JOURNAL OF POLYMER SCIENCE: PART A

VOL. 1, PP. 3231-3260 (1963)

Colligative Properties of Polyelectrolyte Solutions
in Excess of Salt
2. ALEXANDROWICZ and A. KATCHALSKY, Weixmann Institute
of Science, Rehovot, Israel
Synopsis
This work treats the equilibrium properties of polyelectrolyte solutions Containing
an excess of low molecular salt. I n this case the simple rule of additivity, dealt
with previously, fails to describe the experimental results. A detailed treatment,
based on an approximate solution of the Poisson-Boltzmann equation, waa therefore
undertaken. The calculation is based on a subdivision of the electrostatic potential
into two parts corresponding to two regions: ( 1 ) an inner region in the close neighborhood
of the polyion, free of coions and described by the Poisson-Boltzmann equation in the
salt-free case, and (2) an outer region screened off from the central macroion and ads-
quately treated by a Debyean approximation. An analytical solution for the electro-
static potential was obtained and used for the theoretical description of potentiometric
behavior, Donnan distribution of salt, and Donnan osmotic pressure. The predicted
values compare favorably with the measured results in a wide range of experimental
conditions.
I. Introduction
The remarkable fact that osmotic properties of polyelectrolyte solutions
obey a simple rule of additivity was dealt with theoretically in several
previous communications. l--3 This rule permits the calculation with fair
accuracy of the activity of the polyelectrolyte, of the added salt, and of the
solvent in a mixed system of any composition. It was found, however,
that the requirement of additivity is not exact enough for the description
of polyelectrolyte solutions for which very precise measurements are
available. A case in point is the question of activities in polyelectrolyte
solutions containing salt in a large excess. Hence, despite the usefulness of
the simpler rules in describing the colligative properties of the solutions in a
general way, a more detailed analysis becomes necessary if a better approxi-
mation is required.
The fundamental treatment of polyelectrolyte solutions is based on the
evaluation of the electrostatic potential and the distribution of the small
ions around the charged polymeric molecules. Since no exact solution of
the Poisson-Boltzmann equations is available for polyelectrolyte-salt
mixtures, we shall proceed here along the lines proposed by one of us2
earlier The method is based on the division of the electrostatic potential
into two parts: the potential #'"""' in the solution region rlose to the poiy-
3231
3232 Z. ALEXANDROWICZ AND A. KATCEIALSKY
ions where the central electrostatic field is relatively strong, and the poten-
tial $Outer in a region relatively far removed from the charged macromole-
cules. The coions are strongly repelled from the proximity of the poly-
ion, and it is therefore assumed that the inner region contains counterions
only. The value of the potential in solutions of rigid macromolecules
surrounded by counterions was obtained in a rigorous manner by Lifson
and Kat~hal sky,~ and this solution, with suitably chosen boundary con-
ditions, is used here for the evaluation of t,binner. On the other hand, the
influence of the largely screened polyion on the behavior in the outer region
is relatively small, so that ~t,b/kT <<1 and the Debyean approximation
ee+lkT = 1 + Et,b/kT can be used. This approximation leads to an ana-
lytical expression for $Outer. The two solutions for the potential, t,binner
and $Outer are then allowed to meet at a suitably chosen junction point b,
and the integration constants which determine the run of the potential
are thereby fixed.
The results obtained by this procedure lead to a set of theoretical values
for the colligative properties of polyelectrolyte solutions containing mono-
monovalent salt. The calculations predict an additivity of osmotic pres-
sures and of activity coeficients as a good approximation in a wide range of
salt and polymer concentrations. The calculations also show that when
very precise experimental results are considered the additivity rules are
no longer sufficient, and more involved calculations are required. Al-
though the potentials t,binner and $Outer can be expressed in an analytical
form, the evaluation of the parameters requires the use of repetitive numer-
ical approximations. These numerical computations become particularly
unwieldy when the ratio of salt to polymer concentration becomes large.
It is shown below, however, that in the latter case, called here the case of
excess salt, a completely analytical solution can be obtained. Our aim
here is to present this analytical soJ ution and to compare it with results
obtained by several independent methods.
At first the electrostatic potential calculated for the surfarc of the poly-
ion is compared with the results of potentiometric titration. The formulae
obtained have a wider validity and may be used for the evaluation of po-
tentiometric titration in salt-frce as well as in mixed salt-polyelectrolytc
solutions of any composition.
The distribution of small ions in the potential field of the polyions is
next considered. The result is used for the evaluation of the Donnan
distribution and of the osmotic pressure established between the poly-
electrolyte solution and an external salt solution and compared with ex-
perimental results.
11. Preliminary Discussion of the System
1. I n this section we shall introduce briefly the characteristic parameters
of the system and discuss some of their properties. The solution under
cwnsidcration contains n,, polymer molcculcs and n, mono-monovalent salt
PROPERTIES OF POLYELECTROLYTE SOLUTIONS 3233
molecules per milliliter or, alternatively, it contains mp moles polymer per
milliliter and m, moles salt per milliter. It is assumed that the polymeric
salt and low molecular salt have one ion in common known as the counter-
ion. Let us assume that the polyion carries Y negative charges and is
accompanied by v positive monovalent counterions. The concentration
of the counterions is m+ = vm, + m,, while that of the coions is simply
m- = m,. The degree of polymerization of the polymer is called 2, and
if each monomeric unit carries an ionizable group, the degree of ionization
is LY = v / Z. It is often convenient to use the monomolar concentration
of the polymer m, = Zm,. The macromolecules in the present model are
endowed with a cylindrical symmetry, the effective total length of each
molecular cylinder being h and its radius a. We shall return later to the
problem of the real symmetry properties of the macromolecules and their
relation to the parameters of the cylindrical model which is used here for
the sake of mathematical simplicity.
Following the model adopted in previous ~tudi es,~ we shall regard the
solution as an array of parallel rodlike cylinders at an average distance 2R
between the molecular axes. The influence of deviations from this equi-
distant arrangement is discussed below in Section VI . Each macromolecule
serves as the center of an average subvolume V given by the expression
V = l/n, = nR2h
(1)
Since the self-volume of each macromolecule is m2h, the volume fraction of
the polyelectrolyte in solution is
na2h/rR2h = a2/R2 = V,
( 2)
Strictly speaking, a is the radius of closest approach of the counterion to
the center of the polyion, and a2/ R2 is consequently larger than V, by a
suitable correction factor.
2. A cylindrically symmetrical electrostatic potential 1/. is established
around the macromolewles. 1:or symmetry reasons it is clear that the
absolute magnitude of rl. will be maximal on the polymolecule and will pass
through a minimum on the boundary surface between neighboring sub-
volumes. I n other words, (v1/.)~ = 0, or no electrical forces act on the
ions in the surface region. For this reason the solution in the region be-
tween two neighboring subvolumes may be regarded as ideal, at least as
regards the interaction of the small ions with the charged macromolecules.
If the concentration of the positive counterions in the boundary surface
be denoted by m+R and the conwntration of the negative coions is denoted
1)y WL L ~, it is rcadily sem that the consideration of the behavior at thc
siu4ac.c leads to the. followiltg important (l(1uations. For thc IIoiinaii
(vluilibrium of tlic polyclwtrolytc solutiol~I\ it11 ail clxtcm~al salt solution of
cvric*c&ration m', (which is assumcd to bc (vliial to its activity) we obtaiit
3234 Z. ALEXANDKOWICZ AND A. KATCHALSKY
and for the equilibrium osmotic pressure x of the polyelectrolytesalt
mixture with the external solution
T 4- 2m',RT = (m+R + mPR m,)RT (4)
Equation (3) may be obtained in the following way: since the small ions
are subjected to the action of the central field of a polyion, their concen-
tration can be represented by Boltzmann's distribution law or
- -
m+(6 = m+oe --e+(r)/kT
and
-+ -
( 5 )
m- ( r ) = mPoee+(r)/kT
where m+Oand mO are the concentrations at an arbitrary reference point.
From eq. (5) it follows that the product m+(r)m-(r) = m+Rm-R is inde-
pendent of the position vector r . The local chemical potential of the low
molecular salt at point r is
- +- +
-+
-+
- +-
ps = pso + kT In m+'mPr = p 2 + k7' 111rn+'m-"
(6)
-t
and is also independent of r . The potential ps may therefore be identified
with the macroscopic thermodynamic potential of the salt. At Donnan
equilibrium it should be equal to the potential of the salt in the external
solution which is
pLIS = ps" + 122' 111m',?
