90 Starch/Stärke 53 (2001) 90–94

Md. Nurul Islam1, Effect of Temperature and Starch Concentration

Abdul Manan Dos Mohd.2,
Mohd. Azemi Bin Mohd.
Noor2
1 Department of Food
Technology and Rural
Industries, Bangladesh
Agricultural University,
Mymensingh, Bangladesh
2
School of Industrial
Technology, Universiti
Sains Malaysia, Penang,
Malaysia
on the Intrinsic Viscosity and Critical
Concentration of Sago Starch (Metroxylon sagu)
Intrinsic viscosity and critical concentration of sago starch dispersions were studied at
different temperatures and presence of solutes (sodium chloride, glucose and su-
crose). Ubbelohde capillary viscometer was used to measure relative viscosity. Intrin-
sic viscosity decreases with an increase in temperature but the critical concentration
remained fairly constant over the range of temperature studied. Sodium chloride en-
hanced the intrinsic viscosity but sugars somehow reduced it. Critical concentration is
defined as the point where the starch molecules start to entangle with each other and
abruptly enhance viscosity. Sodium chloride enhanced the molecular entanglement
and lowered the critical concentration.

Keywords: Sago starch; Intrinsic viscosity; Critical concentration

1 Introduction tration. McMillan [5] showed that the reduced viscosity

can be written in the form of Huggin’s equation
Pasting and rheological behaviour of starch dispersions
are dependent on the concentration of starch or the num- ηsp/c = [η] + k’ [η]2c (1)
ber of starch chains present in the dispersion. Morris [1]
where ηsp = (ηr – 1), ηr = (η of solution/η of solvent) and
reported that the increase in viscosity at higher polysac-
k is the Huggin’s constant. The intrinsic viscosity can also
charide concentration is due to the overlapping and/or in-
be determined by extrapolation to zero concentration
terpenetrating of its molecular chains with each other. The
using Kramer’s equation [5]
chain overlapping occurs at a certain concentration. Criti-
cal concentration is defined as the concentration where lnηr/c = [η] – k’’ [η]2c (2)
the plot of viscosity against the concentration shows an
abrupt increase in its gradient. In molecular terms this For dilute systems the equation can be shortened by re-
abrupt transition corresponds to the onset of coil overlap- taining only the first order term and [η] can be determined
ping between the polymer chains in the dispersions. The from the slope of the plot of c against lnηr. The intrinsic
entanglement starts above this concentration. The onset viscosity is generally calculated from the equations used
Research Paper

of coil overlapping can be determined by the number of
chains present and the volume faction occupied by each
chain. Coil volume is characterized by the intrinsic viscos-
ity or limiting viscosity number [η ]. The intrinsic viscosity
[η ] is a characteristic of macromolecules that is directly
related to their ability to disturb flow and indirectly to the
size and shape of the molecules [2]. The intrinsic viscosi-
ty is expressed as:
ηsp
[η ] = lim
c →0 c
This value is obtained by measuring specific viscosities at
different concentrations at the same shear rate and ex-
trapolating the course of specific viscosity to infinite dilu-
tion [3]. In dilute solutions the interaction between macro-
molecules are negligible [4] and the reduced viscosity ex-
pressed as [(η–ηo)/ηoc] becomes independent of concen-
Corresponence: Mohd. Azemi Bin Mohd. Noor, School of Indus-
trial Technology, Universiti Sains Malaysia, 11800 Penang,
Malaysia. Phone: (+) 60-4-6 57 78 88, Fax: (+) 60-4-6 57 36 78.
by Tanglertpaibul and Rao [2] for tomato serum
ηr = 1 + [η]c (3)
ηr = exp[η]c (4)
ηr = 1/(1 – [η]c) (5)
The objective of the present study is to determine the
effect of different temperatures and presence of other
solutes (such as sucrose, glucose, sodium chloride etc.)
on the onset of coil overlapping of sago starch molecules
and the intrinsic viscosity of the solution. At the same
time, the relationship of the magnitude of intrinsic viscos-
ity with starch concentration, solutes concentration and
temperature is also studied.
2 Materials and Methods
Commercial sago (Metroxylon sagu) starch, with an amy-
lose content of 27% (w/v) was obtained from a sago
starch factory in Sarawak, Malaysia. Starch at varying
concentrations ranging from 0.2–4.6 g/100 mL salt (sodi-

© WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001 0038-9056/2001/0202-0090 $17.50+.50/0

