JOURNAL OF POLYMER SCIENCE VOL.

XXIII, PAGES 467475 (1957)

Viscometric and Conductometric Titrations of

Polymethacrylic Acid with Alkali Metal and
Quaternary Ammonium Bases*?

I-IAKRY I?. GHEGOR, Department of Chemistry, Polylechnic Institute of

Brooklyn, Brooklyn, New York

DANIEL H. GOLD, American Cyanamid Company, Bound Brook, New

Jersey

and MICHAEL FREDERICK, Newark College of Engineering, Newark,

New Jersey

INTRODUCTION

Previous papers in this series have sliowri that tlie acid strengtli of poly-
meric acids decreascs with increasing size of quatcrnary ammonium counter-
ioiis, both with linear1p2aiid crosslinked3 polyacids. Further, the alkali
metal cations are bound in the sequence Li+ > Na+ > K+, as calculated
from potentiometric data and as measured directly by selectivity coefficients
on crosslinked carboxylic acid resin^.^ This contribution describes the
viscometric and conductometric behavior of polymethacrylic acid when
neutralized with the alkali metal hydroxides and a series of quaternary
ammonium hydroxides.

EXPERIMENTAL

Polymetliacrylic acid (PMA) was obtained tlirougli the courtesy of

Kohm and Haas Company as a laboratory sample, and had a n average
molecular weight of 150,000. Part of the polymer was dialyzed using cello-
phane tubing; no appreciable amount was found to be diffusible. Solutions
of this acid were standardized with base in the presence of 1 M sodium
nitrate, aiid all concentratioiis are expressed as base moles per liter.
The quaternary ammonium bases were prepared from tlie corresponding
analytical-grade halide salts by equilibration with silver oxide, followed by
filtratioii and storage in pol yethyleiie bottlcs uudcr nitrogen.
* This investigation was supported in part by Research Grant RG 2934(C4,)from the
Division of Research Grants of the National Institutes of Health, U. S. Public IIealth
Service.
The Discussion of this paper will be found on page 483.
467
468 H. P. GREGOR, D. 11. GOLD, AND M. FREDERICK

Viscoinetric titrations were carried out in a Ubbelohde viscometer which

allowed the titrant to be added directly to the bulb without affecting the
pressure. The water flow time was 113.60 f 0.06 seconds, such that kinetic
energy corrections were negligible. Constant flow times were obtained
without any time lag, allowing the experiments to be carried out in short
periods of time so that sodium contamination from the glass was always
lower than M. These measurements were carried out at 30.00 f 0.03O.
Duplicate determinations were reproducible to f0.1 sec. or better. Carbon
dioxide contamination from the atomsphere was avoided at all times.
All conductometric titrations were made at 24.98 f 0.05' under flowing
nitrogen. Standard base was added directly into a cell containing a
dipping-type conductivity electrode with platinized platinum electrodes.
Ohmic resistance was measured to =kO.lyo with a Klett conductivity bridge
a t 1050 cps. Stirring was stopped whenever resistance was measured. In
all cases equilibrium was reached in a few minutes after the addition of
base as evidenced by absence of drift.
The reduced specific viscosity (qs,/e) of PMA at three dilutions is shown in
Figure 1 as a function of the degree of neutralization a! with lithium, potas-
sium, tetramethyl-, tetraethyl-, tetra-n-propyl-, and tetra-n-butyl-
ammonium hydroxide. Figure 2 shows the specific conductivity of 0.01
M PMA neutralized wifh sodium hydroxide and the same series of quater-
nary ammonium bases. The inset in Figure 2 is an enlarged portion of the
data a t low values of a.