(7)
ai d by equatiiig ecls. (ti) ai d ('7) we obtain eq. ( : 3 ) .
Equation (4) results directly from the assumption that the field of the
macromolecule at the surface of the subvolume equals zero, so that the
colligative contributions of the ions on both sides of the semipermeable
membrane differ only in the hydrostatic pressure T. The possible effect
of higher order virial coefficients due to non electrostatic phenomena is
neglected here for the sake of simplicity. Equation (4) was derived for a
planar model by Langmuir5 and by Verwey and Overbeek6 and generalized
to any system of charged colloidal part.icles by Marcus.'
Since many solution properties may be represented in terms of the con-
centration at the surface of the subvolumes, it is convenient to identify the
latter with the arbitrary reference concentrations m+O and mPo which
appear in eqs. (5) ; or, fixing the arbitrary reference point at these surfaces
we write
#'R = 0
mf R = m+o (8)
m-" = m - 0
PROPEHTIES OF POLYELECTROLYTE SOLU'TLONS 3235
and in the following the convention of eqs. (8) will be used throughout.
The reference concentrations are related to the overall macroscopic con-
centrations by the following self explanatory normalization conditions :
[Total mole number of counterions in V ]
= (vm, + m,)V = m+o ,fV e-'+'kTdV
(9)
[Total mole number of coions in V ]
= m,V = mO .fv ef*IkTdV
(10)
3. Without going into a detailed calculation of m+R and m-R, which will
be carried out in the following paragraphs, we can make some general
remarks on their magnitude and their relation to the external salt con-
centration m',. Let us consider the potential difference E (see the sche-
matic Fig. 1) which will exist between the subvolume surface layer and the
external salt solution. Putting -eE/kT = q, and making use of Boltz-
mann distribution, we write
m+' = m',eq = mt s( l + q + q2/2 + . . . )
m-' = m',e-q = m',(l - q + q2/ 2 -. . . )
( 1 1 )
( 12)
Throughout the polymer solution the concentration of the counterions
exceeds that of the coions; the difference decreases towards the surface of
the subvolume but retains its positive value everywhere.* For a negative
polyelectrolyte considered here q is therefore positive and m+' > m', >
m-R. Equations ( 1 1 ) and ( 12) evidently satisfy the Donnan equilibrium
of eq. ( 3) . Subtracting eq. ( 12) from eq. ( 1 1 ) gives the quantity m+R
- mPR, which will be shown below to aharacteriee the form of the potential
+Outer
m+R - mPR = 2m',q + m',q3/3 +. . .
( I 3)
while introduction of eqs. ( 1 1 ) and ( 12) into eq. (4) leads to an expression
which correlates q with the Donnan osmotic pressure:
At the surface of a positively charged macroion,
V$ is negative (Gausa theorem). The bulk of the polyelectrolyte solution outside the
polyions contains, on the average, an excess of negative ions. The latter are attracted
preferentially from the bulk of the solution to the vicinity of the polyion, so that an
excess negative charge accumulates at the surface of the polyion and Vz$ is positive
(Poisson's equation). Under
these boundary conditions the potential and the absolute value of the negative V$
must decrease monotonically from a to R in the manner depicted in Figure 1, since any
intermediate extremum would divide the potential curve into two asymmetric parts.
Such an asymmetric curve however would allow for isopotential points, which must
have equal charge density (Boltzmann), to have differently valued Vz$-in contradiction
to Poisson's equation. If the potential and IV$\ decrease toward a minimum mono-
tonically, Vz$ is positive everywhere and, by Poisson's equation again, the number of
the (negative) counterions is everywhere larger than the number of the coions.
* This may be proved as follows.
On the other hand, for symmetry reasons, V$ at R is zero.
3236
Z. ALEXANDROWICZ AND A. KA1'CHALSKY
T/ RT = mp + rn, ' + m-R - 2m',
= mp + mtSg2 + m',q4/i2 +. . .
(14)
-4s is well known, when the ratio of polymer to salt concentration decreases,
the difference between m+R and m-' grows smaller, and the Donnan os-
motic pressure becomes equal to the osmotic pressure of undissociated
polymer molecules (m,,). This result is also obtained from the detailed
calculation of the preceding communication.2 I n the present work we
shall therefore limit ourselves to cases when q is small enough so that terms
Semi p er meab l e
Memb r an e
Fig. 1. A schematic representation of the potential $ inside the polymer solution and
of the potential difference E between the surface layers of the subvolumes on one hand,
and an external salt solution on the other.
of power higher than q2 may be neglected. It should be stressed, however,
that the difference between the concentrations m+R and rn-' becomes zero
only when the polymer concentration itself equals zero; under all other
conditions q #0, and there is a nonvanishing contribution of the counter-
ions to the Donnan osmotic pressure. This point is often overlooked in
treatments which solve the Poisson-Boltzmann equation for polyelectro-
lytes with the tacit assumption that m+R = mFR = m', and use the results
to discuss the properties of solutions in which the ratio of polymer to salt
is by no means small enough to justify this approximation. For example,
the validity of the aforment,ioned rule of additivity cannot be proved on
this basis.3 Furthermore, since q tiirris out to depend mainly on the ratio
of polymer tlo salt concentration, the approximation should be judged in
terms of tht. relative composition of the solution ai d iiot---as is again often
doiie-in terms of the absolute value of the ioiiic strength. A.2nticipatirig
the results obtained below it may be stated that y for thc typicd poly-
cleetrolyte systems considered is found to be of the ordcr of 0.1 rn,,/m's;
PROPERTIES OF POLYELECTROLYTE SOLUTIONS 3237
the range of validity of the present approximation for any given system
may be estimated accordingly.
111. The Electrostatic Potential
1. The electrostatic potential established by a polyelectrolyte in solution
can be obtained by solving the Poisson equation
Vz+ = --4ap/D (15)
= m + O @ - w - m-O&lkT (16)
where the local charge density p is given by the Boltzmann expression
No general solution of eq. (15) has been found for macromolecules of any
symmetry in the mixed salt-polyelectrolyte system. Hence in the follow-
ing the approximate method2 outlined in the introduction will be pursued,
and an attempt will be made to combine in a plausible way two solutions for
the potential: one solution for the potential in the (inner region extending
from the surface of the macromolecules at a to the meeting place b and the
second for the potential in the ((outer region which extends from b to
the surface of the subvolume at R.
I n the inner region qb is on the whole larger that kT and it may be
safely assumed that the coions are so effectively repelled that the region
a < r < b is practically free of their presence. Thus the potential in the
inner region may be given by the solution for a polyelectrolyte surrounded
by counterions only:
(6inner = In [ 2 n ~ ~ m+~ ~ ~ / Dk T / 3 2 sinh2 (p In Ar)]
(17)
where the notation 4 = qb/kT is used. The form of eq. (17) is identical
with that given previously for salt-free solution^.^^^^^ It should be, how-
ever, borne in mind that the integration constants ,6 and A of eq. (17)
differ from those of the salt-free case. They have to be evaluated from
new boundary conditions based on the requirement that at point b the
potential function of the inner region has to merge satisfactorily with that
of the outer region. Furthermore, in salt-free solutions the total number
v of the counterions in subvolume is known, whereas in the present case
the (v + m.V) counterions are divided between the two regions of the
subvolume in a way which has yet to be determined.
The outer region b 6 r 6 R is characterized by a low potential so that
qb <<kT. I n this region we may use the Debye-Hiickel approximation
and solve eqs. (15)-(16) f or the case of cylindrical symmetry2 to obtain
3238 Z. ALEXANDROWICZ AND A. KATCHALSKY
where lo and KO are modified Ressel functions of zero'th order, A and B are
integration constants, while K is defined by
K~ = (4ne2/I>kT)(m+' + m.R) = (8ne2/DkT)m',(1 + (/2/2) (19)
2. The two boundary cwndi ths for 4')'lte', on the surface of the sub-
volume, art'
4R0"t'r = f l f i i ( K/ ? ) + HKo(KI?) + /I = 0
(20)
and
(Vbonter )n = K[ AI I ( KR) - RKI ( KR) ] = 0
or
A = BKI ( KR) / I ~( KR) (21)
Combination of eqs. (20) and (21) with the use of a transformation of the
Ressel functions10 gives
9 = - B/ KRI ~( KB) (22)
The boundary condition for the inner potential at the surface of the polyion
follows from Gauss' theorem
(d$'"""'/dr). = - 4nu/ D (23)
The value of u is evidently u = - ve/2nah, while d$/ dr is readily derived
from eq. (17). Hence we get from eq. (23)
1 + f i cotgh (/3 In A'a) = ve2/DhkT = X
(24)
The dimensionless parameter X appearing in eq. (24) has been called4 the
charge density and was found to be a fundamental parameter for the de-
scription of the electrostatic properties of the polyion. I n eq. (24)' v is
known, and the dielectric constant D is assumed to be equal to that of the
solvent. The effective cylindrical length h of the polyion will be discussed
in more detail below.
