JOURNAL OF POLYMEll SCIENCE VOL.

XXIII, PAGES 451-1165 (1951)

Potentiometric Titration of Polyacrylic and

Polymethacrylic Acids with Alkali Metal and
Quaternary Ammonium Bases*?

HARRY P. GKEGOR and MICHAEL FREDEKICIC,$ Department of

Chemislry, Polytechnic Institute of Brooklyn, New York

INTRODUCTION
While the titratioii behavior of low molecular weight acids and bases is
independent of the nature of the base or acid used as a titrant, this is not
the case with polymeric acids and bases. Here specific effects have been
found t o occur where difl'erent counterions are present. Some of these
specific effects have been observed by Steinhardtl and by Tanford2, who
observed that the titration behavior of proteins was dependent in part 011
the specific acid or base used. Differences in the viscometric behavior of
polyacrylic acid when neutralized with sodium hydroxide aiid with po tas-
sium hydroxide were noted by K a t ~ h a l s k y . ~
A note by Gregor, Luttinger, and Loeb14described the tihalion of poly-
acrylic acid with quaternary ammonium bases, and showed that pK,,, the
negative logarithm of the average ionization constant, was 6.43 with
potassium hydroxide and 6.85 with tetrabutylammonium hydroxide. This
decrease in acid strength with increasing size of the counterion was also
observed with crosslinked polyacrylic and polymethacrylic acids by Gregor,
Hamilton, Becher, and Bern ~ tein .~Swelling measurements of these cross-
linked gels showed that the entropy of the polymer chain decreased with
increasing size of the counterion, a t the same degree of neutralization.
This contribution presents detailed data on the titration of polyacrylic
and polymethacrylic acids with lithium, sodium, potassium, ammonium
tetramethylammonium, tetraethylammonium, tetra-n-propylammonium,
and tetra-n-butylammonium hydroxides in the presence of varyiiig con-
ceiitratioiis of neutral salts of the same cation, aiid also in llie presence of
mixed salts. Following papers in this series will presciit data on the
conductivity aiid the viscosity of polymcthacrylic acid when neutralized
with the same series of bases. A theoretical trcatmeiit of tlicse syslems also
follows.
* This investigation was supported in part by Research Grant, 1ZG 294(C2) from tlic
Division of Research Grants of the National Institutes of Health, U. S. Public Health
Service.
t The Discussion of this paper will be found 011 page 483.
1Newark College of Engineering, Newark, N. J.
451
452 H. P. GREGOR AND M. FREDERICK

EXPERIMENTAL
Samples of polyacrylic and polymethacrylic acids were obtained through
the courtesy of Rohm and Haas Company; these were purified further by
precipitation and by dialysis using cellophane tubing. All of the chemicals
used were of reagent grade. The bases were prepared to be carbonate free
and the systems were kept under nitrogen a t all times.
Contamination of the solutions by potassium chloride diffusing from the
tips of calomel electrodes was kept a t a minimum by carrying out the
titrations using a Beckman p H meter, laboratory model G, with fiber tip
calomel electrodes. A number of these electrodes were tested for leak
of potassium chloride by immersion in distilled water and measurement over
a period of time. Only those tips which showed a leak of salt less than lop5
M in a half-hour period were used. In the previous study4 certain drifts
in the measured p H readings were found to occur. In the work reported
here it was observed that this drift was due either to bubble formation or
t o a skin of adsorbed polymer on the surface of the electrodes. This drift
in pH was eliminated by using a magnetic stirrer and passing nitrogen gas
over the surface of the solutions during the titrations, the stirrer being
stopped for each reading. It was found that no drift in p H took place; the
pH readings obtained almost instantaneously after the addition of base
were constant over a period of hours or days. Each titration was there-
fore performed directly, with a period of about five minutes between suc-
cessive readings. The temperature was compensated in each case to 25°C.
In order to avoid contamination from sodium in glass, polyethylene
beakers were used wherever this problem might have been serious, partic-
ularly with the quaternary ammonium bases. Repeated titration curves
were identical to within *0.02 pH unit.
Measurements of the hydrogen ion activity of polyelectrolyte solutions in
the presence of various salts contain two errors. The first is the so-called
suspension effect, which is primarily due to the presence of the polyelectro-
lyte; discussion of errors of this type is contained in the work of Loojes.G
These corrections are usually minor and since comparisons were made in
most cases between polyelectrolytes of the same conceiitration and type
no correction was deemed necessary.
A somewhat larger error might arise from differences ill the liquid junc-
tion potential be tween solutions of varying salt coiiceiitratioiis arid salt