DISCUSSION

The current-carrying properties of polyelectrolytes as related to ion-

binding phenomena have been the subject of many investigations. Fuoss5
pointed out that even those polyelectrolytes in which the monomeric com-
ponents are completely ionized show the conductometric behavior of weak
electrolytes. Quantitative transport experiments on polyacrylic acid by
Wall et aL6 showed that the fraction of bound sodium was approximately
equal to a! until 6001, neutralization, after which it leveled off. The frac-
tion of current carried by the polyion was 0.4-0.5 over the entire range of cr
values, with the equivalent conductance of the polyanion being in the
range 30-50 ohm.-' cm.-' equiv.-'.
DiDFusion experiments carried out on essentially the same system6 led to
results which agreed with the transport measurements ; the mobility of
unbound sodium was almost the same as the value in free solution.
A subsequent study on the transport of polyvinylpyridine neutralized
with hydriodic acid7showed that binding of iodide ions occurred, the trans-
ference number of the polymer falling from 0.2 to 0.1 for cr = 0.4-0.8. The
equivalent conductance of the polymer (per fraction ionized) was found
to be 25 ohm-' cm.-' equiv.-'.
0 t h and Doty* studied the behavior of polymethacrylic acid neutralized
with sodium hydroxide using the techniques of light scattering, viscosity,
 TITRATIONS O F POLYMETHACRYLIC ACID 469

100 a
Fig. 1. Viscometric titration of 0.00112 M , 0.00337 M , and 0.0103 M polymeth-
acrylic acid with the hydroxides of the lithium (0),potassium (0).
tetramethylammo-
nium (V), tetraethylammonium ( O ) , tetra-n-propylammonium (A),and tetra-n-butyl-
ammonium (m) ions.

potentiometric titration, and conductance. The calculated ratios of the

root mean extension of the polymer from viscosity and titration data were
found to agree, being lower than the ratio obtained from dissymmetry
measurements. The net charge on the polyanion as a function of a was
calculated from conductance and viscosity data, and was found to level
off a t (I! = 0.4.
Turning first to the viscosity data of Figure 1,we find pronounced specific
counterion effects. The specific reduced viscosities increase in the sequence
of increasing counterion size. The increase from potassium to tetrapro-
pylammonium a t the maximum is 25% in 0.01 M solution, 21% in 0.003 M ,
and 4% in 0.001 M solutions.
The lithium and potassium salts have nearly the same viscosity, as ex-
pected. From the previous study' it was shown that, while the lithium ion
was bound preferentially, the binding was quite weak in dilute solution and
particularly in the absence of a salt having the same cation. Using the
calculated value of the formation constant of lithium polyacrylate, one
finds that the degree of association is about 0.01 a t (I! = 0.5 with 0.01 M
PMA neutralized with lithium hydroxide, a degree of binding too low to in-
fluence viscosity measurements.
The increment in the specific reduced viscosity with increasing counterion
size undoubtedly reflects the uncoiling of the polymer chain as a result of its
470 H. P. GREGOR, D. H. GOLD, AND M. FREDERICK

increased charge.2 That the counterion size is not a significant component

of the viscosity increment can be demonstrated by the use of the Einstein
equation, taking the radius of the tetrabutylammonium cation as being 5 A.
The specific reduced viscosity due to the presence of the cations is 0.8, or
about 4% of the observed increase of 250/, in 0.01 M solution.
From Figure 1it appears that the increase in the hydrodynamic volume
of the polymer with increasing counterion size is about the same in 0.01
and 0.003 Msolutions. Here a large portion of the counterions is evidently
close t o the chain so that counterion size is a factor. I n more dilute solu-
tions a larger fraction o l the counterions is separated from the chain by
distances greater than that of closest approach, and specific size effects
decrease. This dilution effect is also observed in the potentiometric be-
havior of these polymers.'
The sequence of hydrodynamic volumes reported here for the linear
polymer in difFerent cationic states agrees with swelled volumes of corre-
sponding crosslinked system^.^ For example, the volume of a PMA gel
crosslinked with 0.2501, divinylbenzene (DVB) and neutralized with base
was 3.05 liters per base mole in the lithium state, 3.10 for potassium, 3.32
for tetramethylammonium, and 4.48 for tetraethylammonium, as measured
directly.
Assuming that the effective volume of the linear polymer is that given
by the Einstein equation, one finds that the base mole volume of tetra-