I n choosing the arbitrary junction between the outer and the inner re-
gions, we shall try to minimize the error introduced by our approximate
expressions for the local charge density in the two regions [c.f. eq. (IS)].
charge density is equal to
[True density] - [approximate density] = [m+Re-9 - m-Re+] - [m+Rr-m]
I n the inner region we neglect the coion concentration so that the error in the local
'v m'R(l - p)e+
I n the outer region we linearize the exponentials or neglect a term equal to
[True density] - [approximate density] =[m+Re-#' - m-Re*]
- [m+R - m- R) - ( m+R + m-R)+]
s+2(+/3 - p)
- - -m'
Since both errors are found to increase towards b, the junction point is preferably placed
in such a way that the absolute values of the errors on both sides of b become equal.
The exact choice of the junction point does not affect the result materially.
PROPERTI ES OF POLYELECTROLYTE SOLUTIONS 3239
The equation which guides our choice of +( h) has therefore the following
form
(1 - q ) P ) N @( b) [ - + ( b ) / 3 + '7 I
(25)
Equation ( 25) det,erniines t,he value of +( h) as function of (I only (for example when
q =0, +( b) 'v -1). The error t8hus introduced in the calculated value of the charge
density seems to be not unduly large, and, even in the "worst" cme, when the polymer
to salt (and hence q ) is equal to zero, the error still does not exceed 16%. Indeed, in
the latter case the vdue of +has also been calculated by a numerical i ntergrati ~n,~ and
the result is practically identical to our approximate analytical solution, as shown in
Figure 2.
Having decided on the principle for the choice of the junction point, we
shall consider the restrictions which this boundary will set upon the inner
and outer potentials. First we require that
+outer ( b) = +inner ( b) = + ( [ I )
(26)
Secondly we require that the division into two regions will leave the po-
tential normalized correctly in the sense of eqs. (9) and (10); or, sub-
tracting eq. (10) from eq. (9), and recalling eq. (16), we obtain
Y = Jv rnf e - + dV - Jv mf eb d~ = ( ~ / t ) J v p d~
(27)
Equation (27) states that the number of charges per macroion is equal to
the total net charge in the subvolume. Utilizing a well known sub-
stitution" based on eq. (15) we may write
v = (--D/47rt) Jv V2+dV = (- DlcTh/2t2) JOR [d/dr](rd+!dr)Idr
= (va/2X) (df$inner/dr)a - (vb/2X) [ (d+i""er/dr)b - (d+""te'/dr),]
(28)
- (VR/2X) (dd""ter/dr)n
From eqs. (23) and (24) we obtain
(d+inner/dr)a = 2X/a
while by eq. (20)
(d+""te'/dr)R = 0
hence, eq. (27) reduces to the simple continuity condition
(d+inner/dr)6 = (d+"uter/dl.)b (29)
The first continuity condition, eq. (as), written for the outer potential with
eqs. (18), ( 21) , and (22), gives for the boundary at b:
+(b) = BKo(Kb) + -AIo(Kb) + '1
(30)
= B[Ko(Kb) f Io(K~)K~(~R)/II(KR) - l/KRIi(KR)]
Equation (26) may be written also for the inner potential, by using eqs.
(17), (l l ), and (19):
e9( b) = 2?r t 2 m..'(l + q + q2/ 2) b2 sinh2 (@ In A'b)/DkTp2
= ( ~ b / 2 ) ~ ( 1 + q ) / [ P2 coth2 (P In A%) - b2]
324,O Z. ALEXANDROWICZ AND A. KATCEIALSKY
or
P2 Coth2 (f l In A'b) = (~b/2)~(1 + q) e- +@) + f l 2
(31)
while the second continuity condition, eq. (29), may be used with the ex-
plicit expressions for V+inner and for V40uter to give
@ coth (P hl A'b) = - 1 - ( ( Kb/ 2H) [Ki(Kb) - Il(Kb)Kl(KR)/ll(KR)])
(32)
Combining eqs. (31) and (32) we get the final expression for p:
~2 = f 1 + ( K ~ / ~ ) B [ K I ( K ~ ) - I~(K~)K~(KR)/I~(KR) 11 2
- ( ~b/ 2) ~( 1 + q)e-+@' (33)
I n this expression /3 is a function of Kb and KR only, since the parameters
q, B, and 4(b) are also determined by Kband KR through eqs. (22), (25), and
(30). The last step to be taken is to combine eqs. (24) and (32), for coth
@ In A'a) and coth ( p In A ' b) respectively, to give an expression which de-
termines the charge parameter in terms of the parameters KD, KR, and KU:
= {1 + (Kb/2)B[Kl(Kb).- I~(K~)KI(KR)/I~(KR)] - P2 - (Kb/2)R
X [Kl(~b) - ~ ( K ~ ) K I ( K R ) / I ~ ( K R ) IP coth (P In b/ a) ] /
[ 1 + (Kb/2)B[Ki(Kb) - Ii(Kb)Ki(KR)/Ii(KR)] $. p coth (P In b / U ) ]
(34)
3. We would like to conclude this section by outlining the mode of calculation with the
aid of the equations presented above. A given polyelectrolyte solution is characterized
by the concentrations m'. and m, and by the radius a and charge per unit length v / h
of the macroion. It would be therefore advantageous to base the calculation of the
potential on a corresponding set of parameters namely on K = ~(m' . l / ~), R = R(mp-1/2);
Q and X = X(v/h). This approach, however, is barred by the transcendental nature of
some of the equations and the following indirect procedure has been adopted instead.
We start with a given set of values of KR, KCL, and K b and proceed to solve eqs. ( 30) and
( 22) to obtain B/+(b) and q/+(b). A calibration curve of +(b) versus q/ +( b) , which is
simply obtained from eq. (25), guides our choice of the appropriate value of the potential
at the junction point. With +( b) thus chosen, B and q become separately available, and
eqs. (33) and ( 34) are solved for p2 and X, respectively.
It is found that in all cases of excess of salt which fulfill our criterion of small q values
(interpreted here as p 5 l/2), the results of the calculation are practically independent of
KR. The range of relative concentrations to which this finding applies may be expressed
in terms of KR = ~ R ( m ~ ' / ~ / m ~ ' / ~ ) and for typical polyelectrolytes is found to correspond
to KR values larger than about 2-3. A considerable simplification becomes thus avail-
able, since the parameters B, @, and X may be calculated for all systems which contain
an excess of salt (of arbitrary KR value exceeding 2-3) on the basis of the equations which
describe the limiting case KR = m. As follows from eqs. ( 25) and ( 22) , in the latter
case @( b) = - 1 and q = 0, while eqs. ( 30) , ( 33) , and ( 34) reduce to
- 1 = BKo( Kb)
(300
B2 = [I + (Kb/2)BK1(Kb)la - e(Kb/2) ( 33' )
PROPERTI ES OF POLYELECTROLYTE SOLUTIONS 3241
I I
-
A = 3 , a = 6 i -
m! =0001
Sol ! Fr et Erccrr of Sol ! Sal t FICC Excess of sol !
-
-
1
I
,
#
I 1 -
5 10 15 20 25
Having evaluated the parameters B, p2, and A for given KU and ~ t ) , we may proceed and
replot the results in order to provide a description which is related in a more natural way
to the known parameters of the polyelectrolyte solution, vis., give B, p2, and Kb as a
function of ~a and X. Since the additional parameters, namely A, q, and A are readily
obtained from eqs. (21), ( 22) , and (24), the set B, p2, and Kb is sufficient for the evaluation
of the potentials +Inner and +Outer and for finding the junction point b. A typical example
of the potential thus calculated is given in Figure 2. I n Figures 3, 4, and 5 we have
plotted R, 8 2 , and ~ b , respectively, for the values of X encountered in practice and for ~a
values which in typical polyelectrolytes correspond to salt concentrations of 10-5 - 1N.