Starch/Stärke 53 (2001) 90–94 Effect of Temperature and Starch Concentration on the Intrinsic Viscosity 91

um chloride) and solutes (glucose and sucrose) solution (Tabs. 1–4). In general the value of the intrinsic viscosity
were dispersed. The salt and solutes solution contained calculated using equation 3 is higher than those obtained
0.05–1.0 g sodium chloride and 0.2–2.0 g solutes, respec- using equations 4 and 5. This observation holds true for
tively, per 100 mL distilled water. The starch dispersions all starches with varying amounts of salts and solutes.
were then heated to gelatinize under constant stirring to The values of intrinsic viscosity gradually decreased with
avoid settling and agglomeration and then autoclaved at the increase of temperatures. Sodium chloride enhanced
121 °C for 30 min to dissolve and disintegrate the starch intrinsic viscosity (Tab. 2) as opposed to glucose and su-
granules completely. The dispersions were then cooled to crose. The result may be explained on the basis that the
60 °C and filtered through glass wool using a suction long chain molecules do not flow as a whole, but in a seg-
pump. The filtrate was used to study its flow properties. A
ments or in a cluster. The viscosity thus depends on chain
Cannon Ubbelohde dilution viscometer (Cannon lnst.
Co.) was used to measure the flow time at each concen- Tab. 1. Intrinsic viscosity of sago starch as affected by
tration with varying temperature ranging from 60–80 °C. temperature.
The temperature was established with a constant temper- Tempe-
ature water bath. The time required to flow from one level rature [°C] [η]1 r1 [η]2 r2 [η]3 r3
indicator to another, known as flow time, was measured.
The intrinsic viscosity could be obtained by using three 60 0.767 0.999 0.563 0.992 0.420 0.972
different methods based on the three different equation. 70 0.763 0.999 0.534 0.992 0.405 0.978
80 0.688 0.999 0.525 0.995 0.380 0.972
2.1 Determination of intrinsic viscosity Intrinsic viscosity expressed according to Tanglertpaibul and Rao
[2]; [η]1 = 1 + [η]c, [η]2 = exp[η]c, [η]3 = 1/(1–[η]c).
The viscometer was rinsed with solvent and drained for r = Correlation coefficient.
excess solvent, thereafter, it was placed in a constant
temperature water bath. Exactly 10 mL filtered solvent Tab. 2. Intrinsic viscosity of sago starch solutions as
was transferred to the viscometer. The viscometer was affected by sodium chloride concentration.
held for a while to equilibrate temperature, then the liquid
Salt (NaCl) [η]1 r1 [η]2 r2 [η]3 r3
level in the viscometer was brought above the upper
[g/100 mL
graduation mark. The liquid was then allowed to flow water]
down through the capillary and the time required exactly
to pass the meniscus of the lower mark of the viscometer 0.00 0.323 0.999 0.254 0.996 0.202 0.986
was recorded. The mean of at minimum three readings 0.05 0.388 0.997 0.277 0.995 0.213 0.983
was taken. The procedure was repeated for each variable 0.10 0.420 0.999 0.311 0.994 0.234 0.979
under study. The relative viscosity (ηr), was then calculat- 0.20 0.474 0.999 0.346 0.993 0.254 0.973
ed as follows: 0.50 0.480 0.999 0.347 0.994 0.256 0.977
ηr = t / to (6) 1.00 0.958 0.989 0.557 0.987 0.337 0.957
Intrinsic viscosity expressed according to Tanglertpaibul and Rao
where t = efflux time for solution, to = efflux time for the [2]; [η]1 = 1 + [η]c, [η]2 = exp[η]c, [η]3 = 1/(1–[η]c).
pure solvent. r = Correlation coefficient.

The intrinsic viscosity was then calculated from the slope Tab. 3. Intrinsic viscosity of sago starch solutions as
of the plots of the equation of 3, 4, and 5 according to the affected by glucose concentration.
hypothesis of McMillan [5].
Glucose [η]1 r1 [η]2 r2 [η]3 r3
[g/100 mL
3 Results and Discussion water]

3.1 Intrinsic viscosity
Equations 3, 4 and 5 were employed to calculate the in-
trinsic viscosity of sago starch. Straight line relationships
with linear regression coefficient of 0.99 were obtained.
Determination of the intrinsic viscosity based on slopes of
plots were reported [5] as having higher correlation coef-
ficients and lower standard errors than those based on in-
tercepts methods. The values of intrinsic viscosities using
the above approaches varied, but showed similar trends
0.00 0.592 0.999 0.404 0.992 0.283 0.968
0.20 0.398 0.999 0.298 0.995 0.226 0.983
0.50 0.363 0.999 0.276 0.996 0.216 0.985
1.00 0.355 0.999 0.275 0.996 0.213 0.984
1.50 0.332 0.999 0.256 0.996 0.199 0.985
2.00 0.288 0.999 0.233 0.997 0.187 0.989
Intrinsic viscosity expressed according to Tanglertpaibul and Rao
[2]; [η]1 = 1 + [η]c, [η]2 = exp[η]c, [η]3 = 1/(1–[η]c).
r = Correlation coefficient.
92 Islam et al. Starch/Stärke 53 (2001) 90–94

Tab. 4. Intrinsic viscosity of sago starch solutions as bridges which may compact the molecules thus lowering
affected by sucrose concentration. the hydration volume and reduce viscosity. Sugar may
disrupt the organization of starch gel from ordered to dis-
Sucrose [η]1 r1 [η]2 r2 [η]3 r3
[g/100 mL ordered structure and as a consequent decreased its vis-
water] cosity [13].

