MEANACTIVITY OF POLYELECTROLYTES

COEFFICIENT 407 1

Mean Activity Coefficient of Polyelectrolytes. XI. Activity Coefficients of

Various Salts of Polyacrylic Acid and Carboxymethylcellulose1

by Kiyotsugu Asai, Katsuhiko Takaya, and Norio Ise

Department of Polymer Chemiatry, Kyoto Univeraity, Kyoto, Japan (Received February 19, 1969)

The osmotic and (mean) activity coefficients of propionates, polyacrylates (PAA), and carboxymethylcellulose
(CMC) salts of various gegenions in aqueous media have been determined a t 25’ by means of the isopiestic
vapor pressure measurement. As had been found in previous works, a marked specificity of gegenions was
noted. For propionates, the osmotic and activity coefficients decreased in the order N(n-C4H9)4 > N(CH3)4
> K > Na > Li. For polyacrylates a t high degrees of neutralization, the order was N(n-C4H9)4 > N(n-CaH?)d
> N(C2H5)4 > N(CH& > Li > K > Na. I n the case of a CMC sample of a higher degree of substitution
(DS = 0.95) the order was N(n-C4H9)4 > N(CK& > Na. Lowering of the DS value changed the order. At
DS = 0.78, NR4(R = alkyl) cs K > Na > Li and a t DS = 0.68 N(CH8)d > Na > N(n-C4H9)4. The order Na
> N(n-C4H9)4 was also found for polyacrylates a t a degree of neutraliaation of 0.2. These results could be
accounted for in terms of the structural influence of ions on water by taking into consideration balancing of two
“counteracting” effects of hydrophobic and ionic groups. The electrostrictional structure formation effect,
which was predominant a t a highly charged state, could be screened off by the cage-like structure formation
of hydrophobic parts a t low degrees of neutralization or substitution. Comparison of the PAA and CMC ions
suggested that the former is more hydrophobic than the latter.

Introduction polyacid solution thus obtained was neutralized with the

In previous papers from this laboratory,2 the mean
activity coefficients of a variety of synthetic polyelec-
trolytes having various gegenions have been measured.
The results have shown that the mean activity coeffi-
cients are largely influenced not only by the character of
macroions but also by that of gegenions; the specificity
of macroions and gegenions was successfully, though
qualitatively, accounted for in terms of the structural
influence of ions on water. Furthermore, it was con-
cluded that the solvent-solute interaction is more im-
portant than the gegenion association, though the re-
verse was often believed to be true. While we intend to
extend the measurements to biologically important
polyelectrolytes, we want to report here the mean activ-
ity coefficient data of various salts of polyacrylic acid
(PAA) and carboxymethylcellulose (CMC) . No other
types of salts than the sodium salt of PAA3l4have been
measured previously. The salts of CMC were thought
interesting because the CMC molecule contains a
number of polar groups and is believed to be compara-
tively stiff.
Experimental Section
The NaPAA was a gift from the Toa Gosei Chem-
icals Co., Nagoya. Its weight-average degree of poly-
merization was 640. T h e NaCMC was kindly fur-
nished from the Daiichi Kogyo. The degree of poly-
merization was estimated by the supplier to be about
400. The NaPAA and NaCMC solutions were puri-
fied by passing through cation- and anion-exchange
resins. Propionic acid was twice distilled at reduced
pressure in a nitrogen atmosphere (42 mm, 65.1’). The
aid of conductometric titration with an aqueous solution
of reagent grade LiOH, NaOH, KOH, (CH&NOH,
(C2Hs).SOH, (n-C3H7)4NOH, or (n-C4H9)4NOH.
The polymer concentration was determined by the ti-
tration data.
The isopiestic measurements were carried out at 25 f
0.005” by using an apparatus and experimental pro-
cedures described previously.6
Results and Discussion
The measured concentrations of the solutions of PAA
salts and potassium chloride (refeyence electrolyte) in
isopiestic equilibria are listed in Table I. The corre-
sponding data for propionates and CMC salts are given
in Tables I1 and 111,respectively.
The practical osmotic coefficient of the electrolyte
wm calculated by the condition of equal solvent vapor
pressure, as previously d e ~ c r i b e d . ~The osmotic co-
efficients of potassium chloride solutions were taken
from the literature.B The osmotic coefficients of pro-
(1) Presented at the 21st Annual Meeting of the Chemical Society
of Japan, Tokyo, Japan, April 1968, and a t the 17th”AnnualMeeting
of the Society of High Polymers, Japan, May 1968.
(2) (a) N. Ise and T. Okubo, J . Phys. Chem., 71, 1886 (1967); (b)
N. Ise and T. Okubo, ibid., 72, 1361 (1968); ( 0 ) N. Ise and K. Asai,
{bid., 72, 1366 (1968); (d) N. Ise and T. Okubo, ibid., 72, 1370
(1068).
(3) N. Ise and T. Okubo, ibid., 69, 4102 (1965).
(4) N. Ise and T. Okubo, ibid., 71, 1287 (1967).
( 5 ) T. Okubo, N. Ise, and E’. Matsui, J . Amer. Chem. Soc., 89, 3697
(1967).
(6) R. A. Robinson and R. H. Stokes, “Electrolyte Solutions,”
Butterworth and Co., Ltd., London, 1959, pp 476, 481.