TABLE I
EFFECT OF SALT
ON p H METERHEADINGS
WITH 0.05 M POTASSIUM BIPHTHALATE
BUFFER
Standard
Salt (no salt) 0.01 M 0.2 M 1M

KCI.. .. .. . . . . . . . 4. 00 3. 96 3.81 3.67

LiCl .... .. . , . . . . . 4.00 3.96 3.78 4.38
 POLYACRYLIC AND POLYMETHACRYLIC ACIDS 453

types and the saturated potassium chloride solution of the calomel electrode.
A discussion of various procedures for the minimization of these errors is
found in Harned and Owen.’ Since in this paper most comparisons were
made between solutions of equal ionic strength but varying in ionic com-
position, the effects of such variations could be corrected for by measuring
the pH of the same buffer in the presence of different salts of the same ionic
strength; these differences could then be applied as a correction. This
experimental method is similar to that used by Harned and Robinson,8and
by others.
Table I presents data on the pH of a potassium biphthalate b d e r
(0.05 M ) in solutions of lithium, sodium, and potassium chlorides a t vary-
ing concentrations.
Titrations of 0.01 M (base moles) polyacrylic acid (PAA) by lithium,
sodium, and potassium hydroxides in the presence of no salt and of 0.01,
0.1,0.2, and 1.0 Msolutions of the corresponding chlorides were carried out.
The experimental results for each titration curve could be expressed in terms
of the modified Henderson-Hasselbalch equation, pH = pK,, - n log (1-
a ) / a ,where a is the degree of neutralization or equivalents of base added
per equivalent of acid present, n is a constant, and KaDis the average ioniza-
tion constant. In each case an appreciable shift in the titration curves to
lower pH values was observed on going from potassium to sodium to lithium.

log .+
- 0.5 -QZS 0 a23 a5
I I I

c G

ry
Fig. 1. Titration of 0.01 M polyacrylic acid with potassium hydroxide ( 0 ) .
sodium hydroxide (A), and lithium hydroxide (0)in the presence of 0.2 M solutions of
the corresponding chlorides.
 PARAMETERS
TABLE 11. HENDERSON-HASSELBALCH FOR TITRATIONS
OF POLYACRYLIC
AND POLYMETHACRYLIC
ACIDSWITH
VARIOUS
BASESAT DIFFERENT
IONICSTRENGTHS
Tetramethyl Tetraethyl Tetraprppyl Tetrabutyl
Salt ammomum ammonium ammonium ammomum
added, Lithium Sodium Potassium
Polyacid M pK.. n pK.. n pK.. n pK.. n pK.. n PK.. n pK.. n

PAA(O.O1 M) ........... 0 6.70 1.96 6.79 2.13 6.79 2.26 6.75 2.72 6.95 2.93 7.12 3.38 7.24 3.62
0.01 5.85 2.13 6.14 2.20 6.14 2.31 6.27 2.57 6.43 2.98 6.55 3.15 6.18 3.98
0.1 5.31 1.87 5.29 1.95 5.35 2.07 5.68 2.51 5.73 2.88 5.96 3.10
0.2 5.08 1.64 5.20 1.87 5.30 1.98
I 4.48 1.48 4.68 1.60 4.67 1.65
PMA(O.O1 M) . . . . . . . . . . 0 7.15 2.05 7.25 2.40 7.34 2.74 7.61 3.12 7.73 3.62
PMA(O.OO1 M) . . . . . . . . . 0 7.90 2.44 7.95 2.66 8.39 3.78
Potassium-tetrabutylammonium Mixture
XE = 1 XK = 0.54 XK = 0.33 X K = 0.12 X K = 0.012 X K = 0.0012 XP = 0

