STUDIES IN POLYELECTROLYTES. II.

GUM ARABATE

Sadhan Basu, Pares Ch. Dasgupta and Anil K. Sircar

Indian Association for Cultivation of Science, Lady Willingdon Road, Calcutta 32, India
Received May 17~ 1951

INTRODUCTION
Natural arabic gum is a mixture of potassium, magnesium, and calcium
salts of a high-polymeric acid, which may be liberated by treatment with
mineral acids. Gum arabic purified by repeated precipitation from water
with alcohol has an equivalent weight of 1000-1200 and a molecular
weight of about 240,000 (1). On hydrolysis it yields a mixture of galac-
rose, arabinose, rhamnose, and as high as 28% of an aldobionic acid which
has been proved to be L-galacturonic acid 6-galactose (2,3). Very little is
known as to the nature of the chemical union between these groups in the
molecule of arabic gum. A ring formula suggested by Norman (4) has been
rejected on the basis of various physicochemical considerations. Strain
double refraction of a thread of arabic gum showed that the molecules are
elongated and most probably linear; but the x-ray examination of the
thread revealed no fiber diagram. A reconciliation between these two
structures has been proposed and it has been suggested that the constit-
uent units in a gum arabic molecule are arranged in a chain, but the
chains are not very regular and therefore cannot fit into a well-ordered
lattice owing to side-branching (5).
An indirect way of deciding the chain-like character or otherwise of the
gum arabic molecule, is to study the folding-unfolding phenomenon of
such a molecule in solution. The folding-unfolding phenomenon in a
high-molecular-weight compound may be strikingly demonstrated by
simple physicochemical measurements if the compound can be converted
into a soluble, ionizable compound; that is to say, into a polyelectrolyte,
as suggested by Fuoss (6).
THEORETICAL
By the term polyelectrolyte is meant a high-molecular-weight compound
which contains a number of ionizable groups distributed along the poly-
mer chain. Polyelectrolytes, unlike their analogs the simple electrolytes,
on the one hand, and neutral polymers on the other, show some character-
istic behavior in solution, e.g., viscosity, conductivity, osmotic pressure,
etc. These peculiar behaviors of the polyelectrolytes arise, according to
539
540 SADHAN BASU, P A R E S Ctt. DASGUPTA AND ANIL K. SIRCAR

Fuoss, due to the presence of high charge densities on the polymer chain in
dilute solution and flexibility of the polymer chain. If the degree of ioni-
zation of the polye!ectrolyte chain is decreased by any factor, say by an
increase of concentration or by adding a suitable electrolyte, the average
distance between the charge centers in the polymer chain increases;
consequently the coulombic repulsion between the charge centers de-
creases and the polymer chain coils u p . Fuoss (6) studied a number of
synthetic polyelectrolytes and interpreted their peculiar behaviors by his
folding-chain theory. Katchalsky (7), by mathematical analysis, also
interpreted the polyelectrolytie behavior in the same light. It has emerged
from these investigations that the folding-chain theory of Fuoss (6) is
almost the only explanation for the peculiar viscometric and other be-
havior of polyelectrolytes, and neither in neutral polymers nor in colloidal
electrolytes could such peculiarities be detected.
It has been shown that arabic gum disperses to molecular units in
solution and the colloidal character of the solution is associated with the
colloidal dimension of the molecule itseif (8). If in the gum arabic molecule
the constituent units are arranged in a chain with the carboxyl group of the
uronic acid distributed along the chain, the solium salt of the acid in dilute
solution will behave as a polyelectrolyte. With this end in view, the present
investigation was undertaken, the results of which are summarized in the
present paper.
EXPERIMENTAL