Volume 73, Number 12 December 1969

 4072 K. ASAI,K. TAKAYA,
AND K, ISE

Table I : Concentrations of Isopiestic Solutions of Potassium Chloride and Polyacrylates a t 25""

1. PAA Salts at a Degree of Neutralization = 1

mKCl Li K N(CH3)r N(CzHs)r K(n-CaH7)4 N(n-CaHs)a
0.0962 0.504 0.550 0.352 0.326 0.300 0.266
0.123 0.667 0.731 0.448 0.408 0.375 0.325
0.151 0.809 0.872 0.542 0.491 0.450 0.392
0.164 0.869 0.933 0.669 0.612 0.564 0.496
0.200 1.03 1.10 0.754 0.685 0.623 0.562
0.241 1.18 1.26 0.945 0.858 0.773 0.707
0.332 1.56 1.65 1.23 1.11 0.986 0.922

2. NaPAA and N(n-C4Hg)4PAA at Degrees of Neutralization of 0.2, 0.4, 0.6, and 0.8

nwci
7

0.2
-NaPAA
0.4 0.6
-- 0.8
,-.----
0.2
N (n-CaHe)aPAA-----------.
0.4 0.6 0.8
0.105 0.248 0.320 0.430 0.523 0.267
0,139 0.331 0.414 0.550 0.668 0.377 0.338 0.356 0.377
0.216 0.503 0.606 0.792 0.969 0.626 0.471 0.481 0.503
0.268 0.628 0.733 0.958 1.17 0.825 0.560 0.560 0.578
0.342 0.819 0.923 1.19 1.43 1.11 0.683 0.660 0.671
0.428 1.03 1.13 1.45 1.73 1.46 0 828 0.778 0.779
0.475 1.14 1.23 1.55 1.84 1.62 0.891 0.824 0.821
0.543 1.31 1.42 1.73 2.03 1.86 0.995 0.901 0.892
0,695 1.63 1.72 2.10 2.41 1.24 1.07 1.05
0.851 1.95 2.07 2.46 2.76 1.47 1.23 1.17
1.36 2.75 2.93 3.40 3.64 1.72 1.56
1.53 3.00 3.19 3.69 3.87 1.92 1.71
2.01 3.62 3.86 4.36 4.47
a mKc1 is in molality; polymer concentration is in equiv/1000 g of water.

Table I1 : Concentrations of Isopiestic Solutions of

Potassium Chloride and Propionates a t 25"

