J. Phys. Chem.

B 2002, 106, 9967-9973 9967

Osmotic Properties of Aqueous Ionene Solutions

K. Arh, C. Pohar,* and V. Vlachy

Faculty of Chemistry and Chemical Technology, UniVersity of Ljubljana, 1001 Ljubljana, SloVenia
ReceiVed: March 29, 2002; In Final Form: July 12, 2002

Osmotic coefficients of aqueous solutions of 3,3-, 4,5-, 6,6-, and 6,9-ionenes with bromide and chloride
counterions were measured at 298 K and in the concentration range from 0.001 to 0.1 mol/dm3. The measured
osmotic coefficients are very low, indicating large deviations from ideality caused by strong interactions in
these systems. The solutions with chloride counterions have a higher osmotic coefficient than the corresponding
bromide solutions, which is in agreement with experimental data for the counterion activity coefficient of
these solutions. The experimental results for osmotic coefficients were analyzed using a cylindrical cell model
where a fixed charge is assumed to be uniformly distributed along the z-axis of a rigid and impenetrable
polyion, in conjunction with the classical Poisson-Boltzmann equation. More refined models in which discrete
charges are located periodically along the z-axis of the polyion were also studied. In the latter case the canonical
Monte Carlo method was used to calculate the osmotic coefficient. In agreement with previous studies of
weak and moderately charged polyelectrolytes, we found the theoretically predicted osmotic coefficients to
be too high in comparison with the experimental data for aqueous ionene solutions.

1. Introduction formed by a vapor pressure osmometer, and in a few cases at

concentrations below 0.02 mol/dm3, also by a membrane
Ionenes are cationic polyelectrolytes with charged groups
osmometer.
located on the main polymer chain.1,2 Ionenes with various
distances between the charged groups on the polymer backbone Theoretical modeling of polyelectrolyte systems is difficult,
can be synthesized, and in this way polyelectrolytes with in part due to the need to deal effectively with both the long-
different charge densities can be obtained. This property of range Coulombic forces and the short-range solvent effects.14
ionenes makes them suitable for a wide range of applications: In addition, the polyions are more or less flexible and change
ranging from use as solid polymer conductors,2,3 or for floc- their conformation due to their interaction with the ionic
culation of clays in solution,4 to modifiers of polymer-coated environment. Considering the complexity of these systems, it
packing materials for capillary electrochromatography.5 From is not surprising that popular polyelectrolyte models15-18 ignore
the theoretical point of view the ionenes seem to be appropriate all conformations other than the fully extended one. Further,
materials for studying the effect of polyion charge density on they neglect the effect of specific interactions, treating the
thermodynamic and transport properties. Despite the wide range solution as a purely Coulombic fluid, where the charges are
of applicability of these systems and the theoretical interest embedded in a dielectric continuum. There are a few exceptions
mentioned above, aqueous solutions of ionenes have not been in this respect,19,20 for example, Jayaram and Beveridge19 used
extensively studied so far. An important contribution toward a modified model that included a Gurney correction term for
understanding of thermodynamic and transport properties of desolvation21,22 to interpret the experimental data. In a similar
aliphatic ionenes was made by Nagaya and co-workers.1,6,7 study, Rebolj et al.20 used the Gurney model to analyze the
These authors studied the conductance and counterion activity experimental results for ion binding in lithium and cesium
of 3,3-, 4,5-, 6,6-, and 6,9-ionenes with various counterions. poly(styrenesulfonate) solutions at various temperatures.
One conclusion of their study is that the measured counterion In the present work we present measurements of the osmotic
activity coefficient is lower than that theoretically predicted.1 coefficient of Br and Cl ionene solutions in water. In the
Polyelectrolyte solutions display strongly nonideal behavior theoretical part, several different models of the polyion-
due to electrostatic interactions between the highly charged counterion interaction were examined and their predictions
polyions and small ions in solution. Valuable information about compared to the experimental data. According to the first model,
these interactions is obtained from measurements of osmotic the polyion is treated as an infinitely long cylinder with the
pressure.8-13 The practical osmotic coefficient, defined as Φ charge uniformly distributed along the z-axis, whereas the
) Π/Πid, is a measure of this nonideality. Note that Πid is the solvent is treated as a continuum dielectric with permittivity r.
ideal contribution to osmotic pressure. Here we present the This model is examined by solving an appropriate Poisson-
results of osmotic pressure measurements of aqueous solutions Boltzmann equation. Note that the separation between the
of 3,3-, 4,5-, 6,6-, and 6,9-ionenes with bromide (Br) and charges on the polymer backbone (length of the monomer unit
chloride (Cl) counterions. The data were obtained for salt-free b) is rather large, for example, for 3,3-ionene it is 0.498 nm
polyelectrolyte solutions at 298 K and in the concentration range and for 6,6-ionene b ) 0.879 nm.1 Accordingly, a uniform
from a polyelectrolyte concentration cm ) 0.001 to 0.1 mol/ distribution of charge on the polyion is not a very realistic
dm3. The osmotic pressure measurements were mostly per- approximation for these polyelectrolytes. To correct for this
deficiency, in the second model discrete charges are assumed
* Corresponding author. E-mail: [email protected]. to be fixed along the z-axis to mimic the charged groups on the
10.1021/jp025858k CCC: $22.00 © 2002 American Chemical Society
Published on Web 08/27/2002
9968 J. Phys. Chem. B, Vol. 106, No. 38, 2002 Arh et al.