Preparation of the Gum Arabic Acid

The arabic gum supplied by Messrs. Bengal Chemical & Pharmaceu-
tical Works, Calcutta, was dissolved in water, filtered, and precipitated
with alcohol. The process was repeated three times. The purified gum was
then dissolved in water and brought to pH 2.5 by adding the requisite
quantities of hydrochloric acid, kept at that pH for 24 hr., and then dia-
lyzed till the dialyzate had an ash content of only about 0.05%, The acid
was titrated electrometrically using a glass electrode in conjunction with a
model G Beckman pH-meter. The equivalent weight was found to be 1208,
a result, in good agreement with the recorded data in the literature, which
is in the range of 1000-1200 (1).
Preparation of Sodium Salt of Arabic Acid
A solution of arabic acid was neutralized with sodium hydroxide
solution, the sodium salt precipitated out of the solution with alcohol,
redissolved in water, and dialyzed for 4 hr. against distilled water in order
to remove any adhering alkali. The concentration of the solution was de-
termined by evaporating and vacuum drying a portion of the solution.
Ash estimation of the gum arabate corresponded to sodium calculated
 POLYELECTROLYTES. If. GUM ARABATE 541

from the equivalent weight of the acid. The solution had a p H of 6.8, and
was used as such, or with dilution wherever necessary, in all subsequent
measurements. The solution remained unchanged, i.e., without any
hydrolysis, for more t h a n 15 days.

M e a s u r e m e n t of Viscosity
The viscosity measurements were done with two Ostwald viscometers
having flow times of 230.7 sec. and 324.7 sec., respectively, with water at
a t e m p e r a t u r e of 35 ± 0.1°C. The specific and relative viscosities were
calculated from the following equations:

relative viscosity = v _ pit1

7o pt
specific viscosity = ~ , = v/v0 - 1
where ~ and T0 are the viscosities, p~ and p the densities and t~, and t the
time of efflux (in seconds) for the solution and solvent, respectively. In
the range of dilute solutions used, the difference in densities of the solution
and water was insignificant and no density measurements were taken.

RESULTS
The results of reduced viscosity (7~,/c, where c is the concentration
in g./100 cc.) measurements at different concentrations of gum arabate
are summarized in Table I and the corresponding w , / c versus c curves are
given in Fig. 1.
TABLE I
Change in Reduced Viscosity with Concentration of Gum Arabate
Concentration
g./100 cc, water y~p/C
1.3140 1.1640
0.8760 1.1760
0.5840 1.2630
0.3893 1.3640
0.2595 1.4810
0.1730 1.6160
0.1153 1.7870
0.0577 1.9670

I t is evident from Table I and Fig. 1 t h a t ~ sp/c rises as the concentra-

tion of gum arabate is reduced.
T h e measurements of reduced viscosity of gum arabate solutions were
done at various constant sodium chloride concentrations, the results of
which are given in Table I I and the corresponding v ,p/c versus c curves
are drawn in Fig. 1.
I t becomes evident from Table I I t h a t the viscosity of gum arabate
solution is lowered by the addition of NaC1, the lowering increasing with
542 SADHAN BASU, PARES C t t . DASGUPTA AND -4,NIL K. SIRCAR

increasing concentration of NaC1. T h e curves at three NaC1 concentra-

tions, viz., 11.518 X 10 -~, 17.277 X 10 -5, and 28.795 X 10 -~ g.-equiv./1.,
show well-defined m a x i m a at nearly equivalent concentrations of g u m
arabates, i.e., 12.62 X 10 -5, 18.32 X 10 -5, and 29.403 X 10 -5 e q u i v . / 1 ,
respectively. At higher NaC1 concentrations, e.g., 17.852 X 10 -4 a n d
46.647 X 10 -4, the ~,p/c versus c curves are similar to those of neutral
polymers.
2oo b~ I I I I I I
\ Viscosity in p r e s e n c e of~
N~cl, O Nil 5 -
ISC - b 0 i'1.518 XIO Qvn.e_ziui/lib~
\ d,7. 7 ',.
D 38.795 ~ ~,
le¢- b ~ l?.ss~ x164 ,, -
~ ( ~ 01"46.647 X 1(~4 ~,

140 m

6O

40 ~ -

20
c (g/100 c.c.)
! I J I I ~ ]
0.2 0.4 0.6 0.8 1.0 1.2 1.4
FIe. 1. Reduced viscosity versus concentration.