I I I I
.z 4 .6 .8 0
d
Fig. 2. Specific conductance of 0.00867 M polymethacrylic acid neutralized with
sodium (A), tetramethylammonium (V), tetraethylammonium ( 0), tetrapropylammo-
nium (A),and tetrabutylammonium (m) hydroxide. The vertical line joins points indi-
cating the corresponding specific conductance of the counterions, calculated from their
limiting conductance values.
 TITRATIONS O F POlJYMFTTTACRYLIC ACID 471

ethylammonium polyacrylate a t different concentrations is: 0.2 (DVB 0.25),

5 liters equiv.-'; 0.05 M (DVB O.l), 18; 0.01 M, 30; 0.003 M , 43; 0.001
M, 60. These comparisons are of course quite crude because of daerences
in molecular weight. Further work in this laboratory on resins of lower
degrees of crosslinking may allow more direct comparisons between hydro-
dynamic and swelled gel volumes.
The conductance titrations of Figure 2 show several interesting effects.
First there is the pronounced drop in K a t low values of a. Cation exchange
is undoubtedly occurring here between the hydrogen ions produced by self-
ionization of the polyacid and the cations of the added base. The con-
ductance a t a = 0 appears to be almost entirely due to the hydrogen
counterions. For example, if it is assumed that the activity coefficient of
the dissociated hydrogen ions is unity, the initial p H 3.70 would correspond
t o a hydrogen ion concentration of 2 X M . Taking A! = 350, one
calculates a specific conductance of 7.0 X lo", close to the experimentally
determined value of 7.2 X
I n Figure 2 it is observed that the specific conductance starts to increase
linearly with a,but falls off as a increases over 0.3. Further, the total con-
ductance K~ is considerably larger than the conductances of the counterions
alone calculated from their limiting equivalent conductivities. This effect
can be observed more conveniently in Figure 3, where the dif€erence be-
tween the observed specific conductance of the polymer-counterion system
( K J and that of the counterion (K!), the latter being calculated from its

limiting conductance, is plotted for the different degrees of neutralization.

Values of the limiting conductance of the counterions were taken €rom the
data of McInnes, Shedlovsky, and L o n g s ~ o r t h ,Jones
~ and Bradshaw, lo
and Daggett, Bain, and Kraus.ll The values of K! are: sodium 50.11 ; tetra-

t
/#?

-%
L .2 .4 .6
bc
Fig. 3. Plot of apparent specific conductance of the polyanion (total con-
ductance miniis Colinterion conductance) for polpmethacrylic acid neutralized
with different bases. A p is the apparent equivalent conduct,ance of the polyanion,
calculated on the basis of added base.
472 H. P. GREGOR, D. H. GOLD, AND M. FREDERICK

methylammonium, 44.92; tetraethylammonium, 32.66; tetrapropyl-

ammonium, 23.45; tetrabutylammonium, 19.13.
Figures 2 and 3 show that the conductance of the polyelectrolyte system
is usually greater than the counterion conductance, calculated using limit-
ing conductance values. These results then offer direct and readily obtain-
able evidence that the pol yanion does conduct an appreciable fraction of
the current. Some of the early investigators of these phenomena assumed
that only the counterions could conduct current. l 2
Figure 3 can be interpreted in various ways. First, it can be postulated
that tetrapropyl- and tetrabutylammonium polymethacrylate are com-
pletely dissociated a t all values of a! and that independent migration occurs.
These two cations are different in volume by about 23%, and give nearly
the same values of K-, the calculated conductance of the polyanion. Then
the equivalent conductance (on the basis of a! values) of the polymer
A p can be calculated, and is shown in Figure 3 falling from 40 a t a! = 0.1 to
13 a t a! = 0.8. This picture is quite different from that presented by
who made use of transference experiments on a sodium polyacrylate system
and found that A p varied from 30 t o 50 over the range 0.1 Q a! Q 1.0. Also,
Wall found that appreciable amounts of added sodium were bound to the
polymer, so that the concentration of dissociated polyanion did not rise
with a!, but was from 0.1 to 0.3 of the polymer concentration over almost the
entire range of neutralization.
On the basis of complete dissociation of the large quaternary ammonium
polysalts and independent migration, one can calculate the degree of asso-
ciation with other counterions. The fraction of bound counterions p is:
p = 1- Kt/(K! + KO)