PAA(O.01 M ) .......... . 0 6.79 2.26 6.78 2.74 6.91 3.01 7.11 3.40 7.05 3.50 7.19 3.42 7.24 3.62
Lithium-tetrabutylammoniummixtureas'
XLi = 1 X L i = 0.10 X L i = 0.01 XLi = 0

PAA (0.01 M)..... . . . . . . 0 6.70 1.96 7.10 3.26 7.17 3.44 7.24 3.62
a X = mole fraction.
 POLYACRYLIC AND POLYMETHACRYLIC ACIDS 43.55

This effect was perceptible but rather small in the absence of salt, steadily
increasing with the ionic strength due to added salt. Figure 1 shows a
plot of titration curves for 0.01 M PAA with lithium, sodium, and potassium
hydroxides in the presence of 0.2 M solutions of the corresponding chlorides.
The Henderson-Hasselbalch plots for these titrations are also shown.
Table I1 presents calculated values of the average ionization constants

PH

I I I I I I
0 0.2 0.4 0.6 0.8 1.0 1.2.
CX
Fig. 2. Titrations of 0.01 M plyacrylic acid with potassium and tetraalkylam-
monium hydroxides in the absence of salt, and in the presence of 0.01 M and 0.1 M solu-
tions of the corresponding halides. Note that the ordinate has been displaced for each
curve. The symbols are as follows: potassium (n),tetramethylammonium (V), tetra-
ethylammonirim ()., tetrapropylarnmonium (A),tetrabutylammonium ().
456 H. P. GREGOR AND M. FREDERICK

pK,, and n for other titrations of polyacrylic acid with various bases in the
presence of varying concentrations of salt, and of 0.01 M and 0.001 M solu-
tions of polymethacrylic acid (PMA) with different bases in the absence of
added salt. In all cases Henderson-Hasselbalch plots of the data gave
straight lines with an excellent fit in the range 0.7 > CY > 0.3, where the
equation is considered to have maximum validity.
Figure 2 shows titration curves of 0.01 M PAA with potassium and the
quaternary ammonium bases in the absence of salt, in 0.01 M and 0.1
M salt solutions. The curves have been moved on the ordinate axis to
show the three sets in a single figure. Titration curves and Henderson-
Hasselbalch plots of 0.01 M PMA are shown in Figure 3 for titrations with
sodium and the quaternary ammonium bases in the absence of salt. Titra-

I-=
‘09 a
-a5 -92’1 0 0.25
12

10

II

10

d
PH

3
0 0.2 0.4 -0.6 0.8 1.0 1.2 1.4
o(

Fig. 3. Titration of 0.01 M polymethacrylic acid with sodium and the tetra-
alkylammonium hydroxides: sodium (A), tetramethylammonium (V), tetraethylam
moniurn ( O ) ,tetrapropylammonium (A),tetrabutylammonium (m).
 POLYACRYLIC AND POLYMETIIACRYLIC ACIDS 457

tion curves with sodium and potassium were nearly identical under these
conditions. Figure 4 presents titration curves for 0.001 M PMA with
potassium, tetramethyl, and tetrabutyl ammonium hydroxides in the
absence of salt.
The polymeric acids were also titrated with mixtures of bases. Figure
5 shows titration curves for 0.01 M PAA titrated with mixtures of potassium
and tetrabutylammonium hydroxide in the absence of neutral salt. The
mole fraction of potassium hydroxide in the mixed bases varied from 0.0012
to 0.54. Figure 6 shows a titration curve for 0.01 M PAA with mixtures
of lithium and tetrabutylammonium hydroxide in the absence of salt.
Figure 7 shows titration curves of 0.01 M PAA with potassium hydroxide
in 1 M potassium chloride, in mixtures of potassium and lithium chlorides
having a total ionic strength of 1.0 and in 1 M lithium chloride employing
lithium hydroxide.
Titrations with potassium and tetrabutylammonium hydroxide in the
absence of salt of an analogous low molecular weight acid, 0.01 N glutaric
acid, are shown in Figure 8. It is seen that the curves are virtually identi-
cal.