polyion. Only Coulombic interactions were included in this

computation. Finally, in the third model the counterion-
counterion and the fixed charge-counterion interactions are
modeled using the interaction potential of Ramanathan and
Friedman22 to account for solvation phenomena.20 The canonical
Monte Carlo method was utilized to obtain numerical results
for the discrete-charge models.23-27
The outline of this paper is the following. After the Introduc-
tion (section 1) we describe the experimental procedure and
present the results for osmotic coefficients in section 2.
Polyelectrolyte models and methods of calculation are intro-
duced in section 3. The comparison of experimental data with
the numerical results obtained by the Poisson-Boltzmann theory
and the Monte Carlo method is given in section 4. Finally, the
conclusions are summarized in section 5.

2. Experimental Section
Figure 1. Experimental values of osmotic coefficients of 3,3- (9),
2.1. Materials. All investigated polyelectrolyte ionene salts 4,5- (b), 6,6- (2), and 6,9- (1) ionene bromide solutions as a function
were synthesized in our laboratory following the procedure of the negative logarithm of the molar concentration.
described by Rembaum et al.1,6,7,28-30 Bromide salts of aliphatic
x,y-ionenes (3,3-, 4,5-, 6,6-, and 6,9-ionene) were prepared in
dimethylformamide (DMF) using appropriate reagents. A solu-
tion of N,N,N′,N′-tetramethyl-1,x-diaminoalkane was mixed with
a solution of a 1,y-dibromoalkane in a 1:1 molar ratio and the
mixture was stirred at room temperature (about 22 °C) under
an argon atmosphere. The following reaction took place:

After 48 h, the precipitated polymer ionenes were filtered

using Teflon filters, washed with a large amount of acetone,
and dried under vacuum at 40 °C. The sample solution was
exhaustively dialyzed (applying cellulose bags SIGMA; MWCO
Figure 2. Experimental values of osmotic coefficients of 3,3- (0),
) 12 000) against water, which was checked every day by 4,5- (O), 6,6- (∆), and 6,9- (∇) ionene chloride solutions as a function
conductivity measurements. Chloride salts were prepared from of the negative logarithm of the molar concentration.
hydroxides by neutralization with HCl. Hydroxides were
obtained from the bromides by ion exchange. Because of the osmometer is the relatively low accuracy of the vapor pressure
instability of the basic (OH-) form, ion exchange was carried apparatus for dilute polyelectrolyte solutions. In the region where
out just before the preparation of the chloride form. Sample accurate results could be obtained, the two methods agree within
solutions were concentrated by vacuum evaporation before use. the experimental uncertainties, i.e., about 4%. Figures 1 and 2
The concentrations of stock solutions were determined by a show that ionene solutions exhibit large deviations from ideality,
standard potentiometric titration of the halogenide counterion which are reflected in the low values of the osmotic coefficient.
with AgNO3, using a corresponding halogenide ion-sensitive As expected, the osmotic coefficient monotonically increases
electrode and a saturated mercury sulfate electrode as a from 3,3- through 4,5- to 6,9-ionenes, i.e., in the direction of
reference. The structure and purity of the polymeric products increasing distance b (length of the monomer unit) between two
were checked by NMR analysis, which showed the absence of consecutive charged groups on the polyion. However, as we
the monomer reactants in all final products. will see later, the increase of the osmotic coefficient as a function
2.2. Osmotic Coefficients. The osmotic coefficient measure- of a polyion charge density is much less than expected on the
ments were performed at 25 °C with a Knauer vapor pressure basis of popular electrostatic theories.
osmometer (Model K-7000) and a Knauer membrane osmometer The osmotic coefficient results for 3,3-, 4,5-, 6,6-, and 6,9-
(Model 7310100000). A detailed description of the osmometers ionenes with chloride counterions are shown in Figure 2. The
and the experimental procedure has been given elsewhere.31-34 values of osmotic coefficients are slightly higher than for
The vapor pressure osmometer was calibrated with standard KCl bromide solutions of the same concentrations. This observation
solutions. In the membrane osmometer cellulose triacetate is in agreement with the measurements of the counterion activity
membranes with MCO 10000 (Sartorius, AG, Goettingen, coefficient of ionene solutions performed by Nagaya and co-
Germany), were used. workers,1 as also with experimental results for aqueous solutions
We start our discussion with the results for 3,3-, 4,5-, 6,6-, of tetraalkylammonium halides.35
and 6,9-ionenes with bromide counterions shown in Figure 1.
The data for concentrations lower than 0.02 mol/dm3 were 3. Theoretical Analysis
obtained by the membrane osmometer and the others by the 3.1. Ion-Condensation Theory. Manning’s ion-condensation
vapor pressure instrument. The reason for using the membrane theory17,18 has proved on many occasions to be very successful
Osmotic Properties of Aqueous Ionene Solutions J. Phys. Chem. B, Vol. 106, No. 38, 2002 9969

in interpreting experimental data on polyelectrolyte solutions. Using the analytical solution of the Poisson-Boltzmann equa-
The model of polyelectrolyte solution is based on the following tion in cylindrical symmetry, the osmotic coefficient Φ can be
assumptions:17 (a) the real polyion is replaced by an infinite written in the form
line charge, (b) interactions between two or more polyions are
neglected, and (c) the dielectric constant is taken equal to that 1 - β2
Φ) (1 - e-2γ) (5)
of water. The most important parameter of the theory is the 2ξ
linear charge density ξ, equal to e02/(4π0rkBTb). As usual, kB
is the Boltzmann constant and T is the absolute temperature, r where γ ) ln(R/a) and β is an integration constant following
is the dielectric constant of the solvent relative to a vacuum, e0 from the solution of the Poisson-Boltzmann equation.15,16 Note
is the elementary charge, and b is the length of the monomer that in the Poisson-Boltzmann theory the ions are treated as
unit carrying charge e0. The theory is based on the observation pointlike charges and their size is reflected merely in the
that the statistical-mechanical phase integral for an infinite line polyion-counterion contact distance a ()0.335 nm). An
charge model diverges for the values of the charge density on expression for the osmotic coefficient equivalent to eq 5, but
the polyion, which yield ξ > 1. The physical interpretation of based on the virial theorem, has also been proposed.38
the divergence of the phase integral is that for ξ > 1 the system 3.3. Discrete Charge Models. Again, the solution is divided
becomes unstable and sufficiently many counterions have to into cylindrical cells as described before. The main difference
“condense” on a polyion to reduce the charge density. The to the model described in section 3.2 is that we assume that the
condensed layer cannot be diluted from the polyion. A short, charges on the polyion are located periodically (at distance b)
but illuminating, review of the characteristic properties of poly- along the z-axis. The centers of counterions are not allowed to
electrolyte solutions in light of this theory has recently been penetrate within the cylinder of radius a, here chosen to be 0.335
given by Manning and Ray.18 According to this approach the nm. Two different discrete-charge models were examined. In
osmotic coefficient Φ, for solutions with monovalent counter- the first case the interaction potential between the various
ions, is given by charged groups is given by

