11.

Polyelectrolytes
11.1 Definitions
Polyelectrolyte = macromolecules build up from monomers with groups which
can be ionized; in polar solvents large number of charged functional groups and
counter ions

Charges along the polymer chain and oppositely charged counter ions in the
solution Coulomb interaction
Strong polyelectrolyte = mostly dissociated if dissolved and the charge
distribution along the chain is basically independent from the pH value of the
solution
Weak polyelectrolyte = charge distribution along the chain is determined by the
pH value of the solution; it has a dissociation constant (pKa or pKb) in the range
of ~2 to ~10, meaning that it will be partially dissociated at intermediate pH
Anionic, cationic
polyelectrolyte

polyelectrolyte

positively,

negatively

charged

Polyampholyte = polyelectrolyte
with both, negatively and
positively charged functional
groups in the chain

Wang et al.; Soft Matter, 2013, 9, 4015-4025

Chapter 11

11.2 Conformation in solution

Typically water is taken as solvent, but other solvents can be taken as well, e.g.
alcohols.
a) infinitely dilute solution

isolated chains
solvent gives background with dielectric constant
Bjerrum length is the separation at which the electrostatic interaction
between two elementary charges is comparable in magnitude to the thermal
energy scale
lB=e2/(40 kBT)
e.g. water at room temperature =78.5 and lB=7.14
mean field approach: free energy given by contribution from Gaussian chain
with an end-to-end distance Re2=Nl2 and the electrostatic energy of N charges

R2
N2
F = k B T 2 + k B Tl B
R
Nl
Minimization with respect to the typical length scale of the system R yields

R N (l B l 2 ) 1 / 3
Which is significantly changed compared to
a Gaussian chain with R=lN
a chain in a good solvent RlN0.6
the long range Coulomb interaction leads to an increase of the typical chain
dimensions proportional to the chain length however, the chain is not fully
extended!
b) finitely dilute solution
single polymer chains, which monomers interact via Debye-Hckel potentials
counterions considered by screening parameter
model of connected "beads"
calculation based on "trial"-Hamiltonian results in an end-to-end distance of
2t T t tN 1
2
2 1 + tT

Re = Nl
+
2
1
t
N

(
t
1
)

T
T

tT: averaged cosine of the angle between two bonds

N: degree of polymerization

In case of flexible chain, given by tT<<1 and N>>1:

Chapter 11

Re2 = Nl 2

With the persistence length

1 + tT
= 2 Nll p = Nll s
1 tT

lp =

l 1 + tT
2 1 tT

and the Kuhn segment length ls=2lp

11.3 Structure in solution
Aside from conformation of polymer chain the structure in the solution is of
importance. It can be probed with scattering experiments.
Polymer Reference Interaction Site Model (PRISM)
Based on the Orstein-Zernike integral equation theory, first proposed by
Chandler and Andersen (1971)
it consists of
g(r): pair correlation function
c(r): direct correlation function
ij: intra-molecular correlation function
h(r)=g(r)-1: total correlation function
contribution of the direct
correlation function c(r) and
the intramolecular correlation
function s to the total
correlation function

R.G. Winkler, 33.IFF Ferienkurs 2002

With contributions from the intra-molecular correlation function of a site i and j

of the same molecule

ij ( ru , r j ) = ij (ri r j ) + s ij ( ru , r j )
r r

r r

a) monomermonomer pair correlation function for various Bjerrum lengths

ranging from very weakly charged systems up to well above the Manning
threshold for counterion condensation (lB/= 1)

Chapter 11

Results for chain lengths N = 10 (a)

and N = 80 (b)
the variation of the Bjerrum length
causes only minor changes in gmm
in contrast to the variation of the
density, which has a rather large
influence on the structure and
therefore on the monomermonomer
correlation function
Notice that all curves for the different
values of lB cross each other at the
same distance r
T. Hofmann et al.; The Journal of Chemical Physics,
114, 1018110188, (2001)

polyelectrolyte solutions have solution-type behavior in case of dilute

solutions (low density 1x10-5), which gets more pronounced at higher densities
(density 1x10-4) until it vanishes at high concentrations (density 1x10-3) and a
bead structure evolves

Dobrynin, et al. Macromolecules 1996, 29, 2974-2979

lB/l is measure for strength of interaction:

small values liquid-like behavior due to "hard core interaction"
large values the equally charged monomers repel each other which reduces
the probability for small distances and makes structures better pronounced
density defines the structure mainly
b) Monomercounterion pair correlation function gmc(r) and Counterion
counterion pair correlation function gcc(r) for various Bjerrum lengths lB
For small lB gmc(r) is nearly constant with a value of about one for all r. Hence,
the local counterion density matches the bulk density almost everywhere, i.e.,
the counterions are distributed homogeneously over the whole system. With
increasing Bjerrum length an increasing peak appears at r = and a much
smaller peak at r = 2. This implies that the counterions are now no longer
Chapter 11

homogeneously distributed, but are found with larger probability in the vicinity
of the chains. It should be noted that the distance r = is the smallest possible
distance between monomers and counterions because of the hard core repulsion.
Results for chain lengths N = 10 (a) and N = 80 (b)