DISCUSSION
The discussion contained herein will concern itself primarily with the

I I I I I I I

a
Fig. 4. Titration of 0.001 M polymethacrylic acid with potassium (O), tetramethyl-
ammonium (V ) and tetrabutylammonium (m) hydroxides.
458 H. P. GREGOR AND M. FREDERICK

P”

0 0.2 0.4 0.6 0.6 1.0 1.2

a
Fig. 5. Titration of 0.01 M polyacrylic acid with potassium-
tetrabutylammonium hydroxide mixtures where the mole
fraction of potassium hydroxide is XK.

qualitative aspects of these phenomena. A subsequent paper in this seriesg

will present a theroretical discussion and treat quantitative aspects.
Almost all of the specifk counterion effects observed were found to
occur in the absence of added salt or in the presence of dilute salt. Ac-
cordingly, the pH shifts cannot be ascribed to specific salt effects, but rather
to polyanion-counterion interactions. Table I shows that the presence of
0.01 M potassium and lithium chlorides led to identical buffer pH readings,
while a difference in only 0.03 pH units was observed a t 0.2 M ionic
strengths. In the 1 M solutions differences in liquid junction potentials
and in activity coefficients of the supporting electrolyte are significant; for
this reason, comparisons here are open to question.
There is thus direct evidence for the binding of lithium and, to a lesser
extent, sodium ions by polyacrylic acid. In the absence of neutral salt,
the average ionization constants are nearly the same but the slopes are
significantly different. As the ionic strngth due to added salt increases,
 459

0 0.2 0.4 0.6 0.8 I .o 1.2

oc
Fig. 6. Titration of 0.01 M polyacrylic acid with lithium-
tetrabutylammonium hydroxide mixtures where the mole
fraction of lithium hydroxide is XLI.

significant changes in pKanbegin to occur, showing a strong effect in 0.2 M

solutions as shown in Figure 1. At a = 0.9 the decrease in p H is 0.35 on
going from potassium to sodium, and is 0.56 on going from potassium to
lithium. These effects are obviously well outside errors introduced by
suspension and liquid junction potential effects. While somewhat stronger
effects are observed in 1 M solutions, these are in part due to those side
effects which cannot be evaluated.
The binding of lithium and sodium by carboxyl groups as compared to
potassium is well known. The alkali metal acetates show activity coefi-
cients which decrease with decreasing atomic weight. This has been inter-
preted as being due to hydrogen bonding, “localized hydrolysis” or to the
entrance of the carboxyl group into the hydration sphere.? These effects
are not observable in 0.01 M solutions of the acetates, but only in relatively
concentrated solutions. With the polymeric alkali metal polyacrylates,
on the other hand, these effects are observed a t low concentration levels,
increasing with metal concentration a t constant polyacid concentrations.
The origin of these effects is undoubtedly the high chain potential
460

0 0.2 0.4 0.6 OQ 1.0 12

a
Fig. 7. Titration of 0.01 M polyacrylic acid with base in 1.0 M lithium
chloride (0), 1.0 M potassium chloride ( 0 ) . and in 0.2 M lithium chloride and
0.8 M potassium chloride or XK = 0.8 (A).