IV. Potentiometric Titration
1. The results of the potentiometric titration are related in a direct way
to the potential of the polyelectrolyte. As is well known, the pH of a
weak polyacid with negligible nearest-neighbor interactions is given by the
equation
pH = pKo + log [a/(l - a)] - 0.434~A$/kT
(35)
pKo is the intrinsic dissociation constant and A$ is the difference in potential
between the surface of the polyion (where the dissociating group is situated)
and a point at which the polyelectrolyte field becomes zero. The term
-0.434eA$/kT is also denoted by ApK, which implies that it is the con-
tribution of the polyelectrolyte field to the standard free energy of ioniza-
tion of a single group, in addition to the free energy of ionization in sur-
roundings in which no such field is acting (pK,). According to our con-
3242 Z. ALEXANDROWICZ AND A. KATCHALSKY
I :
I (
t
B
E
4
~ a = 0 . 6 3
K O =0.2
K a ~ 0 . 0 6 3
0
3
0
x
Fig. 3. The dependence of B (the parameter of on the charge density A at given
~a and for KR = K (c.f. eq. (19)) in excess of salt is identical
with Debye's K , a is the radius of the macroion, and R the radius of the solution volume
per macroion. The values of B at K a = 2 have been reduced by half.
(infinite excess of salt).
vention, the polyelectrolyte field density and potential are both zero at
the same point R, so that
ApK = -0.434eA#/lcT = -0.434e#.,'"ner/kT
(36)
where #ainner is described by eq. (17), while its value at a is determined by
the boundary condition in eq. (24). Thus
ApK = -log ( 2ae2~+nn2/ Dk?' ) + log [ (A - 1)' - P2 ]
= - 2 log (Ka/2) + log [ (A -
- P21 (:37)
which may be written in yet another form
ApK = log [(v/aa2h)/m+"] + log {[(A - 1) 2 - P21/2A}
(38)
I n dilute solutions and at high charge densities the second term on the
right-hand side is generally much smaller than the first, so that to a rough
approximation
ApK = log [ ( v / ~ a %) / m+ ~ ] (39)
PROPERTIES OF POLYELECTROLYTE SOLUTIONS 3247
5
4
3
-P
2
I
0
- 1
I I I I I
0 2 4 6 8
x
Fig. 4. The dependence of (-) p2 (the parameter of +inner) on the charge density A
at given ~a and for KR = (infinite excess of salt); (- -) values of p2 in salt-free soh-
tiom of corresponding ionic activities ( m?) [c.f. eq. (41)] and below. The parameter y of
Lifson and Katchalsky is y = In R/u.
This expression has a rather interesting physical interpretation: v / m2 h is
evidently the concentration of the counterion in the self volume of the
polyion, while m+R, according to eqs. (3) and (4), represents the counterion
activity throughout the subvolume V. If weconsider a hypothetical two-
phase microsystem which consists of the polyion and of the subvolume,
then the logarithmic term of eq. (39) represents the Donnan potential
between the phases. 12713 This rough approximation breaks down, however,
at lower values of charge density and at higher KU values and will not be
further followed up here.
2. Since ApK depends only on $inner and the latter, except for different
boundary conditions, is identical with the potential developed for salt-free
solutions, it is to be expected that a simple formula can describe the titration
behavior of salt-containing and of salt-free solutions alike. We note that
the only terms in eq. (38) which depend on the composition of the solutions
are m+ R, the counterion concentration in the surface of the subvolume, and
the integration constant p. m+R is a complicated function of the composi-
324.4 Z. ALEXANDROWICZ AND A. KATCITALSKY
r
OO r 0.5 I I .5 2
K O
Fig. 5. Kb (the parameter of the meeting point between put e r and $inner) as a function of
KU at given A and for KR = a (infinite excess of salt).
tion of the solution, and its exact evaluation constitutes in fact one of the
aims of this report. However, for the purpose of the logarithmic term of
eq. (38), the aforementioned approximate rule of additivity is accurate
enough. According to this rule,1v2 m+R in a mixed solution of any com-
position is given by
(40) m+ = acp,m, + m,
where p,, the osmotic coefficient of the salt-free polyelectrolyte solution,
is independent of ma and is determined by and large by the degree of poly-
ion ionization. Furthermore, it is noted that (except for very high ionic
strength) when the values of the constant p are calculated for a given X
and m+R, the results in the case of salt-free solutions turn out to be prac-
tically identical to those obtained in the present case of excess of salt
(c.f. Fig. 4). We may therefore rewrite eq. (38) in a generalized form
which gives ApK in polyelectrolyte solutions of any composition
R
APK = log [(v/m2h)/(cppamm + ma>] + log {[(A - 1) 2 - p 2 1 / 2 ~ ) (41)
With the understanding that the values of the constant p, for a given charge
density X and counterion activity mR, are to be taken from the present
work when ap,rn, < m, and from Lifson and Katchalskys work4 when
acppmm > ma. More explicitly, in salt-free solutions @ = p(X, a/ R) and
a/ R is related to m +
by
a2/ R2 = m,Mm/lOOOp = m+RM,/acp,lOOOp
PROPERTIES OF POLYELECTROLYTE SOLUTIONS 3245
1
OO
Q
Fig. 6. ApK of potentiometric titration in excess of salt, as a function of the degree of
neutralization a: (-) calculated for i strotohed/ a' = 3; a = 5 A.; experimental re-
sults of Samelson'3 at salt concentrations m', of ( . ) (V) 10-1, and ( . ) 1 mole/l.;
experimental results of Arnold and Overbeekl6 at salt concentrations of (0) lo-*, (V)
10-1, and ( 0) 1 mole/l.
where M, is the monomer molecular weight and p the density of polymer;
in excess of salt p = p(X, ha) and ( K U ) ~ = 0.108 m+Ruz.] The similar run
of the potential at a given A and m+R, in case of excess of salt and salt-free
solutions, is demonstrated in Figure 2.
The outstanding feature of the potentiometric eq. (41) is, that in the
presence of excess of salt, ApK decreases with log m, and does not depend
on the polymer concentration. On the other hand, in solutions which
contain an excess of polymer, the opposite rule becomes valid; ApK
decreases with log mm and does not depend on whatever small amount
of salt is added. These rules have been formulated by San~elson'~ on the
basis of an extensive experimental study and can be also deduced from
other result^^^-^^ I n the intermediate range, when
cp,am,, and ms are of the same order of magnitude, ApK is determined by the
total effective concentration of the counterions, eq. (40), resembling similar
rules postulated in several previous publications. 19,20
The dependence of ApK on the charge density A, or on (what amounts
to the same) the degree of ionization a, may be likewise given a simplc
qualitative description: at A values higher than about 1.5 the increase of
ApK with the ionizatioii becomes relatively small and is caused only by thc
relatiwly slowly growing term log [ ( A - - p' ]. At low X, however,
the changes grow more pronounced, and ultimately ApK becomes a
linear fuiiction of the degree of' ionization, in close analogy to expressions
based oii the Debyc-Huckel approxiniatioii; a typical example being the
(see Figs. 6 and 7).
3246 Z. ALEXANDKOWICZ AND A. KAL'CHALSKY
0 0.2 0.4 0.6
a
Fig. 7. ApK of potentiometric titration in salt-free solutions, as a function of the de-
gree of neutralization a: (-) calculated for hstretohed/ a = 3, a = 5 A.; experimental
results at polymer concentrations of (0) (0) and ( A) lo-' monomole/l.; as
given in the literature by (1) Sanielson,13 ( 8) Gregor and Frederick,I4 ( 3 ) 0th and Doty,'5
( 4 ) Arnold and Overbeek," (6) Kern," and (6) Katchalsky and Spitnik.'a
formula used by Tanford2' to describe titratioii of proteiiis. This asynip-
totic approach to the linear form may be readily deduced from the potential
in excess salt, as follows. When 6 1 (or when ApK 6 0.43) the func-
tion +Outer extends from R right to the surface of the polyion, since the re-
quirement +Outer < 1 is fulfilled everywhere. Utilizing the boundary eqs.