ξ eiej
Φ)1- ξe1 (1) uij(r) ) rij g rij* (6)
2 4π0rrij

1 uij(r) ) ∞ rij < rij*

Φ) ξg1 (2)
2ξ
where rij* ) (ri* + rj*)/2 and i (j) denotes a charged group on
Note that the osmotic coefficient behaves dramatically different the polyion (P) or the counterion (c). The model above is an
for values above (or below) the critical value of ξ, which for analogue of the so-called primitive model, often used to describe
solutions with monovalent counterions is unity. This approach electrolyte solutions. The parameters used in the actual calcula-
often yields good agreement with experimental results for tions are given in section 4.1.
thermodynamic and transport properties of polyelectrolyte In the second, more refined model, the solvent-averaged
solutions. potential energy between the two charges is given by22
3.2. Poisson-Boltzmann Cell Model. The polyelectrolyte
eiej
solution is modeled as a system of a large number of cylindrical uij(r) ) + CAVij + CORij + GURij (7)
cells of length h ) Nb, equal to the length of the polyions. The 4π0rrij
polyions contain N monomer units of length b (N . 1). The
cell radius R is determined by the concentration of monomer where ei (ej) is the charge of a particular ionic species. The
units cm (eq 3), where NA is Avogadro’s number. Each polyion first term in eq 7 represents the Coulomb interaction. The term
CAVij is zero for our model of a continuous dielectric. The core
1 repulsion term CORij is given by eq 8 where r/i (r/j ) is the
cm ) (3) Pauling radius of an ion of species i (j).39 Further, Fm is the
πR2bNA
Madelung constant and σ is the coordination number.

( )
is placed along its own cylindrical cell. The interactions between r/i + r/j 9
the particles in the adjacent cells are neglected. In this model CORij ) Bij (8)
the fixed charge is assumed to be smeared uniformly along the rij
long polyion axis and a is the counterion-polyion contact
|eiej| 1
distance. The pointlike counterions are distributed within the Bij ) Fm
free volume of the cell, and no additional simple electrolyte is σ4π0 9(r/ + r/)
i j
present. For simplicity, a uniform permittivity was assumed
throughout the solution. This model is very popular and has According to Gurney,21 the isolated ion is surrounded by a co-
been widely studied using the Poisson-Boltzmann (PB) equa- sphere of water of thickness w, in which water has different
tion,15,16 the modified PB theory23-27 by computer simula- properties than in the bulk. When two ions come close enough,
tions,23,27,36 and also by the density functional approach.37 The the sum of their co-sphere volumes is reduced by overlap. The
osmotic coefficient within the cell model can be expressed as water contained in the overlap volume Vs must return to its
the ratio of the ion concentration at the cell boundary c-(R) unperturbed state and Aij is the change in the molar free energy
and the average concentration of counterions c- in the cell, as associated with this process. This Gurney term (GURij) for a
given by pair of ions i and j is given by the expression

c_(R) VS(r/i +w,r/j +w,rij)

Φ) (4) GURij ) Aij (9)
c_ Vw
9970 J. Phys. Chem. B, Vol. 106, No. 38, 2002 Arh et al.

where Vw is the molar volume of bulk water and Vs is the mutual

volume function.22 The parameters used in our study are the
Madelung constant Fm ) 1.76, the coordination number σ ) 6,
w ) 0.276 nm, and again ap ) 0.335 nm. The Gurney
parameters Acc and Apc are not known in advance: in principle,
they can be obtained from fitting of the measured data.22,40,41
The Monte Carlo method has been utilized to obtain results for
the models described in section 3.3.
3.4. Monte Carlo Method. The canonical Monte Carlo
method has been applied to polyelectrolyte solutions before and
it is described in several articles.23-26 In the Metropolis
scheme,42 a sequence of configurational states is generated
according to the condition

f e min[1,e-β∆U] (10)