Viscosity m e a s u r e m e n t s were extended to different solutions of g u m

a r a b a t e neutralized to different extents. T h e results are s u m m a r i z e d in
T a b l e I I I , a n d the corresponding ~l~p/Cversus a (extent of neutralization)
curves are given in Fig. 2.
Calculation of the extents of neutralization were done in the following
w a y : when to a 10 cc, solution of arabic acid (2.628%) 2.65 cc. of 0.0819
N N a O H was added, the acid was completely neutralized, as obtained
f r o m a potentiometric titration curve. T h e resulting solution was t h e n
t a k e n as 100% neutralized. Therefore, when to 10 co. each of the s a m e
 POLYELECTROLYTES. ii. GUM ARABATE 543

TABLE II
Viscosity-Concentration Effect in Presence of NaCl
Concentration of
gum arabate Concentra~on of NaC1 nsp~
g./lO0 cc. g. equiv.fl.
1.0146 11.518X 10-~ 0.9802
0.8117 1.0040
0.6494 1.0260
0.4329 1.0890
0.2886 1.1640
0.1924 1.2310
0.1283 1.2530
0.1015 1.1760
0.0676 1.1040
1.0146 17.277 X 10-5 0.9270
0.8117 0.9452
0.6494 0.9614
0.4329 0.9933
0.2886 1.0390
0.1924 1.0520
0.1283 1.0360
0.0885 0.9891
1.0146 28.795 X 10-5 0.8143
0.8117 0.8268
0.6494 0.8506
0.2886 0.8722
0.1924 0.8476
0.1283 0.8130
0.0855 0.8096
1.0146 17.852 X 10-4 • 0.5805
0.4504 0.5012
0.3006 0.4668
0.2004 0.4321
0.0891 0.4238
1.0146 46.647 X 10-4 0.4058
0.6764 0.3734
0.4509 0.3474
0.3006 0.3303

a r a b i c a c i d s o l u t i o n , 0.4, 0.8, a n d 2.2 cc., etc., of 0.0819 N N a O H w e r e

a d d e d t h e s o l u t i o n s w e r e n e u t r a l i z e d t o t h e e x t e n t of 15.10, 30.19, a n d
8 3 . 0 3 % etc., r e s p e c t i v e l y .
F i n a l l y t h e r e l a t i v e v i s c o s i t y of a s o l u t i o n w a s m e a s u r e d a t c o n s t a n t
c o n c e n t r a t i o n of g u m a r a b a t e w i t h i n c r e a s i n g p H , t h e p t I i n c r e m e n t
b e i n g o b t a i n e d b y t h e a d d i t i o n of a few d r o p s of a l k a l i t o a l a r g e v o l u m e of
t h e g u m a r a b a t e s o l u t i o n s u c h t h a t p r a c t i c a l l y no v a r i a t i o n in t h e c o n c e n -
t r a t i o n a p p e a r e d . A t first t h e v i s c o s i t y fall w i t h p H w a s s m a l l w h i l e a b o v e
a b o u t 9 p H t h e f a l l w a s m u c h m o r e r a p i d . W h e n a g a i n t h e p H of t h i s
544 SADHAN BASU, PARES CH. DASGUPTA AND ANIL K. SIRCAR

final solution was reversed and gradually b r o u g h t b a c k to the initial p H

value b y the addition of acid (viz., 6.8), there was no rise in viscosity,
which remained practically constant f r o m 11 to 6.8 p H . W h e n this final
solution was dialyzed, the viscosity gradually increased with time, till a t
last nearly the original value was regained. All these points are well illus-
t r a t e d in Fig. 3.