possessed by polyelectrolytes. Binding is quite weak a t low degrees of

charge, reaching a maximum a t high degrees of charge. An interesting
comparison of the data of Figure 1 with that of Figure 7 can be made be-
cause in the latter case the total ionic strength is unity while the concentra-
tion of polyacrylic acid and lithium chloride are the same as in Figure 1,
namely, 0.01 M and 0.2 M , respectively. It is interesting to note that a t
the high ionic strength the binding effect is quite weak, undoubtedly re-
flecting the lowered chain potential as a result of shielding by added
electrolyte.
The extent of binding of lithium by polyanion can be calculated by the
method of J. Bjerrum as modified by Gregor.10 Here one assumes no bind-
ing of potassium ions, and uses these values of K,, and n. Then since the
charge on the polymeric chain is a function not only of a but also of the
extent of binding, use is made of the more fundamental relationship:
K,, = 2" [H+] [A-]/[HA]
where 2 is the degree of charge, equal to the ratio of charged to uncharged
groups on the chain and M = n - 1 ; brackets are used to symbolize con-
centrations.
 POLYACRYLIC AND POLYMETHACRYLIC ACIDS 461

0 0.2 0.4 0.6 0.e 1.0 1.2

Q
Fig. 8. Titrations of 0.01 N glutaric acid with potassium liydroxide
( 0 )aiid tetrabutylamrnoiiium hydroxide (w).

From conservation equations and electroneutrality relations, the con-

centration of undissociated acids is :
[HA] = [A,] (1 - (Y - [Hf])
where [A,] is the total concentration of acid. Bjerrum’s value for the
average concentration of ligand carboxylate groups bound per total metal
ion concentration [M,] then is:
a = [A,] - [HA] - [A-]/[ill,] = [MeA]/[M,]
It then becomes possible to calculate the frce carboxylate coiiccntration
[A-] and a. These calculations were performed for the binding of lithium
by the polyacrylate anion in 0.2 M lithium chloride solution, using the data
upon which Figure 1 was based. It was found that the binding was quite
weak in terms of ordinary complexation, the highest value of n being 0.0125
a t = 0.82. The fraction of neutralized carboxylic groups combined with
(Y

lithium ions, or the quantity [LiA]/a[A,] has somewhat more significance

here, and is shown in Figure 9. The average value of the formation con-
stant K,:
462 H. I?. GREGOR AND M. FllEDERICK

Kf = [LiA]/[Li+] [A-]
was fouiid t o be approximately 1.94 f 0.15 for 0.4 < a < 0.9.
Figure 2, which shows titrations of polyacrylic acid with potassium and
various quaternary ammonium bases a t different salt concentrations,
demonstrates the pronounced increase in the slope and the average ioniza-
tion constant of the polyacid with increasing couiiterion size. Since this
point is treated theoretically in detail in a subsequent paperg all that is
required here is to point out that increasing counterion size and the con-
sequent increasing distance of closest approach of the counterion to the
chain makes for an increased chain potential. The electrical free energy
required t o remove a proton from the chain accordingly increases.

- 0
2.0 2.2 2.4 2.6 2.8 3.0
P 1x1

G c

Fig. 9. Plot of the ratio of bound lithium, [LiA], to concentration of

added base, LY [At], as a function of the negative logarithm of the free car-
boxylate concentration, and plot of concentrationsof lithium carboxylate
and free carboxylate groups as a function of degree of neutralization for
the system: 0.01 M polyacrylic acid; 0.2 M lithium chloride; added 0.1 M
lithium hydroxide.

These data also show direct evidence that a significant fractioii of the
counterioiis of polyelectrolytes of high charge have equilibrium positions
in close proximity to the chain, the distance of iiearest approach being
approximately the sum of the ionic radii.
From Figure 2 it is observed that the upward shift in p H with illcreasing
couiiterioii size is approximately the same in the absence as in presence of
salt. This effect appears to be due in large part to the cxclusioii of neutral
salt from the polyanion coil by the high Donnan concentration present there.
It would be expected that the ionic strength effect would be signifcant
only a t high ionic strengths.
Figures 2 and 3 also show that the curves for titrations with the quater-
 POLYACIIYLIC AND POLYMEl’IIACRYLIC ACIDS 463