where f is a random number and ∆U is the difference in the

Figure 3. Calculated and measured values of the osmotic coefficient
configurational energy between the trial configuration and the for 3,3-ionene Br- solution at 25 °C: (9) experimental points; (dotted
previously accepted configuration. The central cell in the line) Poisson-Boltzmann results; (dashed line) Monte Carlo results
simulations is represented by a cylindrical box of height Nb for the discrete charge model with ξ ) 1.43; (dash-dotted line with
and radius R. In all calculations presented in our study, the ×) Monte Carlo data for ξ ) 1.75. The full line represents the results
number of monomer units included in the central cell was N ) of the refined model with Gurney parameters Apc ) -1065 J/mol and
1000. Corrections due to the finite number of particles in the Acc ) 0.
Monte Carlo cell were evaluated as suggested by Bacquet et
al.25 The counterion concentration at the cell boundary c-(R) presented in Figure 3 by a dashed line just below the dotted
(cf. eq 4), needed to evaluate the osmotic coefficient, was line. This result suggests that the discrete-charge model predicts
calculated in two different ways. One is the conventional stronger binding (smaller osmotic coefficient) than the Poisson-
method; c-(R) was obtained by extrapolation from the histogram Boltzmann equation. Also, the discrete-charge model concentra-
points, where each bin has a width δr and extends from r + tion dependence of Φ is slightly weaker than predicted by the
δr. In addition, the modified “test particle method”43,44 was also Poisson-Boltzmann smeared-charge model calculation. A
used. In both cases the z-dependencies due to the discrete similar discrepancy has been found for other thermodynamic
charges on a polyion were averaged out. The results obtained properties, for example, D/D0,20,45 or the Donnan exclusion
by the two alternative methods agreed within the numerical coefficient36 and can, in part, be attributed to neglect of the
uncertainty of the simulation. The statistics were collected over interionic correlation by the Poisson-Boltzmann theory. To
16 million or more of attempted configurations, after an bring the discrete-charge model into agreement with experiment,
equilibration run of at least 5 million configurations. The a considerably higher value of the charge density parameter ξ
uncertainty in the calculated values of the osmotic coefficient must be used in the calculation. This finding is consistent with
is estimated to be about (2%. previous studies of poly(styrenesulfonate) solutions.8 The Monte
Carlo results for ξ ) 1.75 are shown in Figure 3 by crosses
4. Numerical Results and Comparison with Experimental connected by a dash-dotted line. An increase of parameter
Data ξ from theoretical value 1.43 to 2.00 brings the Poisson-
4.1. Results for 3,3-Ionenes. In this section we present Boltzmann theory into agreement with experiment.
numerical results for the models and methods described in In this part we discuss the results for the refined (also called
section 3. Our analysis first focuses on modeling 3,3- and 6,6- Gurney) model. Again, these results were obtained by the Monte
ionene bromides. First, in Figure 3 we present the osmotic Carlo method. The potential function described by eqs 7-9
coefficients for model 3,3-ionene solutions as calculated by the contains several parameters. Again the (Pauling) radius of a
Poisson-Boltzmann equation (eq 5). In this calculation the bromide ion is taken to be 0.181 nm, rp is 0.195 nm, and a )
polyion is represented as a cylinder of diameter 0.335 nm, 0.335 nm and for ξ a structural value equal to 1.43 is used.
whereas the counterions are assumed to be point charges. The Two unknown parameters of the refined model are the so-called
fixed charge is actually modeled as a continuous line of charge Gurney coefficients for the counterion-counterion, Acc, and the
on the z-axis of the cylinder. All calculations for 3,3-ionene charged group (polyion)-counterion interaction, Apc. These
solutions in water apply to T ) 298 K and b ) 0.498 nm, where coefficients can be used as fitting parameters to bring the theory
ξ ) 1.43 (r ) 78.3). These results are shown in Figure 3 by a and experiment into agreement.22,40,41 Fortunately, as found
dotted line. An increase of parameter ξ from theoretical value before,20 an exact value of the coefficient Acc seem to be less
1.43 to 2.00 brings the Poisson-Boltzmann theory in agreement important for the analysis. Namely, this coefficient has much
with the experiment. less effect on the calculated values of thermodynamic properties
In the same figure we also present the results of the Monte than Apc. For simplicity we choose the c-c Gurney parameter
Carlo method applied to the discrete charge model described Acc ) 0, though some other combination of Gurney parameters
in section 3.3 (cf. eq 6). As before, the counterions are excluded could yield better agreement with experimental data.22 With this
from the cylinder with radius a ) 0.335 nm and b ) 0.498 nm. approximation, the only parameter left is Apc, which can be
The Pauling radius39 rc for a bromide ion is 0.181 nm, and the adjusted for the maximum agreement between the measured and
same quantity for the model “charged group” on a polyion, rp, calculated data.
is chosen to be 0.195 nm. This means that the distance of closest The theoretical results for the refined model are shown in
approach of a counterion to the charge on the backbone is (0.181 the same figure (Figure 3) by a full line. For this calculation
nm + 0.195 nm) ) 0.376 nm. The Monte Carlo data are we set Apc ) -1065 J/mol at 25 °C, whereas the other
Osmotic Properties of Aqueous Ionene Solutions J. Phys. Chem. B, Vol. 106, No. 38, 2002 9971

