Polyacrylamide. I.

Polymer Content and Hydrolysis

Level Determination by Potentiometric Titration
J. St. KENYERES and V. URSU, 4400 Nyiregyhbza, Bethlen U.52,Hungary

Synopsis
A method of determining the degree of hydrolysis by potentiometric titration of polyacrylamide
(PAA)with HCI and NaOH was developed. From the titration curves and the control of the degree
of purity it is possible to calculate the level of hydrolysis and the quantity of pure acid contained
in the P A A of a commercial product.

INTRODUCTION
Polyacrylamide (PAA) has, at different stages of hydrolysis, variable viscos-
imetric, flocculent, and absorption properties. Hence different uses of this
polymer are possible.
The PAA chain does not carry a strong electric charge. Its structure can be
written

-CH2+H-CH2-CH-
I
c-0
1
c-0
I
NHZ
I
NH2

and in aqueous solution has a coiled configuration.

The polyamidic chain of hydrolyzed PAA between two amidic groups contains
carboxylic groups introduced by hydrolysis or by copolymerization. The
structure of such a polymer is

-CH2--CH -CH2-CH- CHZ-CH-

I
c=o
I
c=o
I
c=o
I
NH2
1
OH
I
NHZ
In distilled water it also has a coiled configuration because of the low disso-
ciation constant of the carboxylic groups.
The PAA found most frequently in industry is a sodium salt of the inserted
carboxylic groups:

-CHZ+H-CH2-CH- CH2 -0CH-

I
c=o
I
c=o
I
c-0
I
NHz
I
0Na
I
NHZ

Journal of Polymer Science: Polymer Chemistry Edition, Vol. 18,275-281 (1980)

0 1980 John Wiley & Sons, Inc. 0360-6376/80/0018-0275$01.00
276 KENYERES AND URSU

Pure polymer in the form of sodium salt, when dissolved in water, shows an
extended chain due to the dissociation phenomenon. Hydrolyzed PAA is a
polyelectrolyte whose properties depend on the degree of purity, hydrolysis, and
neutralization. Leyte and Mandell have described how a strong micromolecular
electrolyte can screen the polyelectrolytic character of the polyacrylic acid so-
lution. This can be explained by the steric structure of the dissolved polymer,
which presents a varied number of water dipoles around the carboxylic groups.
The more chain is charged (the carboxylic groups are more dissociated), the more
water dipoles around the polymer. If the concentration of a micromolecular
electrolyte increases, the number of water dipoles around the carboxylic groups
decreases, which leads to screening the polyelectrolytic character. This feature
appears at potentiometric or conductometric titration, obtainable only a t low
electrolyte levels.
PAA can contain different kinds of impurity due to its processing. The water
content must also be considered. Sometimes the neutralization level of the
carboxylic groups of the polymer is less than 100%.
It is necessary to explain what is meant by “polymer content” as a physical
value. In this article polymer content refers only to the acid form of PAA and
the degree of hydrolysis is computed for it.
In the following the different stages of determination are discussed.

THE HUMIDITY OF PAA

During the determination any degradation is to be avoided. If the polymer
is dried at more than 60-70°C, the amidic groups are transformed in imidic
groups by an uncontrolled process and weight loss. The extraction methods are
to be preferred.
Taking 1.0000 g of the sample, we have
u = (1- G ) x 100 (1)
where U is the percentage humidity of PAA and G is dry part of the sample. If
we denote the weight of the sample by q , the dry part of which is p , the correlation
is
q x (100 - U )
‘P (2)
100

THE IMPURITIES
The dry polymer can contain different quantities of NH4+,Ca2+,so42-,C0s2-,
and so on. These impurities can be determined by different methods.
Let us denote the percentage of impurities of the sample by r. The total im-
purities from p will be pr/100.
Let w be the weight of the pure polymer in salt form in the dry sample p . We
then have

and from (2)

w =
q X (100 - U)(lOO -r)
(4)
10,000
 POLYACRYLAMIDE. I 277

It must be taken into account that w varies with the hydrolysis and the neu-
tralization level; hence it cannot characterize the polymer content.