(23) and (32) for A+Outer we obtain
= (KLZ/2)BKl(KU) (42)
ApK = 0.434 4=Out er = 0.434 (KU/2)-'K,(KU)/K1(KU) (43)
and
which makes ApK depend on ams-'/'. At higher A, however, this linear
dependence breaks down, as has been observed even in the case of the mod-
erately charged protein polyions.22
I n order to compare eq. (41) to experimental results obtained for flexible
polyions we have yet to decide what is the length h of the equivalent cylin-
der, which determines the charge parameter A. As shown in Figure 2, the
main increase in the potential occurs very close to the surface of the poly-
ion; it seems therefore reasonable to assume that (& - 412) or ApK, is
PHOPEK'I'IES OF POLY ELECI'HOLY1'E SOLUTlOlU s 3247
determined by and large by the contour length of the polyion h = 21,
where I is the contribution of the monomer unit to the fully extended chain.
This choice has been adopted in calculating the theoretical ApK's, so that
for polyvinyl polymers, for example, X = 7.4 A. - l / l = 3.
I n Fig. 6 we have plotted results for ApK in polymethacrylic and poly-
acrylic acids measured in solutions which contained an excess of salt, for a
hundredfold change of salt concentrations; the theory appears to predict
reasonably well the experimental behavior. I n Figure 7 we have plotted
results obtained in solutions which contained relatively little or no added
salt and again the theory appears to give a reasonable description of the
behavior observed for a hundredfold change in concentration. At low
degrees of ionization, below Q: = 0.2, the agreement with the experimental
results becomes increasingly poor, and the latter in fact do not exhibit
the expected tendency to decrease linearly toward zero. This behavior
may be probably attributed to the strong coiling of the polyion which
makes untenable the fully extended cylindrical model.
V. Donnan Equilibria in Excess of Salt
1. The results of the Doniian distribution of a low molecular salt are
often characterized by the ratio
r = (mIs - m,)/vm,, (44)
where r is the salt excluded per unit macromolecular charge. Wheii the
ratio of the polymer to salt decreases to zero, the salt exclusion effect be-
comes a single-molecule phenomenon and as such is expected to reach a
constant value independent of m,,. I n other words, when vmp/mrs --t 0,
I' should approach a limiting value determined solely by the properties of
the single polyelectrolyte molecules and by the nature and the ionic strength
of the salt solution. The limiting value of r is easily calculated for the
ideal case, when the activities of the ions are equal to their concentrations.
I n view of our representation of activities by the surface concentration
[cf. eq. (4)] in the ideal case we have
m+R = vm, + m,
m-R = m,
(45)
On the other hand, taking into account the Donnan equilibrium of eq. (3),
r may be also written as
r = [(m+Rm-R)1'2 - m,)]/vm,
(46)
Combination of eqs. (45) and (46), with the neglect of terms higher than
vm,/m,, leads immediately to the well known result
liniump,m+,, r = [(vm, + ms)"2m,1'2 - m,l/vm, = 1/2 (ideal CBSC)
(47)
3248 2. ALEXANDROWICZ AND A. KATCHALSKY
An identical calculation may be carried out for systems described by the
aforementioned rule of additivity according to which
wR = cppvmp + m,
m-R = m,
which gives
limump/ms-l,-, r = qp/2 (rule of additivity)
(49)
At higher vm,/m, or amm/m, ratios r is no longer expected to remain con-
tant and is found to decrease from its limiting value to zero.2 I n the pres-
ent treatment, however, we shall restrict ourselves to low m,/m, ratios,
which is the case studied in the majority of the experimental reports. As
has often been observed, eq. (47) is generally not satisfactory for the de-
scription of the actually measured limiting values of I?. Equation (49)
provides a better description, yet it is not precise enough for a quantita-
tive description. Its weakness becomes more evident at high ionic
strengths when r is found to increase ~t r ongl y, ~~~~ whereas cpJ2 is a constant
quantity, which by definition [see eq. (-lo)] does not depend on the salt
concentration. It is therefore of interest to calculate r in a more syste-
matic manner on the basis of the theoretical treatment presented here.
2. The theoretical evaluation of r requires the calculation of ms only,
since the external salt concentration m', and the equivalent charge density
of the ionized groups vmp are specified in the experiment. On the basis of
the normalization eq. (10) and in view of the discussion presented in
section 111-1, we may write for m,
(50)
+ 2x kB$F [ &( KT) + I o ( K ~ ) KI( KIZ) / II( K&) 1 r d ~ )
Using the appropriate integration formulae'O and taking note of eq. (20),
and of the correlations V = mP-l and K% = 8rhXmt, (1 + q2/ 2) we obtain
as a result eq. (51).
m, = mIs{ I - q2/2 - (Kb)2vm,/8hmt, + (KE)vmP/4Xm',)
x B[ K~( KD) - I~(K~)K~(K~)/I~(KR) I ) (51)
I n deriving eq. (51) we omit b2p2/R2 which is proportional to (m,/m,)3.
If the limiting case of low m,/m, ratios is considered, the terms of the argu-
inent ( KR) go to zero while B becomes equal to - 1/Ko(~b) as has becn shown
before. The simplified rrsult for m, inay be iiow iiitroduccd into thcdefiiii-
tion eq. (44) to give the required expression for 1'
lini mm,ms-to r = ( l / i X) [ K ~ K ~ ( K ~ ) / K ~ ( K ~ ) + (Kb)2/2] ($2)
PROPERTIES OF POLYELECTROLYTE SOLUTIONS 3249
At higher m,/m, ratios a more complicated but analogous expression holds,
while for very high ratios, when the salt is no longer present in excess,
higher order terms than q2/2 have to be included, and the present approach
is no longer feasible. I n practice, however, detailed calculations show that
the limiting value of eq. (52) provides a reasonable approximation up to
about m,/m, 5 1. I n what follows we shall refer only to this limiting
value of r.
3. Equation (52) may be given the following simple physical interpreta-
tion. If the salt (or coion) concentration inside (m,) were to equal the ex-
ternal concentration (ms), then the exclusion factor I would equal zero.
The two factors which make for a smaller m, (and hence positive I) are the
total exclusion of the coions from the inner volume (viz., the term-a b2h in
eq. (50)) and the partial repulsion of coions from the outer volume (viz.,
the integral of +Outer over the outer volume) which are represented by the
second and first terms, respectively, on the right-hand side of eq. (52).
The magnitude of these effects may be also expressed in a simple way.
The calculation shows that, at very low ionic strengths and for all charge
densities of actual interest, Kb varies only between the limits of about
0. 64. 8. This makes the first and second term of the order of 1/4 X and of
0.3/4 A. On the other hand, we know also that the limiting value (calcu-
lated from Lifson and Katchalskys work4) of pp/2 at low polymer concen-
tration is 1/4 X with an increase of some 50% at higher concentrations.
This leads to the qualitative similarity between eq. (49) derived from the
rule of additivity and our theoretical eq. (52). At higher ionic strengths
however, the calculated Kb increase strongly and so do both terms of our
equation, leading to r values much higher than pp/2.
Equation (52) may be also compared to another description put forward
by Strauss and Ander.23 The latter have assumed that an electroneutral
central core, which roughly corresponds to our inner volume rb2h, is
totally excluded to the coions, while in the remaining outer volume the
salt is uniformly distributed. This should lead to the effect given by our
second term of eq. (52) and indeed, when Strauss and Anders eq. (7) is
transcribed to the present notation, it reads
r = mf, rb2h/v = (Kb)2/8A
An interesting situation arises when the polyelectrolyte potential is
sufficiently suppressed either by high ionic strength or by low charge density
so that the linearized potential +Outer may be used up to the surface of the
polyion, or when b = a. Using eq. (42) developed for this case and eq.
