International Journal of Food Properties, 9: 889–896, 2006

Copyright © Taylor & Francis Group, LLC

ISSN: 1094-2912 print / 1532-2386 online
DOI: 10.1080/10942910600763783

A TENTATIVE EXPLANATION FOR THE SUBSTANTIAL

RISE OF THE GELATINIZATION TEMPERATURE OF
STARCH BY ADDING SALT AND HYDROXIDE

J.O. Brumovsky and L.A. Brumovsky

Facultad de Ciencias Exactas Químicas y Naturales, Universidad Nacional de
Misiones, Posadas, Misiones, Argentina

D.B. Thompson
Penn State University, University Park, PA, USA

The effects of three saline solutions, LiCl, NaCl, and KCl, on the gelatinization temperature
of starch-salt systems were studied. The same but systems with the addition of NaOH were
also studied. A rise of gelatinization temperature of all starch-salt-water systems studied
was observed. The gelatinization range (ΔTgr) of starch-salt-water systems, was not
affected by the nature of the cation; instead it was affected by its concentration; the rise of
the gelatinization temperature (ΔTgel) and gelatinization enthalpy (ΔH) were not affected
by the nature and concentration of the cation. The rise of the gelatinization temperature
(ΔTgel) of starch-salt-NaOH-water systems was significantly affected by the nature and
concentration of the cation, and by the concentration of NaOH. Li+ was responsible for a
smaller rise of gelatinization temperature and K+ for a greater rise of gelatinization temper-
ature. Increases in the gelatinization temperature of up to 48.0°C were measured. These
results may indicate that the rise in gelatinization temperature of starch-salt-NaOH-water
systems could be explained based on the assumption that starch behaves as a weak ion
exchanger governed by the Donnan potential.

Keywords: Gelatinization, Starch, Donnan potential, Differential scanning calorimetry.

INTRODUCTION
The gelatinization temperature of a starch suspension is an important feature in the
manufacture of starch derivatives with the condition that the granule structure must be pre-
served. If in these processes the temperature of the suspension rises beyond the gelatinization
temperature, the starch will start to gelatinize and become soluble in water. Under this fact,
the derivatization process cannot be continued. Consequently, the product is lost and there is a
large amount of work involved in cleaning out the equipment.[1] In addition, the derivatization
produces a decrease in the gelatinization temperature of the starch. Therefore, only a limited
degree of derivatization can be obtained. Some derivatization processes are highly exothermic
and require complex temperature controls in order to avoid gelatinization and to maintain an

Received 20 September 2005; accepted 19 April 2006.

Address correspondence to L.A. Brumovsky, Faculdad de Ciencias Exactas Quimicas y Naturales, Uni-
versidad Nacional de Misiones, Felix de Azara 1552, Argentina. E-mail: lab@fceqyn.unam.edu.ar