mIm Na Li K N(CHs)4 N(n-C4H9)4

0.144 0,143 0.145 0,142 0.131 0.128 1.2

0,188 0.185 0.187 0.185 0.169 0.165
-8
0.420 0.386 0.405 0.381 0.364 0.347
0.880 0.800 0.836 0.777 0.729 0.660
10
. Na
Li
pionates (+) are given in Figure 1, together with the +
values of the sodium salt reported previously (given by 0 . 8 U - - l I.o
the filled circles).' The osmotic coefficients of poly- 0 0.2 0.4 0.6 0.8
m
acrylates (4J*are given in Figure 2. The +E values for
Figure 1. Osmotic coefficients of aqueous solutions of
NaPAA were obtained from the results previously pub- N(n-C4&)*-, N(CH3)4-, K-, Na-, and Li propionates (25').
lished by using the observed value of the polymer a: data for the sodium salt taken from the work cited in ref 6.
charge f r a ~ t i o n . ~Figure 3 gives the t # ~as
~ a function of
polyelectrolyte concentrations for salts of CMC of a de-
gree of substitution (DX) of 0.95 (carboxymethyl whereas the reverse was the case in Figures 1 , 2 , and 3.
groups per glucose unit). From Figures 1, 2, and 3, it Figure 6 gives the +* values of sodium salts of the poly-
is seen that alkali metal salts of electrolytes have lower (7) Taken from ref 6,p 484,Appendix 8.10.
osmotic coefficient values than tetraalkylammonium (8) The $a valucs were calculated on the assumption that the elec-
salts. For CMC salts having lower DX values, how- trolyte is fully dissociated. For polyelectrolytes, it is possible to
define another osmotic coefficient on the basis of the number of free
ever, the situation is different; as shown in Figure 4,a t gegenions, which has been denoted by 4 without suffix in a series of
+
DX = 0.78, the values of the tetraalkylammonium our work. We note that it is not necessary to distinguish between
6 and 4. for simple electrolytes, since the so-called gegenion associac
salts fell on a curve and were as large as those of KCMC. tion does not so markedly occur for this kind of electrolytes as for
It is seen from Figure 5 that at DX = 0.68 N(n-ChHa)r polyelectrolytes. We further note that the mean activity coemcient
y* to be discussed in the present paper corresponds to 4s by the
CMC showed smaller values than N(CH3)&MC,
C#J~ fundamental thermodynamic relation, but not to 4.

The Journal of Physical Chemistry

MEANACTIVITY OF POLYELECTROLYTES
COEFFICIENT 4073
~
~~ ~

Table I11 : Concentrations of the Isopiestic Solutions of Potassium Chloride and Salts of Carboxymethylcelluloses at 25""

1. CMC (DS = 0.78) 2. CMC (DS = 0.78)

mKCl Na K Li mxc I N (CHs)4 N (Ca&)c

0.143 0.333 0.239 0.391 0.155 0.260 0.276

0.176 0,456 0.329 0.493 0.195 0.328 0.345
0.219 0.598 0.425 0.636 0.255 0.400 0.419
0.305 0.741 0.524 0.783 0.336 0.535 0.553
0.424 0.964 0.676 1.03 0.459 0.740 0.762
0.623 1.38 0.924 1.47 0.665 0.964 0.997
0.956 1.99 1.30 2.15

3. CMC (DS = 0.95 and 0.68)

0.108 0.364 0.271 0.243 0.258 0.228 0.293

0.128 0.430 0.325 0.288 0.308 0.268 0.340
0.209 0.637 0.472 0.406 0.477 0.386 0.479
0.244 0.749 0.546 0.466 0.566 0.446 0.550
0.268 0.840 0.616 0.520 0.621
0.338 1.01 0.722 0.601 0.767 0.581 0.716
0.427 1.24 0.855 0.703 0.927 0.689 0.854
0.493 1.43 0.987 0.794 1.07 0.747 0.979
0,672 1.80 1.21 0.972 1.35 0.914 1.21
'mxcl is in molality; CMC concentration is in equiv/1000 g of water.

I
1.4c os=o.'7*
I Bu I

Figure 2. Osmotic coefficients of aqueous solutions of Figure 4. Osmotic coefficients of aqueous solutions of
N(n-C4H~)4-,N(n-CsH&, N(CzH&, N(CH&-, Li-, K-, N(n-C4Ho)4-,N(CHs)4-, K-, Na-, and LiCMC at a degree of
and Na polyacrylates (25'). substitution of 0.78 (25').