(30) we obtain for I
r = l/z + (Ta2h/v)mts
( 53)
which incalls that, except for the cffect of the excluded volume of the poly-
ion itself, r obeys the ideal law of cq. (47). This seems puzzling, since we
have not postulated that the electrostatic potential + vanishes and required
only that e may be linearized everywhere. The same result may be also
3250 Z. ALEXANDROWICZ AND A. KATCHALSKY
obtained in a different way, which throws light on the meaning of this
pseudo-ideal behavior. Using the alternative eq. (46) for r and combin-
ing it with the linearized normalization integrals of eqs. (9) and (10) we
obtain
.fyoukr (I + ~ o u t e r ) ~ ~ ] z - m,) N / z + ( m2h/ v) mS
This alternative derivation shows that although both m+R and m-R differ
from uniform distribution as indicated by the presence of the 4 terms, the
latter cancel out mutually in the final expression for r. I n other words, in
the linear case the counterions are attracted towards the polyion in the same
degree as the coions are repelled, so that the activity of the salt (a, = m+R-
mWR) remains unaffected. This rather unexpected behavior according to
which in certain cases the salt behaves ideally, or even in a sense more than
ideally (I > /2) because of the presence of the excluded volume term, has
been observed experimentally as shown below in Figure 9. We have
assumed here that the polyion is wholly impermeable to the small ions;
if it were not and a completely permeable behavior were exhibited, the
maximum value of r would be /Z. (In this case b in the equations should
be replaced by b - a.) The different real polyions might be well expected
to exhibit various intermediate modes of behavior.
4. The theoretical evaluation of r for polyions which are not fully
stretched rigid cylinders requires a further assumption regarding the value
of A. This implies some information on the effective length of the macro-
molecules. Since no convincing theory on the relation between viscosity
and molecular dimensions exists for polyelectrolyte solutions and since the
viscometric radius need not necessarily be the factor which determines the
electrostatic interaction, we prefer to derive from a colligative property
related to Doniian equilibria. As shown by Lifson and Kat~hal sky,~ the
osmotic coefficient of salt-free polyelectrolyte solutions pP is given by
and since @ = /3(m,X) therefore at a given polymer concentration (pP is
determined by X or vice versa.
The concept of (pP osmotically active counterions also retains its validity in
the presence of salt as shown in previous reports.-3 The effective value of
X derived from eq. (54) on the basis of experimental values of pP, may there-
fore be regarded as an adequate charging parameter for the calculations.
The semiempirical aspect of this procedure may be made more palatable
by the observation that in many cases of different flexible macroions, such
as the vinylic polyelectrolytes at sufficiently high degrees of ionization,
Xef f eot i ve is invariably found to be about twice the magnitude calculated for
the wholly stretched chain. We recall that the latter is defined by
325 1
0.1 4
0.1 2
0.1 0
-
1
OQ
- 0.00
-
\
U
9.
-
0.06
0.04
a
b
0 0 0- C
0
0 - m 3
I I
0. I 0.2 0.3 0.4
Q/ l i - l
Fig. 8. cp,(a/l), (the number of osmotically active ions per unit length of macroion,
as a function of the total (stoichiometric) number of such ions (a/l): (--) values
calculated from Lifson and Katchalsky's4 equation for cpp in salt-free solutions at y = 3
for ( a) Xeffeotive = Xstretahed, ( b ) Xeffeetive = 1.5 Xstretohed, ( c ) Xeffeotiye = 2Xstrmthed; experi-
mental results for (0) polyacrylates,2,17,s ( 0) polymethacrylate~,~~#2* ( 8) polyphos-
phates, ( 0) carboxymethyl cellulose,29." and (m) alginate~.3~
1 being the length per monomer of the fully stretched chain. On the other
hand, it was found that stiffer molecules, such as the substituted cellulose
derivatives, or polyelectrolyte salts of extremely bulky counterions, obey a
different relationship, with heffoctive = 1.3 &etched. This general behavior is
illustrated in Figure 8, in which we have collected the currently available
data on (pp. Since our procedure substitutes the actual potential of flexible
niacroions-which is not cylindrical-by a hypothetical cylindrical potential
and corrects for the approximation by the use of Xeffective, the latter will
clearly depend on the physical property considered, since different proper-
ties depend in a different way on potential. The colligative properties of the
small ions are determined by the volume integrals of the type J e *@ dV,
and all of them are expected to give the same value of Xettective. The
outstanding feature of these volume integrals is that the outer layers, in
which e+/kT is very small, still play an important role in the integral since
the total volume of these layers (which increases with r) is relatively large.
Consequently, the effective cylinder length which determines heffective of the
osmotic properties, will lie somewhere between the contour length and the
actual end to end distance. I n contrast the potentiometric potential-
which (as has been pointed out above) is closely related to the immediate
surrounding of the polyion-is determined mainly by the contour length
of the polyion and described by hstretched.
I n conclusion we would like to emphasize that whatever be the choice of
hetfective for a particular polyion, this value was found to describe the colliga-
3252 2. ALEXANDROWICZ AND A. KATCIIALSKY
0.8, I I I I
I
0
0 02 0.4 0.6 0.8
f l
Fig. 9. The dependence of the salt exclusion per polymer r on the salt concentration
rn'* (in moles/l.): (-)calculated for Xefreetive = 4; 2.4 and 1.25, respectively, and with
a polyion radius a of ( a) 6 A. and ( b ) 5 A.; experimental results obtained with PAA at
degrees of ionization 01 of ( A) 0.8,(0) 0.3, and ( 0) 0.1. (Note that heffectioe reevaluated
from experimental results are slightly different from those found previously.2)
0.6
0.4
I I I I I I
0.2
I I I I I I
0. 2 0.4 0.6 0.8 1.0 1.2
6
Fig. 10. The dependence of the salt exclusion per polynier I' on the salt concentration
m'. (in moles/l.: (-) calculated for Xeffeetlre = 6 with ionic radii a of ( a ) 5 A. and ( b )
4 A. and for Xeffective = 3.5 with ionic radii a of ( a) 6 A. and ( b ) 5 A.; experimental
results of Strauss and AnderZ3 for (0) Na polyphosphate, ( 0) Li polyphosphate, and
( 0) tetramethylammonium polyphosphate.
PROPERTIES OF POLYELECTROLYTE SOLUTIONS 3253
tive properties at all ionic strengths of the polymer and of the salt (other-
wise of course the concept of Xeffectivc would become valueless). The
changes in the end to end distance which presumably occur upon variation
of the ionic strength, do not therefore influence markedly the effective
cylinder length. This indicates that fairly long segments of the polyion
retain their conformation at different ionic strengths.
I n Figures 9 and 10 we have drawn theoretical values of I ' , based on
Xeffeative which are calculated from eq. (54), on the basis of the experimen-
tally determined (pp. The (pp values of the polyphosphates were specially
measured for the purpose of this work. The results at m, = 0.02 were (pp
= 0.13 for Li and Na polyphosphate and, at m, = 0.014, (pp = 0.22 for
TMA polyphosphate. The values Xeffective = 6.6 and 3.5 were adopted
accordingly. The theoretical r are compared in Figure 10 to the experi-
mental results obtained by Strauss and Ander23 with three different poly-
phosphate salts. I n Figure 9 the r are compared to results obtained by
us with sodium polyacrylate at three degrees of ionization. The experi-
mental technique and the results for 'pp, from which Xeffective were estimated
are described elsewhere. 2* 24 Considering the fact that no freely adjustable
parameter is used here, we consider that the agreement between the cal-
culated and measured r values is satisfactory.
VI. Donnan Osmotic Pressure
1. The hydrostatic pressure required to maintain equilibrium of a poly-
electrolyte solution with an external solution through a membrane per-
meable to both salt and water, is called the Donnan osmotic pressure. The
Donnan osmotic pressure of an elementary volume V = l/np, comprising a
single macromolecule and numerous small ions and at equilibrium with ex-
ternal salt solution of concentration mf s, is obtained by combining eqs.