riary ammoriium bases show inflection points a t a = 1which decrease with

increasing molecular weight. While many explanations might be offered,
the most plausible one is advanced by R. M. Fuoss, who pointed out
(private communication) : “In aqueous solutions, the dielectric constant
is so high that ion association due to Coulomb forces cannot occur. Quater-
nary ammonium ions, however, have a hydrophobic exterior and if it were
not for electrostatic repulsion, would tend to cluster in aqueous solution due
to van der Waals attraction between their hydrocarbon chains. It seems
possible that a pair of quaternary ions might be stabilized by the presence
of an anion, to give a triple ion configuration in which van der Waals
attraction plus two electrostatic attraction terms would be greater than
the single electrostatic repulsion term.”
These general results are also observed with polymethacrylic acid. Fig-
ure 3 and Table I1 show that the increases in pKaband n are approximately
the same for both acids. Some slightly stronger effects which were ob-
served are undoubtedly due to additional shielding by the methyl groups.
A comparison of the effects observed with linear polycarboxylic acids
and with corresponding crosslinked polyacids5shows that the increments in
the slopes and average ionization constants were greater with crosslinked
than with the linear polymers. The considerably greater Donnan exclusion
exhibited by the crosslinked polyelectrolytes is doubtless the causative
factor here, plus the increased steric hindrance due to the high concentra-
tion of polymer in the resin form.
All of the titrations described previously were carried out with 0.01 M
polyacids. The titration of 0.001 M polymethacrylic acid (Fig. 44) in-
dicates that the counterion size effect becomes smaller with increasing
dilution. This is as expected, since the average distance of approach of
the counterion atmosphere must increase with dilution and specific effects
due to the size of the counterion would correspondingly decrease. However,
even in 0.001 M solutions of polymethacrylic acid there is considerable
“clustering” of the counterions about the polymer coil.
When polyacrylic acid was titrated with mixtures of the hydroxides of a
large and a small counterion in the absence of salt, the curves were inter-
mediate between those obtained with the single cations. With potassium-
tetrabutylammonium mixtures, the upward shift in pH a t 90% neutraliza-
tion was not proportional to the mole fraction of the larger cation, but
rather larger. For example, the curve for XK = 0.33 was approximately
midway between those for potassium and tetrabutylammonium, wliilc
only one-fourth of the pII increment was observed with X , = 0.54. 011
tlic other hand, as much as 10% of potassium had to be added to the titraiit
solution before a really significant downward shift in pH was observed.
In view of the specific binding of lithium exhibited by polyacrylic acid,
titrations were carried out with mixed lithium-tetrabutylammonium
hydroxide titrant solutions. When the mole fraction of potassium (see
Fig. 5 ) was 0.012, no effect was observed. However, in Figure 6 a signifi-
cant change is observed when the mole fraction of lithium was 0.01.
464 €1. P. GRI3GOR AND M. FREDERICK

When the mole fraction of lithium was increased tb 0.1 the effect was
significantly greater than that observed with potassium. It would appear
that the specific binding of lithium is enhanced by the high chain potential
of tetrabutylammonium polyacrylate.
When low molecular weight acids are titrated with cations of m e r e n t
sizes, 110 significant differences appear. Figure 8 shows that, even when the
counterions are as different as potassium and tetrabutylammonium, the
titration curves for glutaric acid were identical.

