should
like a how the be continuous with
dielectric polyelectrolyte the movement of
constant conformation green button.
controller changes with
) change in 2. Also each figure 1a,
dielectric 1b, and 1c should
constant of the wiggle along with
solvent. negative and positive
ball
 Master Layout
1 This animation consists of three parts:
Part 1: Neutral polymer and polyelectrolyte
Part 2: Effect of dielectric medium
Part 3: Effect of ionic strength of the solvent
2

4
After adding a
pinch of NaCl
salt…..

5
Part 3: Step 1

1 Effect of ionic strength of the

solvent Add a pinch of
Na+
NaCl salt in
polymer solution Cl-
NaCl beaker….

3
4 Aqueous
polyelectrolyte
solution Conformation of polyelectrolyte in aqueous solution

5
Part 3: Step 2

1 Effect of ionic strength of the

solvent Then.....
Na+
Cl-
2

3
4 Conformation of polyelectrolyte in aqueous solution

5
Part 3: Step 3

1 Effect of dielectric medium

After adding a pinch of
salt polymer
conformation has Na+
changed…Why…??
Cl-
2

3
4 Now what if, you add
some more amount of
salt…??How the
conformation will
change..??

5
Part 3: Step 4

1 Effect of ionic strength of the

solvent
Na+
Cl-
2

3
4

5
 Part 1,Step 8:

Action Description of the action Audio Narration

1 As shown in 1. Slide no 27, 28, 29 and 30 should come 1. Let us discuss the effect of ionic
animation one after another. strength of the solvent on the
polyelectrolyte conformation. We
shall answer the question like
what would happen to the
conformation of polyelectrolyte
when you keep on adding salt in
2 2.
polyelectrolyte solutions.
As you keep adding salt,
Conformation of polyelectrolyte
changes from rod like to that of
neutral polymer. That is

3
polyelectrolyte become less stiff.
3. Say for example if sodium chloride
is added in to the polymer
solution, sodium chloride will
dissociate into cation and anion.
4. As a result, sodium cation would
sit on Polyanion backbone to
neutralize the backbone and
corresponding chloride anion will
4 react with counterion ions present
in the solvent.
5. This leads to screening of charges
which in turn decreases
electrostatic repulsion along the
backbone. This will eventually
caused polyelectrolyte chain to
5 coil up and thus take the
conformation of neutral polymer.
APPENDIX 1
Questionnaire
1. What is polyelectrolyte ?
a) Polymer which has charges on its repeating units

b) Polymer with larger end to end distance

c) Polymer which behave like ideal chain

2. Which of the following system/polymer solution will show rod like conformation ?

a) Polystyrene sulfonate dilute solution

b) Sodium polystyrene sulfonate dilute solution

3. Suppose, you are given two polyelectrolyte solutions in beaker (A and B) with the same
polyelectrolyte but different solvents. Beaker A and beaker B has solvent of dielectric
constant 80 and 50 respectively. In which beaker polymer conformation will be more stiff or
rod like ?

a) Beaker A

b) Beaker B
C) Both beaker
d) None of the these

4. In case of polyelectrolyte solution with no added salt, end to end distance of the chain is small
compare to that of polyelectrolyte solution with added salt.

True or False
APPENDIX 1
Answers
1. What is polyelectrolyte ?
a) Polymer which has charges on its repeating units

2. Which of the following system/polymer solution will show rod like conformation ?
a) Polystyrene sulfonate dilute solution

3. Suppose, you are given two polyelectrolyte solutions in beaker (A and B) with the same
polyelectrolyte but different solvents. Beaker A and beaker B has solvent of dielectric
constant 80 and 50 respectively. In which beaker polymer conformation will be more stiff or
rod like ?

a) Beaker A

4. In case of polyelectrolyte solution with no added salt, end to end distance of the chain is small
compare to that of polyelectrolyte solution with added salt.

False
APPENDIX 2

Links for further reading

• Reference websites:
• pslc.ws/macrog/styrene.html
• http://en.wikipedia.org/wiki/Sodium_polystyrene_
sulfonate

• Research papers:

• Colby, R.H.; Rheological Acta, 2010, 49,

425-442
APPENDIX 3
Summary

1. Polyelectrolyte is a polymer having ionic groups on its

repeating units where as in neutral polymer there is no
ionic groups.
2. Conformation of neutral polymer in its dilute solution
depends on the type of the solvent depending upon
monomer-monomer interaction and solvent-polymer
interaction.
3. Polyelectrolyte takes the conformation of rod like when
salt is not added in the solution.
4. As dielectric constant of the solvent increases,
polyelectrolyte becomes more stiff and stretches
themselves due to more dissociation of ionic groups.
5. As salt concentration increases, polyelectrolyte chain
behaves like neutral polymer due to screening of
charges.