acrylic acid a t degrees of neutralization of 0.2, 0.4, 0.6,

and 1.0 and of carboxymethylcellulose samples a t ap-
proximate degrees of substitution of 0.7, 0.8, and 1.0.
For both PAA and CMC, the & becomes larger as the
charge density on the polymer chain decreases.
The mean activity coefficient was calculated using
0 "
the Gibbs-Duhem relation, as reported previously.4
The assumptions involved in the calculation of the co-
I I I I efficient of the polyelectrolytes were, again, that (1) the
0 0.5 1.0
m cube-root rule holds down to infinite dilution and (2)
Figure 3. Osmotic coefficients of aqueous solutions of
the polyelectrolytes have the same activity coefficient
N(n-C4H&, N(CH&, and NaCMC at a degree of a t infinite dilution (TO*), irrespective of the gegenion,
substitution of 0.95 (25"). the degree of substitution, or the degree of neutraliza-
VoZume 78, Number 18 December 1960
 4074 K. ASAI,K. TAKAYA,
AND N. ISE

DS = 0.68

g-I l -

0 0.5 1.0 -I 3-

Figure 5. Osmotic coefficients of aqueous solutions of a

N(CH&-, N(n-C4Hg),-, and NaCMC a t a degree of substitution
of 0.68 (25'). -1.5 06 07 08 09 1.0 II
m

I I No-Salt

!
-0.2 -x-x-x -x4- - xc*
Bu

Pr
*xo
....*
x
-cn

--1.0
O , ~

06 0.8 I.o I.2

Figure 6. Osmotic coefficients of sodium salts of carboxy-
methylcellulose and polyacrylic acid a t various degrees of
neutralization and of substitution (25'). CMC, 0.7,0.8, and
1.0 denote the samples a t degrees of substitution of 0.68, 0.78,
and 0.95,respectively. 0.2,0.4, 0.6, and 1.0PAA denote the
degrees of neutralization of 0.2, 0.4, 0.6, and 1.0,respectively,
1 I I I I and tetraalkylammonium salts of the polyacrylic acid,
0.4 0.6 0.8 1.0 1.2
m
1
'
3 respectively. The cube-root rule is seen to hold a t low
Figure 7. The cube-root plot of the activity coefficients of
propionates (25 ').
tion. Obviously the second assumption is questionable
and will be considered in the latter part of this paper.
Figure 7 gives the activity coefficients of propionates
as a function of the cube root of electrolyte concentra-
tion. It is seen that the cube-root rule is not valid in
13'
Figure 8. The cube-root plot of the activity coefficients of
polyacrylates at a degree of neutralization of 1.0 (25').
the concentration range studied. Furthermore, the
activity coefficient decreased in the order
K = Na > Li (A)
and
N(n-CdHa)r > N(CHa)4 (B)
The order (A) is the same as found for acetates,loand is
the reverse of that observed for polyvinyl sulfates, poly-
styrenesulfonates, polyethylenesulfonates, and poly-
phosphates.2 The order (B) was also found for all these
polyelectrolytes examined so far2 and for tetraalkylam-
monium halides in a dilute region." Figures 8a and 8b
give the mean activity coefficients of alkali metal salts
concentrations. The upper bound of the range of fit
(9! For earlier references on the cube-root rule of the activity coef-
ficient of electrolytes and for the related problem, see H. S. Frank
and P. T. Thompson, "The Structure of Electrolytic Solutions,"
W. J. Hamer, Ed., John Wiley and Sons, Inc., New York, N. Y.,
1969,Chapter 8.
(10) Reference 7,pp 492,494.
(11) (a) S. Lindenbaum and G. E. Boyd, J. Phys. Chem., 68, 911
(1964); (b) W. Y. Wen, S. Saito, and C. M. Lee, ibid., 70, 1244
(1966) I