Figure 4. Calculated and measured values of the osmotic coefficient Figure 5. Calculated and measured osmotic coefficients of 3,3-, 4,5-,
for 6,6-ionene Br- solution at 25 °C. Notation as for Figure 4. 6,6-, and 6,9-ionene bromides at 0.001 mol/dm3. The theoretical results
are for the Manning theory (eqs 1 and 2) shown by the dashed line,
parameters are given in the previous paragraph. As we can see and the Monte Carlo data are presented by the full line connecting
from this plot, the inclusion of the short-range interaction circles.
significantly lowers the value of the osmotic coefficient.
However, the influence of the short-range potential due to the consecutive charges on the polymer backbone b ) 1.06 nm and
nonzero (negative) Apc Gurney term, is stronger at higher therefore ξ ) 0.67. It is of considerable interest to present the
concentration, which yields an incorrect concentration depend- osmotic coefficient data for these solutions as a function of the
ence of the osmotic coefficient. charge density parameter ξ. These results are shown in Figure
4.2. Results for 6,6-Ionenes. We have also performed 5, where the predictions of various theories are compared to
calculations for models mimicking 6,6-ionene solutions in water. the experimental data here presented by symbols. All the
We present these results in the next figure, Figure 4. The experimental results apply to ionene solutions with Br ions as
Poisson-Boltzmann results presented in this figure apply to counterions at a concentration of 0.001 mol/dm3 and T ) 298
ξ ) 0.81 (b ) 0.879 nm), whereas the other parameters are as K. The same holds true for the theoretical results, an exception
for the 3,3- case. These results are shown by the dotted line. being Manning’s condensation theory (eqs 1 and 2) calculation,
The discrepancies between the purely electrostatic Poisson- which applies to the infinite dilution limit.17 The latter results
Boltzmann theory and the experimental results are, as expected, are shown in Figure 5 by a dashed line. The predictions of the
even larger here. The Poisson-Boltzmann calculation can Manning theory are in good agreement with the measurements
be brought into reasonable agreement with the experiment for for solutions with ξ > 1, but for lower values of ξ the calculated
ξ ) 1.54. This finding is in agreement with previous studies of values are too high. The same behavior has been noticed
osmotic coefficients of polyacrylic acid45 and maleic acid/ previously by Manning (see Figure 5 of ref 17) for the sodium
ethylene copolymer solutions.10 In particular, Kozak10 studied salt of polyacrylic and poly(methacrylic acid) and also by
solutions of the copolymer of maleic acid and ethylene at various Kozak,10 who studied maleic acid/ethylene copolymer solutions.
degrees of neutralization R. The agreement between the The Monte Carlo results are presented in Figure 5 by a full
measured and the Poisson-Boltzmann values of the osmotic line. The conclusion is that the theories examined here
coefficient is semiquantitative; more precisely, by decreasing overestimate the osmotic coefficient and that the discrepancies
the charge on the polymer (low R), the agreement between increase with the decreasing charge on the polyion. It is quite
theory and experiment becomes worse. The same holds true clear from this figure that the Coulomb interaction between the
for the Monte Carlo data for the discrete charge model obtained counterions and the charges on the infinitely long polyion, as
with a structural value of ξ ()0.81), cf. the dashed line in this taken into account in this study, is not the only source of
figure. Theory for the discrete charge model can be brought nonideal behavior of ionene solutions. The contribution of the
into better agreement if we increase the value of ξ to around interaction not included in modeling to polyelectrolyte non-
1.43. These results are shown in Figure 4 by crosses connected ideality is more important for lower values of ξ. If we are
with the dashed-dotted line. Finally, we also present the results allowed to speculate and extrapolate the ξ dependence of the
for the refined model. The two Gurney parameters were chosen measured data given in Figure 5 to ξ ) 0, we obtain a value of
to be Apc ) -1860 J/mol and Acc ) 0, whereas for the charge the osmotic coefficient for a hypothetical discharged ionene
density parameter, ξ, a structural value of 0.81 was used. These polyion somewhere between 0.75 and 0.85. To show that this
results are shown by a full line. As already noticed for 3,3- is not an isolated result in Figure 6, we present a compilation
ionenes (Figure 3), the refined model does not correctly predict of osmotic coefficient data for various polyelectrolytes (for
the concentration dependence of the osmotic coefficient, though, details see the legend to this figure) as a function of the charge
a more complete analysis in which both Gurney parameters density parameter ξ. The results for several different weak
would be varied, could yield a better agreement between theory polyelectrolytes, including maleic acid/ethylene copolymer
and experiment. solutions10 and poly(acrylic acid)),10,45 show that the osmotic
4.3. Effect of the Polyion Charge Density. The ionenes coefficient does not approach unity as ξ approaches zero. The
studied in the present work differ significantly in their charge osmotic pressure results for HPSS solutions (poly(styrene-
density parameter. For example, for 3,3-ionenes the length of sulfonic acid), a strong polyelectrolyte), where the charge on
the monomer unit b ) 0.498 nm, which yields ξ ) 1.43. On the polyion is partly blocked by addition of a surfactant,49 show
the other hand, for 6,9-ionenes the distance between the two similar behavior (cf. Figure 6). From the experimental results
9972 J. Phys. Chem. B, Vol. 106, No. 38, 2002 Arh et al.