Refcrenccs
1. J. Steinhardt, Ann. N. Y. Acud. Sci., 41,287 (1941).
2. C. Tanford, J. Am. Chem. Soc., 72, $41 (1950).
3. A. Katchalsky, J. Polymer Sci., 7, 393 (1951).
4. H. P. Gregor, L. B. Luttinger, and E. M. Loebl, J. Am. Chem. Soc., 76, 5879
(1954).
5. H. P. Gregor, M. J. Hamilton, J. Becher, and 17. Bernstein, J. Pliys. Chem., 59,
874 (1955).
6. R. Loosjes, Thesis, Utrecht, 1942.
7. H. S. Harned and B. B. Owen, Physical Cliernistry of Electrolytic Solutions, Rein-
hold, New York, 1943, p. 316.
8. €1. S. Harned and R. A. Robinson, J. Am. Cliem. Soc., 50,3157 (1928).
9. I. Kagawa and H. P. Gregor, J. Polymer Sci., 23,477 (1957).
10. H. P. Gregor, L. Luttinger, and E. M. Loebl, J. Phys. Chem., 59,34 (1955).

Synopsis
Lithium ions, and, t o a lesser extent, the sodium ions are bound by polyacrylic acid,
as evidenced by pII titrations of polyacrylic acid in dilute (0.01 M ) solutions of the
alkali metal bases and solutions of their corresponding salts. The formation constant
for the binding of lithium to polyacrylic acid was found t o be 1.9. When dilute solutions
of pol yacrylic and polymethacrylic acids were titrated with quaternary ammonium
bases, the polyacids became progressively weaker with increasing size of the counterion.
These phenomena suggest that the counterions are largely held in close proximity t o the
polyanion chain, with distances of approach comparable t o the sum of the ionic radii.
Titrations of these acids with a mixture of a large and small cation also served t o point
up the increased chain potential in the presence of large cations. All of these effects are
absent with the analogous low molecular weight acids.

RCsumi:
Ides ions lithiques, e t en rnoindre irnportaiice lcs ions sodium, sorit l i b par I’acide poly
acrylique, ainsi que le montrent les titrations au pfI de I’acide polyacrylique en solutions
diluCes (0,Ol M) au moyen de bases des mCtaux alcalins e t de solutions de leurs sels
correspondants. La constante de forinaticn de liaison de lithium P I’acide polyacrylique
a 6th trouvCe Cgale P 1.9. Lorsque des solutions diluCes d’acides polyacrylique e t poly-
mCthacrylique Ctaient titrCes par des bases ammoniques quaternaires, les polyacides
deviennent progressivement plus faibles suivant la grandeur croissante de I’ion de signe
contraire. Ces phCnom&nessuggerent que les ions de signe contraire sont gardCs dans
le voisinage immCdiat de la chaine polyanionique des distances comparables P celles de
la somme des rayons inoiques. Les titrations de ces acides avec un melange de cations
grands et petits ont Cgalement CtC utilisCs pour dCmontrer le potentiel de chaPne croissant
avec la presence de larges cations. Tous ces effets sont absents avec les acides analo-
gues de faible poids molCculaire.
 POLYACRYLIC AND POLYMETHACRYLIC ACIDS 465

Zusammenfassung
Lithiumionen und in geringerem Ausmasse Natriumionen werden durch Polyacryl-
saure gebunden, wie durch pH-Titrationen von Polyacrylsaure in verdunnten (0, 01 M)
Lijsungen der Alkaliinetalbasen und Lijsungen ihrer entsprechenden Salze gezeigt wird.
Es wurde gefunden, dass die Bildungskonstante fiir die Bindung von Lithium an Poly-
acrylslure 1,9 ist. Wenn verdiinnte Losungen von Polyacryl- und Polymethacryl-
sluren mit quaternaren Ammoniumbasen titriert werden, wurden die Polysauren mit
zunehmender Grosse des Gegeniom fortschreitend schwacher. Dime Vorgarige lassen
annehmen, dass die Gegenionen in der Hauptsache sehr nahe der Polyanion-Kette gehal-
ten werden, wobei die AnnEherungsabstande der Summe der Ionenradien vergleichbar
sind. Titrationen dieser Sluren mit einer Mischung eines grossen und kleinen Kations
dienten auch dam, das erhijhte Kettenpotential in Gegenwart grosser Kationen zu
zeigen. Alle diese Wirkungen bestehen mit den analogen Sluren von niedrigem Mole-
kulargewicht nicht.