DETERMINATION OF THE DEGREE OF HYDROLYSIS AND

NEUTRALIZATION LEVEL OF THE CARBOXYLIC GROUPS
Hydrolyzed PAA has a weak-acid character and theoretically can be titrated
with strong bases or with strong acids if it is in salt form.
During the titration difficulties may occur because of the polydispersity.
To obtain an accurate titration the reagents must be added gradually in the
smallest quantities possible. After one addition the relaxation time is 5-10 min.
The longest time was observed when the carboxylic groups were transformed
into acid form. This length of time makes necessary a steady current source.
The variations on the potentiometer are not so sharp and the determination
should be performed carefully. The titration has to be done from alkaline to
acid to avoid hydrolysis. If the polymer is alkaline, as in Separan AP30, titration
will also give the content of sodium carbonate and bicarbonate.
If the sample has carboxylic groups that are less than 100%neutralized, ti-
tration with an acid will give the neutralization level. T o ensure that the ob-
tained value will represent the total quantity of the carboxylic groups or only
the neutralization level, the titration should be done with an alkaline solution
in the opposite direction. The representation of a full determination is given
in Figures 2,3, and 4.
From the titration curve and the purity and humidity data the degree of hy-
drolysis and the polymer content may be computed as follows: The solutions
used: 0.1N HCl and 0.1N NaOH; used segment weights: MI = 71 for acryl-
amide units, Mz = 72 for acrylic acid units, M s = 94 for sodium acrylate
units.
The equivalency between 0.00365 g of HC1,0.0023 g of Na+, 0.0001 g of H+,
0.0094 g of -CHFCH.COONa, and 0.0072 g of -CH-CH.COOH is the basis
of the existing values.
By definition, the degree of hydrolysis gives the percentage of acrylamide
groups in the PAA chain that are transformed into acrylic acid groups and de-
noted by H .
Let m be the volume of chlorhydric acid and n, the volume of sodium hydroxide
used to transform the sodium acrylate into acrylic acid and vice versa. In a
comparison of these values there are three possibilities: m = n for a neutral, pure
PAA, m < n for a partly neutralized PAA, and m > n for a sample with excess
alkalinity.
To express the degree of hydrolysis it is necessary to know the quantity of pure
acid form of PAA. Let us denote it by W ,which for m = n is obtained from the
relation
W =w - 0.0023m + 0.0001m = w - 0.0022m (5)
From W only 0.0072m is hydrolyzed. Then the degree of hydrolysis is
0.72m
HI = 0
w - 0.0022m
If m < n, the quantity of hydrolyzed groups is O.O072n, but the Na+ remaining
is 0.0023m. Thus the degree of hydrolysis is
278 KENYERES AND URSU

Fig. 1. Diagram of the bridge used. The notation is explained in the text.

0.72n
H Z= 0 (7)
w - 0.0022m
For m > n we need supplementary information. In the diagram in Figure 2
the first part of the curve shows the neutralization of the carbonates in two steps.
The quantities of carbonate and bicarbonate can be determined by comparing
them. Let us denote the first step by k and the second by 1. Between the two
quantities the correlation is 1 2 12.
For sodium carbonate and bicarbonate the equivalent data are 0.0106k and
0.0084(1 - k), respectively. The total pure polymer in acid form is
W =w - 0.0022n - 0.0106k - 0.0084(1- k)
and the degree of hydrolysis becomes
0.72n
H3 = %
w - 0.0022 (n k) - 0.00841 +
The quantity of pure acid form of PAA is computed from (4) and (5).
For m 6 n:

-b
a-b
FP
A

' I
II 1
4
I
I

Fig. 2. Titration curves obtained for Separan AP30 (A) titration with 0.1N HCI; (B)titration
with 0.1N NaOH, (I) a red solution; (11) a yellow solution; (111) a light red solution; (- - -1 color change
-
of phenolphthaleine; (- - .) color change of methyl orange.
 POLYACRYLAMIDE. I 279

q X (100 - U)(lOO - r ) - 22m

w1= 10,000
g
and for m > n:
q X (100 - H)(100 - r ) - 22n
w2 = g (10)
10,000
The percentage of pure hydrolyzed PAA in acid form can be computed
from