where K! and KO- are the cationic and polyanionic specific conductances,
respectively. Since the value of KO- is itself a function of 0, an iterative
technique is adopted for the calculation, taking a final value of KO- a t a
point a t which p is equal to the value of a! for the tetrabutylammonium
system. Figure 4 shows the fraction of bound sodium, tetramethylammo-
nium, and tetraethylammonium ions, calculated on this basis.
On the other hand, if a value of Ap is taken which corresponds to A, a t
a! = 0.1 and is constant for all other values of a! (A, = 40 ohm-' cm.-'

equiv.-l), then the calculated values of p are considerably higher, as shown

in Figure 4.
There appears to be little choice in the two sets of values; those which
correspond t o the findings of Wall6-' are obviously more correct. One
would not expect t o find any association between quaternary ammonium
cations and nonpolymeric carboxyl anions in aqueous media with its high
dielectric constant. I n fact, binding is not observed in these systems, as
has been shown by Schwarzenbach'3~14and by Gregor.1 However, with
polymeric systems the situation is obviously quite different. In fact, since
the potentiometric data show that the counterions are close to the poly-
anionic chain, a high degree of binding is required for the interpretation of
 TITRATIONS OF POLYMETI-IACRYLIC ACID 473

d
Fig. 4. Fraction of bound cations B as a function of degree of neutraliza-
tion (Y of polymethacrylic acid with various bases. Calculated on the basis
of zero association of tetrabutyl polymethacrylate (- - -), and on the basis that A,
= 40 for all values of (Y (-). The curve given by Wall6 is shown for comparison.

the potentiometric, viscometric, and conductometric data to be consistent.

Rate data16 on ion-exchange processes that give calculated diffusion co-
efficients for counterions which are considerably lower than those in free
solution also point up the requirement that the counterions are held in closc.
proximity t o the fixed charge sites.
0 t h and Dotys have combined viscometric and conductometric data t o
calculate ion binding. Treating the polymer coil as a single molecule, they
defined the equivalent conductance of the polysalt in terms of its charw
2:
AD = Z(X! f A!)

The mobility of the polyanion is:

where v is velocity, X is field strength, and Fy is the Faraday. Assuming

that Stokes hydrodynamics holds:
ZeX = 67rqorv- = krv-
where 9 0 is the solvent viscosity and r the radius of the polymer coil (as-
sumed spherical), from the Einstein equation, qrp = k‘+ and (qSp)”’
k”r. Combining these equations:
-
+
A22/(qsp)’’1 ZX: - A p = 0
474 H. P. GREGOR, D. H. GOLD, AND M. FREDERICK

Z *1 1
oc
Fig. 5. The fractional charge of polymethacrylic acid as a func-
tion of degree of neutralization a with the following bases:
sodium (A), tetramethylammonium (V), tetraethylammonium ( 0),
tetrapropylammonium (A), and tetrabutylammonium (W) hydroxide.

This expression differs from that of 0 t h and Doty only in that they set the
frictional coefficient proportional to T ~ The
~ . same data give plots which
are quite similar. The value of A in the expression above is evaluated by
setting Z = a! at low values of a,and a plot of Z 8s. a! is obtained, as shown in
Figure 5.
The charge plots shown in Figure 5 do not show up specific counterion
effects for the different ammonium cations. However, the charge plots
are calculated from a rather different set of assumptions than the binding
plots; the sole conclusion which can be drawn is that the large quaternary
ammonium cations are not bound so strongly to the polyanion as is the
sodium ion,