cylindrical symmetry may not be a good representation of the

actual average conformation. The correlation between the
polyions and counterions occupying adjacent cells is not
included in the calculation. There is some indication that this
interaction may increase the nonideality in the system.50 Further,
the models applied in our analysis ignore the molecular nature
of the solvent, and also the dielectric discontinuity at the
polyion-solution boundary. In addition, the theories used in
the present analysis ascribe all the deviations from ideality to
the electrostatic counterion-polyion interaction. In other words,
for a charge density parameter ξ approaching zero, the poly-
electrolyte solution should exhibit ideal behavior. The experi-
mental results for several weakly charged polyelectrolytes
presented in Figures 5 and 6 show that this is not the case. An
important future goal of the theoretical research in the field of
polyelectrolyte solutions should be to explain and quantify this
Figure 6. Compilation of osmotic coefficient data for various remaining nonideality.
polyelectrolytes as a function of the linear charge density parameter ξ.
Experimental values: (b) maleic acid/ethylene copolymer solutions;10
Acknowledgment. We are indebted to Professor Jože
(2) ionenes; (O) polyphosphates;46 (∆) carboxymethyl cellulose;46 (0) Škerjanc for initiating this work and for many fruitful discus-
polyacrylates;47,48 (1) HPSS, where the charge on the polyions was sions. This work was supported by the Ministry of Education,
partly blocked by addition of a surfactant.49 In all cases c ) 0.06 mol/ Science, and Sport of Slovenia under Grant No. PS 506-0103-
dm3. 02.

collected in Figure 6 we may conclude that the osmotic References and Notes
coefficient does not approach the ideal value when the charge (1) Nagaya, J.; Minakata, A.; Tanioka, A. Langmuir 1999, 15, 4129.
on the polymer backbone decreases toward zero. Accordingly, (2) Rembaum, A.; Baumgartner, W.; Eisenberg, A. J. Polym. Sci. B
1968, 6, 159.
there must be another source of nonideality present, not (3) Somoano, R.; Yen, A. P. S.; Rembaum, A. J. Polym. Sci. B 1970,
accounted for by purely electrostatic polyelectrolyte theories 8, 467.
applied in this work. (4) Casson, D.; Rembaum, A. J. Polym. Sci. B 1970, 8, 773.
(5) Pirogov, A. V.; Buchberger, W. J. Chromatogr. A 2001, 916, 51.
(6) Nagaya, J.; Minakata, A.; Tanioka, A. Rep. Prog. Polym. Phys.
5. Conclusions Jpn. 1997, 40, 123.
(7) Nagaya, J.; Minakata, A.; Tanioka, A. Colloids Surf. A 1999, 148,
Experimental results for the osmotic coefficients of 3,3-, 4,5-, 163.
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