889
890 BRUMOVSKY, BRUMOVSKY, AND THOMPSON

adequate reaction rate. In these processes, it is usually necessary to ionize the hydroxyl groups
of starch. This ionization is best accomplished by making the starch suspension highly alka-
line. A pH of at least 9 is required, and one above 10 is preferred, taking care not to exceed a
pH of 12 since the starch granules would swell and start to gelatinize. Sodium hydroxide is
the most commonly alkali used for starch modification reaction. However, to prevent a pH
rising above 12 in any part of the reaction vessel, the sodium hydroxide is usually diluted to a
concentration less than a 4% by weight before injecting it into the starch slurry. This produces
an increase of the reaction vessel capacity in order to hold the excess water introduced with
the sodium hydroxide. Moreover, the dilution of starch slurry causes a loss in reaction effi-
ciency and more reagents are needed to complete the reaction.[2]
In practice, it has been found that the gelatinization temperature of starch can be raised
by adding some salts like sodium sulphate, sodium chloride, etc.[3,4,5,6] The presence of salts
also allows the pH rising up to 12.5 without causing swelling or gelatinization. Salts concen-
tration can reach values as high as 55% by weight and even higher values, with a great reduc-
tion of the amount of water introduced into the slurry with the pH adjusting agent.[2] Several
authors have tried to explain how electrolytes affect the gelatinization temperature of starch,
but they have not succeeded because they have assumed a mechanism that did not perform
were in some simple systems.[4,7] Oosten[1] has proposed a hypothesis to explain electrolyte
effects on gelatinization temperature based on the assumption that starch behaves as a weak
ion exchanger governed by the Donnan potential. However, there are not enough experi-
ments to support his hypothesis. Ion exchangers, are insoluble solid materials which carry
exchangeable cations or anions. They consist of a framework, which is held together by cova-
lent bonds or lattice energy. This framework carries a positive or negative electric charge,
which is compensated by ions of opposite charge, called counter ions. The counter ions are
free to move within the framework and can be replaced by other ions of the same charge. The
framework of a cation exchanger is usually a macromolecular or crystalline polyanion.[8]
When a cation exchanger is placed in an electrolyte solution, both the electrolyte solu-
tion and the exchanger will exchange counter ions with each other until equilibrium is reached.
Although the driving force for the counter ion exchange is a simple diffusion, the process dis-
turbs the electroneutrality. An accumulation of negative charges will occur in the cation
exchanger and an accumulation of positive charges will occur in the solution. Consequently,
the concentration ratio of counter ions will not necessarily be the same in both phases. The
electric potential difference generated between the two phases is called Donnan potential. In
general, an ion exchanger prefers some species instead of other compounds because of interac-
tions between the charged framework and counter ions. As a rule, a cation exchanger prefers
the counter ion of highest valence, and of smallest solvated equivalent volume (solvated equiv-
alent volume for Li+ > Na+ > K+ > Rb+ > Cs+), and the least associated with the co-ion.[8]
Oosten[9] observed a substantial rise of the gelatinization temperature by adding NaCl
and NaOH, when compared with NaCl. Oosten used a Brabender amylograph to determine
the gelatinization temperature of different salt systems. The limitation of Brabender amylo-
graph to work above 100 °C did not let him detect substantial increases of Tgel in some salt
systems. DSC (Differential Scanning Calorimetry) is particularly useful to investigate the
phase transitions of starch-water[10] systems because it allows: (1) the study of starch gelati-
nization over a wide range of starch/water ratios, (2) the determination of gelatinization tem-
peratures above 100 °C, and (3) the estimation of transition enthalpies.[11,12,13,14,15,16,17,18]
The effects of three salt solutions, LiCl, NaCl, and KCl, at different concentrations
on the gelatinization temperature of starch-salt systems were studied. The same systems in
the presence of NaOH were also studied. Weak-acid cation exchangers have an increased
 GELATINIZATION TEMPERATURE OF STARCH 891

selectivity for the cation of these salts (selectivity of K+ > Na+ > Li+). Based on the Don-
nan potential to explain the rise in the gelatinization temperature by adding salt and
hydroxide, we hypothesize that the use of salts with the same anions and different univa-
lent cations in starch-salt-NaOH-water systems should increase the gelatinization temper-
ature in a proportion related to the selectivity of cations. The aim of this study was to try
to explain the effect of the substantial rise of gelatinization temperature of starch by add-
ing salts and sodium hydroxide.

MATERIALS AND METHODS

Common corn starch (CCS) was obtained from the National Starch and Chemical
Company. CCS was washed with dionized water twice to remove possible traces of ions
and was then filtered and dried overnight in a vacuum oven at 50°C. AACC standard
method[19] was used for moisture determination. All reagents used were analytical grade
or better (Fisher Scientific Company).

Preparation of Salts-NaOH Solutions

Salt solutions of LiCl, NaCl, and KCl (2 and 4 molal) were prepared. Additional salt
solutions were prepared by adding NaOH to a portion of the previous salt solutions to
obtain 0.25 m and 0.5 m NaOH, respectively.

Differential Scanning Calorimetry

Thermal analysis was performed using a differential scanning calorimeter (DSC 7,
PerkinElmer Corp., Norwalk, CT) equipped with a thermal analysis data station
(PerkinElmer). Indium was used as a calibration standard. The reference cell contained a
sealed, empty, stainless steel pan. Starch samples (∼ 15.0 mg, dwb) were weighed into
preweighed stainless steel pans (Perkin-Elmer). Deionized water or salt solutions were
added to obtain ∼ 30% (w/w) starch suspensions. The samples were stirred with a needle.
Pans were sealed, the total weights were determined, and the suspensions were stored
overnight at room temperature. All samples were heated at 5°C up to 180°C, at a heating
rate of 10°C/min. Gelatinization enthalpy, onset, peak and end transition temperatures
were calculated (7 Series Software, Perkin-Elmer). Analyses were performed in duplicate
and mean values and standard deviation are reported.

Statistical Analysis
Statistical analysis was made using the program Statgraphics plus.[20] To compare
values of temperature and gelatinization energy, an ANOVA test was used. To compare
individual means an a posteriori test (LSD) was used.