p = -lOOW ~

THE EXPERIMENTAL PROCEDURE

The instrument used was a Poggendorf bridge (Fig. 1) constructed by the
authors. The notation in Figure 1 is the following: C, measuring cell with
platinum electrodes a t a distance of 40 mm and a surface area of 1cm2; inside
the cell is a constant mixing rate mixer; R, resistance box with a total resistance
of 1 M Q for the equilibrium of the bridge a t the beginning of the titration; A,
lightspot microampmeter with 5 X Ah00 divisions; E, stabilized 6-V dc
source; B, 12-m circular Kantal potentiometer with a wire diameter of 0.2 mm;
the errors in the measuring system were less than 1 mm; S, switch in the
system.
To facilitate the calculation an Obach-type table was computed by
L=- b (12)
a-b
where L is determined for a value of length b measured on the potentiometer
when the current on the bridge is zero and a = 11,990mm is the exact length of
the potentiometric wire.

B
I- ' !

i
I
I
i I Vml

Fig. 3. Titration curves of Separan NP10. Symbols are as those in Fig. 2.

280 KENYERES AND URSU

I
I
I ,
I
I
U- I
a
I
,
I

4- 7-$T
i i
I I 71II
I
8 ,
I
2- I
I
1
I
I
I

Fig. 4. Titration curves obtained for Medasol Me-H. The symbols are as those in Fig. 2.

The method was applied to a quantity of 0.2000 g of solid PAA with known
humidity and purity. The sample was introduced in a 400-ml Berzelius glass
that contained 200 ml of distilled water and a drop of phenolphthaleine and
methyl organge. The electrodes were introduced and the solution was mixed
until the end of the titration at a mixing level that did not permit bubble for-
mation.
The dissolution was accomplished in 3-4 hr after the lightspot of the mi-
croampmeter remained fixed for at least 10 min, when it was moved to zero with
the help of the resistance box or the potentiometer. The first reading on the
potentiometer was made and the titration began. During the experiment the
equilibrium of the bridge was maintained whenever 0.1 ml of solution was added,
a value of b was noted, and a change of color was observed.
After representation of L versus 1 ml of HCl and NaOH, respectively, m, n,
12, and 1 were determined from the diagram. Together with U and r, H , W , and
P were computed.

TABLE I
Determination of H,W , and P for Different PAA Samples
Skparan Separan Medasol
Type of sample AP30 NPlO MG-H
Total sample q (g) 0.2000 0.2000 0.2000
Humidity V(%) 4.01 3.58 12.45
Dry sample P (g) 0.1920 0.1928 0.1750
Impurities r(%) 13.23 0.0 0.0
Pure sample w(g) 0.1666 0.1928 0.1750
k ml of 0.1N HCl 2.0 - -
1 ml of 0.1N HCl 2.5 - -

m ml of 0.1N HCl 11.1 1.8 6.9

n ml of 0.1N NaOH 6.6 2.0 7.0
Degree of hydrolysis H(%) 31.2 7.6 31.5
Pure acid form PAA W(g) 0.1522 0.1884 0.1597
Percentage acid form PAA P(%) 76.1 94.2 79.8
 POLYACRYLAMIDE. I 281

For three successive determinations the error was less than 1%.
A titration curve for Separan AP30 is shown in Figure 2. For Separan NPlO
the data were determined from Figure 3. An intermediate case is that of Medasol
(an experimental Romanian PAA). This polymer has a degree of hydrolysis
similar to that of Separan AP30 and a weak acidity like that of Separan NP10.
The titration curves are represented in Figure 4.
Characteristic values are presented in Table I. It can be observed that even
a t high purities, as in Medasol MG-H,the sodium content is high enough to modify
the value of the polymer content ( P )considerably.

CONCLUSIONS
The PAA content of a commercially available product can be computed from
humidity, purity, degree of hydrolysis, and neutralization level. The degree of
hydrolysis can be determined accurately by the potentiometric method.

Reference
1. J. C. Leyte and M. Mandel, J . Polyrn. Sci. A, 2,1879 (1964).

Received May 31,1978

Revised December 13,1978
Accepted December 13,1978