(14) and (Z)
rcal c V/ kT = 1 + vB2/8XI, 2(~R)
(55)
where R is the integration constant plotted in Figure 3 and KR is determined
by the relative concentrations mts and mp. For polyions of given charge
density and at constant external salt concentration KR is simply proportional
to 1'
where
u = (8Xmf ,/V)1/2
Under those conditions the second term on the right-hand side of eq. (55)
depends on V only and is denoted as p(V)
For many purposes it may be assumed that no fluctuations occur and that
the volume elements are all equal to the average value V. I n this case the
3254 Z. ALEXANDROWICZ AND A. KATCHALSKY
product of the macroscopic pressure ( TO) and a unit volume u, may be ob-
tained by summing over the n, elements of the volume
~o v / k T = C ~o a i c P/ kT = c [1 + p(V)] = n,~C,icV/kT
fip n p
since
-
n,V = v = 1
TO = Tcalc (58)
or the macroscopic pressure in the absence of fluctuations is equal to that
calculated for a single volume element. Since the Donnan osmotic pres-
sure depends strongly on the absolute magnitude of V, the approximation of
equally sized cells is not precise enough. We have therefore to consider
explicitly the fluctuation of the volume per macromolecule V. (The
fluctuations are negligible in salt-free solutions when the electrostatic re-
pulsion keeps the macroions in relatively fixed position; they become im-
portant, however, when the macroions are largely screened by the presence
of excess salt.2s) Let us denote the fluctuating volume of the ith element by
Vi, with the condition C V, = 1. The activity of the relatively numerous
salt ions is assumed to be constant and equal for all the fluctuating volumes,
so that the osmotic pressure in the element ( TJ is related to Vi by the theo-
retical eq. (55), or
n p
~i Vi / kT = 1 + cp(Vi) (59)
Let the real macroscopic pressure be T ; then the work of a single fluctuation
is given by (T - Ti)V,. The total work of fluctuation of the np elements
at equilibrium is zero, so that
C (T - 7ri)Vi = TC vi - C Ti Vi = 0
n p np n p
or
together with eq. (59) weobtain
cp(Vi) may be developed in Taylor series, up to the second term, around the
average value P
cp(V,> = cp(P) + 6i(P'(P) + 6,2P"(P)/2
where 6, is the derivation from the mean value 6, = 'Irt - p.
of cp(V,) over all the elements then gives
Summation
(62)
c u?(V*) = n,cp(V) + d( P) c 6i + cp"(P!/2 c 6i2
n p n p nP
PROPERTIES OF POLYELECTROLYTE SOLUTIONS 3255
The sum of the linear fluctuations 6i at equilibrium is zero, while 6,?:
according to a well known result of fluctuation theory, is
= ?Lp1;l/(8?G/bT.2)t.
= n,kl/ -(br, /dV)v
With these resultP eq. (61) becomes
r / kT = np + n, p( Y) 4- [ n p p ( ~ ) k T / - 2 ( b r / b V) ~ ] (63)
Comparing eq. (63) to eqs. (58) and (55) we observe that the real pressure
r exceeds To (or rcelr) by the last term on the right-hand side of eq. (63).
To calculat,e p(V) we use the asymptotic formula for large values of
KR:O
I I 2( ~R) N e%R/2rKR = e. 2uv/2/2r~4V1/2
so that
p(V) N ( v B ~ ~ R u / ~ X ) V / ~ ~ - ~ ~ ~ / ~
and with this approximation obtain
p(V) = - [U~(V)/V1/*][l - (1/ 2uV/ ?)]
v - KRp(V)/V (65)
and
p(V) = [u2p(V)/2V][l - (1!2~V/) - (1/4u2V)]
(66)
_L (KR)2p(V)/2V2
while eqs. (65) and (59) give an estimate for ( br / dV)
- d( r/ RT) / dV = 1/ V2 + p(V)/V2 - pO(T;)/V
= [I f (1 + KR) ( P( V) I / V~ (67)
Introducing eqs. (66) and (67) into eq. (63) leads to the required expression
for the macroscopic osmotic pressure:
r / kT = np + npp( P) + n, ( ~R) ~p( P) / 2 11 + ( 1 + KR)p(p)] (68)
The Donnan osmotic pressure is usually plotted as the reduced pressure
For the monomolar scale of con- ( r / c ) versus the polymer concentration.
centration, where
m, = m,Z = Z/ VN
N being the Avogadro number, eq. (68) becomes
(r/RT)/m,moles/l. = 1 / ~ + (1 + (KR)2/2[1 + (1 + .R)~(V)I}~(V~/Z
(68)
3256 Z. ALEXANDROWI CZ AND A. KATCFIATSKY
0.1 5
0.1
\
F
c
E
\
-
0.05
I
1
A I
rnl =0.001 mol e / I.
m m
Fig. 11. The dependence of the reduced Donnan osmotic pressure (r/RT)/m,, on
the polymer concentration mm in monomoles/l.: (-) calculated for Xeffective = 4
and a = 5 A,;
(- -) calculated as above, but corrected for Azm, = 0.03 m,; (---.-)
calculated from the additivity rule;2 ( A) experimental results obtained2 for polyacrylic
acid of (Y = 0.8 at salt concentrations wi', = 0.001, 0.01, and 0.1 mole/l.
Except for a relatively minor variation of the constant B with m', the func-
tion p(V), as defined by eq. (57), is determined by KR. The second term
on the right-hand side of eq. (68') (which expresses the electrostatic con-
tribution to T) is seen therefore to be a function of KR or of the ratio of salt
and polymer concentrations. Since p(V) is proportional to Y, cp(V)/Z
does not depend on the molecular weight.
With the commonly used polymer concentration c, (in grams/100 ml.)
and the pressure n expressed in grams/cm.2, the eq. (68') becomes
r/cP = (2.4 X 106/M,) l /Z f ( 2.4 x 105/~,)
{1 -I- (~E>'/2[1 f (1 f KR)P(V)I]P(V)/Z (68")
where M, is the molecular weight of the monomer and
KR = (8XM,/10a)1/2(m',/c,)'/'
Following the reasoning of the preceding section the effective values of
A (which are determined from experimental pp values on the basis of eq.
(54)) are t80 be used in calculating the osmotic pressure.
2. Using eqs. (68') and (68") we have calculated t,he reduced osmotic
pressure for polyacrylic acid (PAA) of a = 0.8 and for a fully neutralized
(a = 1) carboxymethylcellulose (CMC) of a degree of substitution D.S. =
PROPERTIES OF POLYELECTROLYTE SOLUTIONS 3257
110 I I I
; I m; =0.002 mole/L
,P
c p ( g r n / 100c r n ~)
Fig. 12. The dependence of the reduced Donnan osmotic pressure ( r/cP), on the poly-
mer concentration cp in g./100 cm.3: (--) calculated for Xeffeotive = 0.8 and a =
6 A, ; (- -) as above, but corrected for Azc, = 20 cp. Experimental results obtained by
Inagaki and HiramiZ6 with methyl cellulose of D.S. = 0.45 at salt concentrations of (0)
0.002, ( 0) 0.004, ( 0) 0.02, and (V) 0.05 mole/l.
0.45 and dd, = 435. The effective charge parameter for CMC is Xeffective
N 1.3 &etched N 0.8 (Fig. 8 and other resultsz9) while for PAA, at a! = 0.8,
Xeffective e 1.8 &etched
I n Figures 11 and 12 these
values are compared to the experimental results, which have been reported
by one of us2 and by Inagaki and HiramLZ6 The overall agreement between
theory and experiment is moderately satisfactory. The theory predicts
that at low cP/ mf s ratios the virial term will decrease towards zero so that a
nonlinear plot of T/ C, versus c, will result. The experimental results in-
dicate that the decrease in T / C , is smaller than that predicted theoretically,
but they do provide a clear enough confirmation of the nonlinear behavior
at low ionic strengths. It should be realized that this deviation from linear
behavior is of basic importance in relation to the linear extrapolation of
r/cP results to zero concentration for the evaluation of molecular weight.
I n our treatment we have neglected the nonelectrolytic second virial
coefficient which is always present in polymer solutions, except at the e
temperat~re.~ This coefficient, commonly denoted as Az, should be added
to eqs. (68) and (68). I n order to estimate its magnitude we shall utilize
the fact that the theoretically evaluated electrostatic virial term depends
strongly on the ionic strength, being roughly proportional to rn.-l. On the
4 (as in section v-4).
3258 Z. ALEXANDROWICZ AND A. KATCHALSKY
other hand, the coefficient Az does not depend markedly on the composition
of the solution and is determined by and large by the excluded volume of the
polyion. The latter is affected strongly by the degree of ionization hut not.
strongly, if at all, by the ionic strength, as indicated by the validity of the
present model according to which a nearly fully st,retrhed cylinder of con-
stant length is seen to represent the macroion at all ionic strengths. r H i ~ >
intercept, at mS-l = 0, of the plot of some average values of the experimen-
tal slopes d(r/c, )/dc, versus mS-l should therefore give an estimate of the
magnitude of Az. Having thus determined Az we have added the terms
A2mm or A&, to eqs. (68') or (68"), respectively; the result is described
by the broken line in Figures 11 and 12 and is seen to bring the calculated
curves closer to the experimental results.