TABLE I I I
Viscosity Variation with the Extent of Neutralization
Concentration of Per cent
gum acid neutralized ~sp/C
%
1.3140 100.00 1.164
93.09 1.223
83.03 1.141
72.97 1.094
50.31 0.908
30.19 0.748
15.10 0.615
0.00 0.518
0.6570 100.00 1.229
93.09 1.342
83.03 1.295
72.97 1.249
50.31 1.049
30.19 0.871
15.10 0.719
0.00 0.613
0.3285 100.00 1.406
93.09 1.483
83.03 1.588
72.97 1.444
50.31 1.246
30.19 1.053
15.10 0.864
0.00 0.735

DISCUSSION
I t has been found t h a t the ~ p / c versus c plot (Fig. 1) of sodium a r a b a t e
solution increased sharply with dilution, which evidently indicates some
increase in the h y d r o d y n a m i c volume unit. This p h e n o m e n o n m a y reason-
ably be explained f r o m the consideration of the folding-unfolding proper-
ties of the high-polymeric chain compounds. At a finite concentration of
the g u m a r a b a t e in solution some of the sodium ions dissociated f r o m one
molecule, a n d are drawn b a c k b y a n o t h e r molecule, so t h a t on a time aver-
age, a polyion always has some a m o u n t of oppositely charged ions closely
associated with it. As the solution is diluted, i.e., as the concentration of
 POLYELECTROLYTEB. II. GUM ARABATE 545

16 I I I I I

14 ~ =. ~ 8 5 #..

Iz

10

6
¢ ?
o¢ ( / neuteahsat~on) ~ 1
• , I, t ,, l ~ I
20 40 60 80 iOO
FIG. 2. Reduced viscosity versus per cent neutralization.

the gum arabate is reduced, the probability of a polyion finding an oppo-

sitely charged ion near its vicinity diminishes, and as a result the effective
charge on the polyion increases with dilution. Repulsion between similarly
charged centers on the gum arabate chain causes the molecule to extend
which evidently increases with an increase in the dissociation of the gum
arabate molecule, i.e., the extension of the chain increases with dilution.

2.7 I I I I t

2,5

Z.3

Z.I

1.9

1,7
HCI

i5 ,. 1 I I I I
6 7 8 9. I0 II

FIG. 3. Relative viscosity versus pH.

546 SADttAN BASU, PARES CH. DASGUPTA A N n ANIL K. SIRCAR

This explains the rapid rise in viscosity of a gum arabate solution at lower
concentrations.
Various v~p/c versus c curves f o r g u m arabate solution in the presence
of different amount of NaC1 are also given in Fig. 1. It has been found that
by the addition of 11.518 X 10-5 g. equiv. NaCl/1. the sharp risein the
~,/c versus c curve vanishes, the curve showing a well-defined maximum
which appears when the stoichiometric concentration of the Na ion from
the polymer .becomes nearly equal to that from the added NaC1. With
increasing NaC1 concentration, the maximum shifts toward higher values
of sodium arabate concentration till at last it vanishes completely and
the curves resemble those of the neutral polymer. This type of peculiar
viscosity behavior has been noticed in the case of a large number of p01y-
electrolytes, e.g., polyacrylic acid (11), pneumococcus polysaccharides (9),
sodium pectinates (10), and a number of polyvinyl pyridonium deriva-
tives (6), and fits with the general behavior of polyelectrotytes.
There is another important characteristic of a solution of gum arabic
acid which can also be explained by the folding-chain theory. As the acid
is neutralized, the reduced viscosity of the solution increases. This is
evident from the curves in Fig. 2. As the acid is neutralized with sodium"
hydroxide, more and more sodium salt of the acid dissociates, the effective
charge on the polymer goes up, and, hence, the reduced viscosity increases.
Nearabout the poin t of complete neutralization, the ~ ~p/c value decreases
although slowly. This fall in v ~,/c value has been explained by Katchalsky
and Kuhn (7) as due to a high charge density on the polymer chain and an
increased concentration of oppositely charged sodium ions. This viscosity
behavior is exactly the opposite of what happens to, and is expected of,
a weakly acidic Colloidal electrolyte.
The viscosity of the gum arabate solution (even of a dilute solution)
changes markedly with pit. It will be evident from Fig. 3 that at pit 9.5,
obtained by adding few drops of alkali to the gum arabate solution, the
viscosity of the 1.05% solution of sodium gum arabate falls sharply.
When the pH is reversed from 11 to 6.8 by neutralizing the alkali with
acid, the curve is not retraced and the viscosity remains nearly constant,
showing a slight fall with diminishing pit. If, after bringing the pH back
to the original value with acid, the solution be dialyzed, the viscosity
gradually rises with time and the original viscosity is nearly recovered
after about 8-10 hr.
If this effect be due simply to pit, then there is no reason why the
viscosity behavior should depend on the mode of pH variation. Further
this pH effect cannot be due to breakdown of micellar units since in dilute
solution gum arabate is dispersed to molecular units. It has been shown
by Tendeloo (12) and also by us (Table II and Fig. 1) that a similar fall
in viscosity takes place when, instead of sodium hydroxide, an increasing
 POLYELECTROLYTES. II. GUM ARABATE 547