0.00 2.133 0.999 0.879 0.965 0.403 0.865

0.20 2.071 0.999 0.812 0.967 0.373 0.868
0.50 1.659 0.999 0.770 0.973 0.356 0.895
1.00 1.653 0.999 0.729 0.957 0.355 0.862
1.50 1.576 0.999 0.707 0.975 0.342 0.901
2.00 1.454 0.999 0.690 0.973 0.346 0.894
Intrinsic viscosity expressed according to Tanglertpaibul and Rao
[2]; [η]1 = 1 + [η]c, [η]2 = exp[η]c, [η]3 = 1/(1–[η]c).
r = Correlation coefficient.
length [6]. When a solution is heated at constant pressure
both factors – thermal energy of the molecules and inter-
molecular distance – increase. These combined factors
consequently reduce its viscosity. Elfak et al. [7] also re-
ported that molecular vibration increases with the in-
crease in temperature causing thermal instability of the
polymer molecules. Starch molecules thus become insta-
ble at higher temperature and their molecular chains
break down and consequently the viscosity is reduced. At
higher temperature the hydrogen bonding system in
starches or in between starch and water molecules may
have weakened and/or broken down which may result in
a reduction in hydration volume of the molecules which
may contribute to the reduction in intrinsic viscosity. The
relatively lower viscosity at higher temperature may also
be due to the tendency of complete release of linear
chains surrounding the starch molecules into the solution.
3.2 Critical concentration
Fig. 1 shows that the relative viscosity of sago starch so-
lution increases linearly with concentration. The viscosity
increases rapidly above 1.8 g starch per 100 mL solvent
(distilled water). The effect of temperature up to this con-
centration is negligible. According to Morris [1] this con-
centration may be regarded as critical concentration for
sago starch. The starch solution is stable at or below the
critical concentration and the viscosity is independent of
concentration and temperature. Above this critical con-
centration the entanglement starts and the viscosity
rapidly increases. The gradient of the plot decreased as
the temperature increased implying viscosity reduction
at higher temperature. Above the critical concentration in-
crease in temperature will disrupt hydrogen bonding and
accordingly the viscosity is decreased. However it was
observed that starches treated with sodium chloride, glu-
cose and sucrose behaved differently (Figs. 2–4). The
critical concentration increased with increasing amount of
glucose added and decreased as the amount of sodium
chloride increased. Sucrose did not influence the critical

When starch is added to sodium chloride solution, sodium

salts of starch are formed. Since starch is acidic in nature
[8] and is negatively charged, chloride ions are repelled
by the starch molecules and sodium ions penetrate into
the starch chains, replacing the H+ ions which migrate to
the water phase. As a result the solution becomes more
acidic. Due to this high acidity extensive expansion and
unfolding of starch molecules occurs [9], resulting in high-
er hydration volume of the molecules with subsequent in-
crease in viscosity.

Sugar alters the properties of the solvent by lowering the

dielectric constant [10] and thus decreasing the availabil-
ity of water molecules for hydration of the starch polyan-
ion. The reduction in dielectric constant would suppress
the dissociation of the starch polyanion and its counter
ions [11] thus producing a less extended configuration of
starch molecules and lowering the viscosity. Spies and
Hoseney [12] reported that sugar may penetrate into the Fig. 1. Relative viscosity versus sago starch concentra-
amorphous regions of the starch molecules and form tion.
Starch/Stärke 53 (2001) 90–94 Effect of Temperature and Starch Concentration on the Intrinsic Viscosity 93

Fig. 2. Effect of sodium chloride concentration on the crit- Fig. 4. Effect of sucrose concentration on critical concen-
ical concentration of sago starch solutions. tration of sago starch solutions.

concentration. Above the critical concentration, sodium

chloride enhanced relative viscosity but the opposite
holds true for glucose and sucrose.

4 Conclusion

The intrinsic viscosity of dilute solutions of sago starch is

affected by the temperature, the presence of sodium chlo-
ride and Iow-molecular weight sugars. Sodium chloride
enhances the intrinsic viscosity whereas increase in tem-
perature, sucrose and glucose concentration decreases
the intrinsic viscosity. However, critical concentration is
somehow unaffected by temperature but affected by con-
tent of sodium chloride and sugars. Critical concentration
decreased as the amount of sodium chloride increased.
Glucose somehow delayed onset of molecular entangle-
ment, suggesting the ability of glucose to stabilise the in-
trinsic viscosity. Below the critical concentration the intrin-
sic viscosity of sago starch remained unaffected by tem-
perature and added ingredients.

Acknowledgment

This work was funded by the “Land Custody and Devel-

Fig. 3. Effect of glucose concentration on the critical con- opment Authority (LCDA)” of the Government of Sarawak,
centration of sago starch solutions. Malaysia.
94 Islam et al.
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(Received: September 8, 1997)
(Revision received: November 21, 2000)