3. I n conclusion, some remarks may be made regarding the description
of the osmotic pressure in the total ra.nge of polymer concentrations which
includes solutions of high polymer-to-salt ratios, when the salt is no
longer in excess. I n the latter case the parameter R which determines
~ ( K R ) can be no longer evaluated from t,he simplified eq. (30'), which was
found to hold up to KR values of 2-3. This put.s the limit of the treatment
at m,/m, ratios smaller than 5-10 or 2-4 for polyacrylics and carboxy-
methyl celluloses, respectively. Above t,his level the more exact eq. (30)
could be used, but in this range the theory ceases t,o be valid due to the
neglect of q4/12 and higher t,erms in the basic expression for n[eq. (14)].
At high m,/m, ratios the r/m,,, lines become concave down and eventually
reach the limiting value for salt-free solutions ( r/ RT) / m, = p,. The
theoretical description in this region is given by the more complete (and
much more complicated) calculation in which no assumption of excess salt
is made; but, as the result of t,his calculat.ion has shown,2 an equivalent and
much simpler description of tthe osmotic pressure in this region is provided
when the additivity rule [eq. (48)] is used in conjunction with eq. (14).
The result at low %/m, ratios is
(.r/RT)/m, = l/Z + a2qp2mm/4m', (69)
At higher rnm/mfs ratios the required concave down curve is obtained, and
the limiting value of 9, is ultimately reached.? The portion of the curvc
which obeys eq. (69) is linear only in so far as vp is truly constant. Since,
however, pp decreases to a certain degree with the polymer concentration,2*A
a somewhat concave up curve is obtained at low m,/m', ratios. The r/ m,
curve in the total range of polymer concentrations 0 6 m,/m, 6 03 is
therefore S-shaped. The experimental results are usually measured in the
middle and lower portion of the S and this fact probably explains the often
reported linear behavior, which contradicts the findings obtained from the
present theory on the one hand, from the additivity rule on the other, and
confirmed experimentally by several workers.2~26~28 The theoretical treat-
ment predicts however that the electrostatic contribution to the second and
higher virial coefficients vanishes when m,/m, - 0, whereas according to
the additivity rule the contribution reaches a finite value since pp -+ lj2X
PROPERTI ES OF POLYELECTROLYTE SOLUTIONS 3259
when mm +- 0. The experimental data available at present do not permit
a decision t o be reached on this point.
I n fact in the whole range of mJms ratios the description provided by
the simple additivity rule fits the experimentally determined osmotic pres-
sures as satisfactorily as do the more complicated theoretical calculations;
the latter, however, constitute part of a more comprehensive framework
which derives all equilibrium properties from the electrostatic potmtial
of the polyions.
References
1. Katchalsky, A., and Z. Alexandrowicz, J . Polymer Sci., Al , 2093 (1963).
2. Alexandrowicz, Z., J . Polymer Sn., 56,97, 115 (1962).
3. Kotin, L., and M. Nagasawa, J . Chem. Phys., 36,873 (1962).
4. Lifson, S., and A. Katchalsky, J . Polymer Sci., 13,43 (19.53).
5. Langmuir, I., J. Chem. Phys., 6,893 (1938).
6. Verwey, E. J. W., and J. Th. G. Overbeek, Theory of the Stability of Lyophobic
7. Marcus, R. A., J . Chem. Phys., 23,1057 (1955).
8. Alfrey, T., P. W. Berg, and H. Morawetz, J . Polymer Sci., 7,543 (1951).
9. Fuoss, R. M., A. Katchalsky, and S. Lifson, Proc. Natl. Acad. Sci. ( U. S.), 37,
10. McLachlan, N. W., Bessel Functions for Engineers, Oxford Univ. Press, London.
11. Rutgers, A. J ., Physical Chemistry, Interscience, New York, 1954, p. 437.
12. Cox, R. A., and A. R. Peacocke, J . Chem. SOC., 1956,2499.
13. Samelson, H., Dissertation, Columbia University, 1952.
14. Gregor, H. P., and M. Frederick, J. Polymer Sci., 23,451 (1957).
15. Oth, A., and P. Doty, J . Phys. Chem., 56,43 (1952).
16. Arnold, A,, and J. Th. G. Overbeek, Rec. Trav. Chim., 69,2 (1950).
17. Kern, W.: 2. Physik. Chem., A184,197 (1937).
18. Katchalsky, A., and P. Spitnik, J. Polymer Sci., 4,432 (1947).
19. Kagawa, I., and H. P. Gregor, J. Polymer Sci., 23,477 (1957).
20. Katchalsky, A,, N. Shavit, and H. Eisenberg, J . Polymer Sci., 13,69 (1954).
21. Tanford, C., S. A. Swanson, and W. S. Shore, J . Am. Chem. Soc., 77,6414 (1955).
22. Foster, J. F., in The Plasma Proteins, F. W. Putnam, Ed., Academic Press, New
23. Strauss, U. P., and P. Ander, J . AWL. Chem. SOC., 80,6494 (1958).
24. Alexandrowicz, Z., J . Polymer Sei., 43,337 (1960).
25. This has been suggested to us, by Prof. U. P. Strauss.
26. Inagaki, H., and M. Hirami, 2. Elektrochem., 63,419 (1959).
27. Eisenberg, H., and D. Woodside, J . Chem. Phys., 36,1844 (1962).
28. Orofino, T. A., Rec. Trav. Chim., 78,434 (1959).
29. Alexandrowicz, Z., unpublished results.
30. Kagawa, I., H. Yamada, and I. Imai, J . Chem. SOC. Japan Znd. Chhem. Sect., 53,
31. Katchalsky, A., R. E. Cooper, J . Upadhyay, and A. Wasserman, J . Chem. SOC.,
Coolloids, Elsevier, New York, 1948, p. 92.
579 (1951).
2nd Ed., 1955, pp. 201,204,220,221.
York, 1960, Vol. I, p. 188.
I20 (1950).
1961,5198.
R6sum6
Ce travail traite des propri6Gs d6quilibre de solution de poly6lectrolyte renfermant un
Dane ce cas, la loi simple dadditivit6 utilishe
On a d b
excb de sel de faible poids mol6culaire.
antArieurement, tombe en d6faut pour d6crire les r6sultats exp6rimentaux.
3260 Z. ALEXANDROWICZ AND A. KATCHALSKY
lors entrepris un traitement d6taillB bas6 sur line solution approximative de 16quation de
Poisson-Boltzmann. Le calcul est bas6 sur une subdivision du potentiel electrostatique
en deux parties correspondant A deux rBgions: (1) une region interne dam le voisinage
immBdiat du polyion, libre de co-ions et d6crite par lequation de Poisson-Boltamann
en absence de sel libre, et ( 2) une region externe, s6par6e du macro-ion central et traitke
de faCon ad6quate par une approximation suivant Tlebye. On a obtenu une solution
analytique pour le potentiel Blectrostatique et on a utilisd pour la description thBorique
du comportement potentiomBtrique, la distribution de sel et la pression osmotique de
Donnan. Les valeurs prBdites se comparent favorablement avec les rBsultats mesurds
dans un large domaine de conditions expBrimentales.
Zusammenfassung
I n der vorliegenden Arbeit werden die Gleichgewichtseigenschaften von Polyelektro-
lytlosungen mit einem Uberschuss an niedermolekularem Salz behandelt. I n diesem
Fall versagt das fruher mitgeteilte einfache Additivitatsgesetz bei der Beschreibung der
Versuchsergebnisse. Es wurde daher eine auf einer Naherungslosung der Poisson-
Roltzmann-Gleichung beruhende eingehende modellmassige Rehandlung durchgefuhrt.
I)ie Berechnung beruht auf einer Unterteilung des elektrostatisrhen Potentials in zwei,
xwei Bereichen entsprechenden Teile: ( 1 ) Ein innerer Bereich in der unmittelbaren
Xachbarscliaft des Polyions, frei von Coionen und ini salz-freien Fall durch die Poisson-
Boltzmann-Gleichung beschrieben und ( 2 ) ein ausserer Bereich, von Zentralmakroion
abgeschirmt und durch eine Debye-Naherung zu behandeln. Fur das elektrostatische
Potential wurde eine analytische Losung erhalten und zur theoretischen Beschreibung
des potentiometrischen Verhaltens, der Donnan-Verteilung des Salzes und des Donnan-
schen osmotischen Druckes angewendet. Die berechneten Werte stimmen uber einen
grossen Bereich der Versuchsbedingungen mit den Messergebnissen gut iiberein.
Received Septembcr 19, 1962