amount of sodium chloride solution is added step by step to the gum ara=
bate solution. Thus if the fall in viscosity in the presence of N a 0 H be
attributed to the presence of sodium ion, then the explanation of the
above phenomenon will follow simply from the folding-chain theory of
polyelectrolytes. When the pH is reversed from 11 to 6.8 by the addition
of successive quantities of HC1, the N a 0 H present is simply neutralized
to NaCI. There is no change in Na ion concentration and hence the vis'
cosity of the solution remains unaltered because the coiling of the chain
remains constant. But when this solution is dialyzed, the sodium salt
present in the system passes out, and as a result the viscosity increases
owing to an increased extension of the polymer chain.
It is evident, therefore, that all the peculiar viscometric characteristics
of the gum arabate solution may satisfactorily be explained by the folding=
chain theory of polyeleetrolytes which presupposes the existence of flexible
chain molecules in solution. As the chain is irregular due to side branching,
the coiling up of the molecules cannot proceed to a great extent, and
consequently the relative rise in viscosity on dilution is much less in the
case of gum arabic as compared to other polyelectrolytes recorded in the
literature (6,10).

ACKNOWLEDGMENT
Thanks are due to Prof. S. R. Palit, Indian Association for the Cultivation of Science,
for his keen interest, helpful suggestions, and constant encouragement during the course
of these investigations.

SUMMARY
Measurements of viscosity with varying concentration of solute,
added sodium chloride, and the extent of neutralization of the solutions of
gum arabate and arabic acid have been reported. A connected explanation
for all the different observations has been formulated b y the assumption of
the existence of flexible chain molecules in solutions of gum arabate. From
the same considerations the effect of pH variation with alkali on the
relative viscosity of gum arabate solution has been attributed to the
effect of sodium ion from alkali rather than the particular pH value.

REFERENCES
1: O~KLEY, H. B., Trans. Faraday Soc. 31, 136 (1935).
2. HEIDELBERGER, .¥[., AND KENDALL, F. E., J. Biol. Chem. 84, 639 (1929).
3. CHALLINO~, S. W., HAWORTH, W. N., AND HlSST, E. A., J. Chem. Soc. 1931, 258.
4. NORMAN,A. G., The Biochemistry of Cellulose, the Polyuronides, Lignin, etc., p. 125.
Oxford Press, London, 1937.
5. IV[EYEa,K. H., Natural and Synthetic High Polymers, Vol. IV, p. 375. Interscienee
Publishers Inc., New York.
6. Fuoss, R. M., Science 108, 545 (1948); J. Polymer. Sci. 3, 246, 602 (1948); ibid. 4,
97 (1949).
548 SADttAN BASU~ PARES OH. DASGUPTA AND ANIL K. SIRCAR

7. KATCHALSK¥,A., KUttN, W., AND KU~ZLE, O. Helv. Chem. Acta, 31, 1994 (1948).
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