The JOUTnd of Physical Chemistry

MEANACTIVITY OF POLYELECTROLYTES
COEFFICIENT
of the rule is about 1 equiv/1000 g of water for the in-
organic salts and about 0.5 equiv/1000 g of water for
the organic salts. The slopes are -0.82, -1.00,
-1.30, -0.40, -0.60, -0.80, and -0.95 for Li-, K-,
Na-, N(n-C4H9)4-r N(n-C3H7)r, N(CSH~)~-,and
M(CH3)4-PAA, respectively. The activity coefficients
of polyacrylates decreased in the order
Li > K > Na
and
N(n-C4H9)4 > N(n-C3H,)4 > N(CzHs)4 > N(CHB)Q (D)
While the order (D) was already found for polyelectro-
lytes studied so far,2 for tetraalkylammonium halides”
and for the propionates, the order (C) is new in two re-
spects: it differs from the order (A) found for propion-
ates or acetates, and also from the order Li > Na > K
observed for polyelectrolytes studied in this laboratory.2
According to the existing theories of structural influ-
ences of ions on ~ a t e r , l l b , l 2 -the
~ ~ structural salting-
out and salting-in effects result in the high-lying and
low-lying activity coefficient concentration curves, re-
spectively. The observed order for propionates (E( >
Na > Li) indicates that the propionate ion is a struc-
ture-former in the same sense as for L i + ion. As was
earlier suggested by Gurney,16 the acetate ion is a struc-
ture-former. Therefore, the propionate ion would be
structure-forming also, though probably even less so
than the acetate ion because of the presence of an ethyl
group which is a structure former of a mode incom-
patible with the carboxylate group.’6 The order (C)
for the polyacrylates (Li > K > Na) suggests that the
polyacrylate ion is a weaker structure former than the
propionate ion. This would be understood as follows.
The -CHs-CH groups present in the polymer chain could
I The CMC salts a t DS = 0.78 represent an intermediate
show a stronger cage-like structure-forming tendency
than the CH3-CH2 groups in the corresponding mo-
nomer unit, Le., the propionate ion. I n other words, we
can expect a cooperative influence by the repeating
units in the polymer chain on the water structure. As
a consequence, the electrostrictional influence of the
carboxylate group would be weakened more strongly for
the polyacrylates than for the propionates. Thus, the
order (C) differs from the order (A). As for the orders
(B) and (D), which agree to each other, it is useful to
point out that the organic ions are strong cage-like struc-
ture formers. The incompatibleness of the modes of the
water structure around the organic ions and the pro-
pionate or polyacrylate ions gave rise to the observed
order.
The foregoing discussion was clearly based on two
“counteracting” structural influences on water struc-
ture, namely the cage-like structure formation by the
hydrophobic part (methyl and ethyl groups for ace-
tates and propionates) and the electrostrictional struc-
ture formation by the ionic part (carboxylate ion for
4075
(C)
1
- 1.0
Figure 9. T h e cube-root plot of the activity coefficients of
N(R-C*HB),-and Na polyacrylate at degrees of neutralization of
0.4 and 0.2.
acetates and propionates). The relative magnitudes of
these two effects determine the position of the activity
(or osmotic) coefficient-concentration curves. l7 Thus,
the CNIC salts of DS = 0.95 (Figure 3) showed in the
order
N(n-C4H9)4 > N(CH& > Na (E)
which agrees with the finding for the polyacry-
lates. When the charge density (or the degree of sub-
stitution) is lowered, the contribution of the electro-
strictional factor becomes smaller and the hydrophobic
influence becomes more important. I n other words,
the structure-forming character of the CMC ions be-
comes closer to that of the organic gegenions with de-
creasing DS. Therefore N(n-C4H9)4-CMC a t DS =
0.68 has smaller osmotic coefficients than N(CH3)4-
CMC, as shown in Figure 5
N(CH,), > Ma = N(n-C4H9)4 (F)
feature, as seen from Figure 4. At this degree of sub-
stitution, the osmotic coefficients of the tetraalkylam-
monium salts fell on the same curve; no observable
difference was observed between N ( Y L - C ~ Hand ~)~
N(CHS)~ salts.
It would be interesting to examine the order of the
(12) H. S. Frank and W.-Y. Wen, Discussions Faraday SOC.,24,
133 (1957).
(13) H. S. Frank, J . Phys. Chem., 67, 1554 (1963).
(14) H. S.Frank, 2. Phys. Chern. (Leipzig), 228,364 (1965).
(15) R. W. Gurney, “Ionic Processes in Solution,” McGraw-Hill
Book Co., Inc., New York, N. Y., 1953,Chapter 16.
(16) The reasoning that the structureforming tendency of the pro-
pionate ion is weaker than that of the acetate ion is substantiated by
the fact that sodium propionate has larger activity coefficients than
sodium acetate. See ref 6, p 484,Appendix 8.10.
(17) The structural influences can be discussed in terms of the os-
motic coefficient,instead of the activity coefficient. When comparison
of various polyelectrolytes is sought, the use of the osmotic coef-
ficient is convenient because the activity coefficient at infinite dilu-
tion varies from sample to sample. The activity coefficients of
CMC samples are not given in the present paper, because the iso-
piestic data were not reliable enough a t higher dilutions to allow
the cube-root extrapolation.
Volume 73, Number 12 December 1969
4076 0. B. VERBEKE,V. JANSOONE,
R. GIELEN,and J. DE BOELPAEP