T. Hofmann et al.; The Journal of Chemical Physics, 114, 1018110188, (2001)

The counterioncounterion correlation function gcc provides a deeper insight into

the issue of counterion condensation. For very low lB gcc is constant for almost
all distances, corresponding to a homogeneous distribution of the counterions.
An increase of the Bjerrum length first leads to a decrease of the contact value
gcc() and the overall function value for short distances. A further increase of lB
reverts this behavior and a peak appears at r = 2. The height of the peak
increases with increasing lB and its width decreases. This behavior can be
explained by counterion condensation.

Peak at r=2l due to smallest distance of counterions

If the Bjerrum length is further increased the counterions are attracted by the
polyion and start to condensate on the chain, which must be accompanied by a
Chapter 11

decrease of the mean separation between ions. Consequently, gcc starts to

increase at short distances. Hence, despite the repulsive Coulomb interaction the
counterions are, for sufficiently strong interactions, subject to an effective
attractive potential next to a polymer chain.
11.4 Counterion condensation
The counterion condensation phenomenon is commonly described by
Mannings theory (Manning 1969), which assumes that counterions can
condense onto the polyions until the charged density between neighboring
monomer charges along the polyion chain is reduced below a certain critical
value. In the model the real polyion chain is replaced by an idealized line
charge, where the polyion is represented by a uniformly charged thread of zero
radius, infinite length and finite charge density, and the condensed counterion
layer is assumed to be in physical equilibrium with the ionic atmosphere
surrounding the polyion.
Simple model: infinitely long, thin, charged rod with charge density l=e/l and
potential R=l(x)(y) with orientation along the z-axis

Solve the 2dim Poisson equation

R (r) =

2e
ln( r )
l

The partition function of a single charge in front of the line charge is

Z R exp( (l B / l ) ln r )2rdr = r 1 2l B / l dr
The integral diverges at the lower limit for 1-2lB/l1 or lBl
Which means that this regime is unstable and counterions will condensate on the
line charge as long as lBl is no longer valid = counterion condenstaion
critical value lB=l
only valid for an infinitely long wire or the extreme case of infinitely small
concentration

Chapter 11

Mannings theory does not take into account the molecular details of real
polyion chains, like e.g. local solvation effects or atomic partial charge
distributions.
strong influence on the structure of the polyelectrolyte:
lB/l=0 (top left): conformation of chain in good solvent
lB/l=1.3 (top right): chain completely stretched
lB/l=9.7 (bottom left): counterion condensation polymer chain gets
flexible
lB/l=19.7 (bottom right): compact, globular structure caused ion-pair
formation

R.G. Winkler, 33.IFF Ferienkurs 2002

11.5 Classification of polyelectrolyte systems

1) class 1: amorphous macromolecule-salt complexes
Typically based on polyethers
Example: PEO (polyethylene oxide) -(CH2CH2O)n- with Tm65C
Complexation increases Tg by 50-100 K, thus increases toughness of material
and increases conductivity by a factor of 105 or more
PEO12LiClO4 conductivity
= 5.6 10-6 S/cm
PPO9LiCF3SO3
= 2.2 10-5 S/cm
Ge
= 5.0 10-2 S/cm
Chapter 11

Low conductivity can by compensated by the use of thin films.

2) class 2: plasticized systems = class 1 polyelectrolyte with the addition of a
small amount of low molecular and polar solvent molecules
Example: Propylenecarbonate or other modified carbonates as additives
increases conductivity by a factor 100
3) class 3: polyelectrolyte with negative or positive charged ions, which are
covalently bound to the polymer backbone, mostly swollen by solvent molecules
Example: groups which carry charges are typically -SO3- and -COOConductivity Nafion
= 10-2 S/cm
copolymer
of
tetrafluorethylen
(Teflon) and perfluor-3,6-dioxo-4methyl-7-octen-sulfonacid

4) class 4: polyelectrolyte gels = increase in viscosity by addition of solvable

polymer or incorporation of electrolyte solution into an inactive polymer matrix
Example: LiClO4-PC/EC solvent:salt=8.8:1 conductivity = 5.2 10-3 S/cm
(a) hydrogels or organic
gels
(b) polyelectrolyte gels
(c) swollen gels

TAKIRON Co., LTD

5) class 5: polyelectrolyte rubbers = polymer with high molecular weight Mw

which is dissolved in low-temperature salt mixture
Maximum conductivity = 10-3 S/cm
6) class 6: polyelectrolyte composites = addition of nanoparticles or fillers or
based on block copolymers
maximum conductivity = 10-3 S/cm
but improved mechanical behavior
Chapter 11