References
1. H. P. Gregor and M. Frederick, J. Polymer Sci.,23,451 (1957).
2. I. Kagawa and H. P. Gregor, J. Polymer Sci.,23,477 (1957).
3. H. P. Gregor, M. J. Hamilton, J. Becher, and F. Bernstein, J. Phys. Chem., 59,
874 (1955).
4. H. P. Gregor, M. J. Hamilton, R. J. Oza, and F. Bernstein, J. Phys. Chem., 60,
263 (1956).
5. D. Edelson and R. M. Fuoss, J . Am. Chem. Soc., 72,306 (1950).
6. J. R. Huizenga, P. F. Greiger, and F. T. Wall, J. Am. Chem. Soc., 72, 2640, 4232
(1950).
7. F. T. Wall, J. J. Ondrejcin, and M. Pikramenon, J. Am. Chem. SOC., 73, 2821
(1951).
8. A. 0 t h and P. Doty, J. Phys. Chem., 56,43 (1952).
9. D. A. McInnes, T. Shedlovsky, and L. G. Iangsworth, J. Am. Cliem. Soc., 54,
2758 (1932).
10. G. Jones and B. C. Bradshaw, J. Am. Chem. Soc., 55,1780 (1933).
11. H. M. Daggett, Jr., E. J. Bain, and C. A. Kraus, .I. Am. Chem. Soc., 73, 799
(1951).
 TITRATIONS O F POLYMETHACRYLIC ACID 475

12. W. Kern, 2.physik. Chem., A181,268 (1937-1938).

13. G. Schwarzenbach and W. Biedermann, Helv. Chim. A d a , 31,311 (1948).
14. G. Schwarzenbach, E. Kampitsch, and R. Steiner, Helv. Chim. A d a , 28,828 (1945).
15. M. Tetenbaum and H. P. Gregor, J. Phys. Chem., 58,1156 (1954).

Synopsis
The reduced specific viscosity of polymethacrylic acid increased with counterion size
a t the same degree of neutralization for the cations: sodium < tetramethylammonium
< tetraethylammonium < tetrapropylammonium < tetrabutylammonium. The in-
crease on going from sodium t o tetrapropylammonium a t 50-70% neutralization was
20-25% for 0.003-0.01 M polymer, about 4% in 0.001 M solutions. These data indi-
cate that a significant fraction of even large counterions are close t o the chain. Conduc-
tometric titrations showed that the equivalent conductance of the polyanion was about
40 for most of the salts studied and at low values of a. The binding of counterions
based upon the assumption that this value was constant over a led t o values which were
in reasonable agreement with those determined by Wall using transport experiments.
RBsumB
La viscosit.6 specifique rCduite de l’acide polym6thacrylique croft avec la grandeur de
I’ion de signe contraire pour un meme degrC de neutralisation, i savoir sodium < tetra-
methylammonium < tetra6thylammonium < tetrapropylammonium < tettrabutylam-
monium. A 50-70% de neutralisation l’accroissement comporte, en passant du sodium
au tCtrapropylammonium, 20-25% pour une solution de polymbre 0,003-0,Ol M, et
environ 4% en solution 0,001M. Ces resultats indiquent qu’une partie importante d’ions
de signe contraire meme volumineux sont retenus prbs de la chaine. Les titrations
conductomhtriques ont montrC que la conductance equivalente du polyanion est d’envi-
ron 40 pour la plupart des sels 6tudiCs et aux faibles valeurs de a. La liaison des ions
de signe contraire, basCe sup I’hypothbe que cette valeur est constante par rapport 1
a, fournit des valeurs qui s’accordent raisonnablement. avec celles dkterminees par Wall
ail depart d’experienres de transport d’ions.
Zusammenfassung
Die reduzierte spezifische Viskositat von PolymethacrylsCure nahm mit der Gegenio-
nengrosse bei gleichem Neutralisationsgrad fur die folgenden Kationen zu: Natrium <
Tetramethylammonium < Tetraathylammonium < Tetrapropylammonium < Tetra-
butylammonium. Die Zunahme auf dem Weg von Natrium zu Tetrapropylammonium
bei 50-7070 Neutralisation war 20-25% fiir 0,003-0,Ol M Polymer, ungefChr 4% in
0,001 M Losungen. Diese Daten zeigen an, dass eine erhebliche Fraktion sogar grosser
Gegenionen nahr der Kette liegen. Konduktometrische Titrationen zeigten, dass die
aquivalente LeitfChigkeit des Polyanions fiir die meisten der untersuchten Salze bei
neidrigen a-Werten ungefihr 40 war. Das Binden von Gegenionen war auf der Ann-
ahme gestiitzt, dass dieser Wert uber a konstant war, und fiihrte zu Werten, die in
zufriedenstellender Ubereinstimmung mit den von Wall bestimmten standen, die
Transport Experimente benutzten.