activity coefficientsof PAA salts at lower degrees of neu-
tralization. Figure 9 shows that a t a degree of neutral-
ization = 0.4 we have the order
N(n-CeHe) > Na (GI
which is the same as found a t a degree of neutraliza-
tion = 1 (see Figures 8a and 8b). However, when we
go down to 0.2, we have
Na > N(n-CkH9) (H)
I n words, the inversion of the order of the activity (or
osmotic) coefficients can occur not only for CMC salts
but also for PAA salts. This fact strongly supports the
validity of the above-mentioned explanation in terms
of the shift of balance between the structural influences
of ionic and hydrophobic groups with varying charge
density.
Finally, we compare the ipz values of the PAA and
CMC. As was mentioned before, the linear charge
density of a CMC having a DS = 1.0 is about the same
as that of a PAA of a degree of neutralization of 0.3.
Figure 6 shows that the ipz of this PAA sample is larger
than that of the corresponding CMC salt. This result
indicates that the PAA anions are more hydrophobic
than the CMC anions. This is consistent with the
information derived from the solubility measurements
of naphthalene and biphenyl in solutions of water-
soluble polymers.18
Acknowledgments. The sodium polyacrylate and so-
dium salts of carboxymethylcellulose were gifts of the
Toa Gosei Chemicals Co., Nagoya, and the Daiichi
Kogyo Seiyaku Co., Kyoto, respectively.
(18) T . Okubo and N. Ise, J. Phys. C h m . , 73, 1488 (1969).

The Equation of State of Fluid Argon and Calculation of the Scaling Exponents

by Olav B. Verbeke,
Institute for Molecular Physics, University o j Maryland, College Park, Maryland

Vik Jansoone, Rik Gielen, and Jan De Boelpaep

Fysisch Instituut, Universiteit van Leuven, Leuven, Belgium (Received February 19, 1869)

Experimental P-V-T data of fluid argon are presented. Most of the data cover the volume range from 28 to 132
cm8 in the range from 90 to 200’K and below 150 atm. Special attention is paid to the critical region. One
isochore, however, is measured up to 2000 atm and in the high-density range. In the high-density range with
molar volumes below 38 cms a Tait-like equation of state is fitted to the data. I n the range from 40 to 132
cma/mol, a new type of equation of state is proposed which fits the data through the critical point. It is shown
that the latter equation is compatible with the power laws, and the exponents are derived. From these equa-
tions different thermodynamic properties are calculated.

Apparatus and Method
The apparatus used for this experiment is a modifi-
cation of the equipment used with liquid hydrogen by
Van Itterbeelr, el al.’ (See Figure 1.) The 99,99G%
purity gas is liquefied in a formerly evacuated high-
pressure volume HP in a cryostat K. By means of
thermal compression the experimental volume VM is
filled through I<1 to the desired pressure whiIe K2 is
closed. This pressure can be 2000 atm in one stroke,
under the condition that VM has already been filled
with liquid up to 150 atm at the desired final tem-
perature. Care must be taken in order t o avoid the
melting curve and blocking of the capillary tubing CT.
While pressurizing at pressures in excess of 200 atm,
care must be taken of the differential gauge DM since the
pressure difference across the membrane may not ex-
ceed 200 atm. Subsequently, valve K1 will be closed
and by changing the temperature in cryostat K and
measuring pressure and temperature, pseudo-isochores
can be determined.
The quantity of gas can be determined by subsequent
expansion of the fluid at room temperature and a t
1 atm in the so-called expansion volumes VE1 and
VE2 while measuring temperature of thermostat T
and of the pressure by means of the oil-differential
gauge D and the mercury gauge M.
Temperature measurement in the experimental
(1) A. Van Itterbeek, 0. Verbeke, F. Theeuwes, and V. Jansoone,
Physica, 32, 1691 (1966).

The Journal of Physical Chemistry