RESULTS
A rise of gelatinization temperature of all starch-salt-water systems studied was observed.
Gelatinization range (ΔTgr) was affected by cation concentration (p < 0.026) but not by its
nature. Rise of gelatinization temperature (ΔTgel) was affected by both variables, cation nature
(p < 0.018) and concentration (p < 0.0001); but gelatinization enthalpy (ΔH) was not affected by
892 BRUMOVSKY, BRUMOVSKY, AND THOMPSON

these variables (see Table 1). The addition of NaOH at different concentrations affected ΔTgr
(p < 0.0001), ΔTgel (p < 0.0001) and ΔH (p < 0.0001). Moreover, this addition produced a sig-
nificant influence of cation nature in ΔTgr and cation concentration in ΔH, not found in systems
without NaOH, ΔTgel varied with both variables in the system without NaOH.
The CCS-LiCl 2 m systems reduced ΔTgel by adding NaOH. The effect was dimin-
ished in CCS-LiCl 4 m systems. The CCS-NaCl 2 m systems increased ΔTgel by adding
NaOH. However, this effect was enhaced in CCS-NaCl 4m systems by adding NaOH. The
CCS-KCl 2m systems increased ΔTgel by adding NaOH. This effect was enhanced in CCS-
KCl 4m systems, as shown in Table 2. The CCS-LiCl 2 m and CCS-LiCl 4 m systems
increased ΔTgr by adding NaOH 0.5m. The CCS-NaCl 2 m and CCS-NaCl 4 m systems
increased ΔTgr by adding NaOH. The CCS-KCl 2 m systems increased ΔTgr by adding
NaOH. This effect was enhanced in CCS-KCl 4 m systems by adding NaOH 0.5 m, as
shown in Table 2. In all starch-salt-water systems the ΔH was reduced by adding NaOH, as
shown in Table 2. The DSC thermograms of CCS, starch-salt systems (2 m and 4 m salt),
starch-salt-NaOH systems (0.25 m and 0.5 m NaOH) are illustrated in Fig. 1. All starch-salt-
NaOH-water systems showed an exotherm with a peak (Tp) located between 125 – 135°C.

DISCUSSION
The weak acid character of the starch chain in the dissociation of alcoholic groups
present in the polymer is expressed according to the following equation:

St − OH ↔ St − O − + H + (1)

When starch granules are in suspension they absorb water and dissociate shown in Eq. 1 and
this dissociation has a pKa = 12.5. The concentration gradient of H+ will induce the H+ to

Table 1 Thermal analyses of CCS-water and CCS-water-salt systems.

Toa Tpb Tec ΔTgrd ΔTgele ΔHf

Samples (°C) (°C) (°C) (°C) (°C) (J/g)

CCS 60.36g 66.33 73.22 12.86 – 18.85

(± 0.47) (± 0.51) (± 0.31) (± 0.56) (± 0.64)
CCS + LiCl (2m) 71.3 78.33 85.45 14.15 10.94 20.1
(± 0.27) (± 0.42) (± 0.37) (± 0.46) (± 0.54) (± 0.7)
CCS + LiCl (4m) 66.97 73.67 81.44 14.47 6.61 20.58
(± 0.51) (± 0.45) (± 0.43) (± 0.67) (± 0.58) (± 0.61)
CCS + NaCl (2m) 70.09 76 83.12 13.03 9.73 20.63
(± 0.55) (± 0.41) (± 0.37) (± 0.66) (± 0.75) (± 0.55)
CCS + NaCl (4m) 67.06 73.83 81.28 14.22 6.70 19.42
(± 0.5) (± 0.37) (± 0.51) (± 0.71) (± 0.74) (± 0.51)
CCS + KCl (2m) 68.94 73.83 81.36 12.42 8.58 19.55
(± 0.45) (± 0.43) (± 0.39) (± 0.65) (± 0.67) (± 0.55)
CCS + KCl (4m) 65.64 71.7 79.8 14.16 5.28 19.28
(± 0.49) (± 0.5) (± 0.43) (± 0.65) (± 0.67) (± 0.47)
b p c e
a
To = onset temperature; T = peak temperature; Te = end temperature; dΔTgr = gelatinization range; ΔTgel =
f g
rise of gelatinization compared with CCS-Water system; ΔH = gelatinization enthalpy; Mean of two observations.
 GELATINIZATION TEMPERATURE OF STARCH 893

Table 2 Thermal analyses of CCS-water-salt-NaOH systems.

Samples Toa (°C) Tpb (°C) Tec (°C) ΔTgrd (°C) ΔTgele (°C) ΔHf (J/g)

LiCl (2m) + NaOH (0.25m) 70.86g 77.5 84.77 13.91 10.50 15.52
(± 0.39) (± 0.41) (± 0.47) (± 0.61) (± 0.61) (± 0.6)
LiCl (2m) + NaOH (0.5m) 62.1 70.83 80.26 18.16 1.74 9.93
(± 0.41) (± 0.39) (± 0.52) (± 0.66) (± 0.62) (± 0.5)
LiCl (4m) + NaOH (0.25m) 69.7 76.33 82.98 13.28 9.34 13.39
(± 0.47) (± 0.42) (± 0.51) (± 0.69) (± 0.66) (± 0.47)
LiCl (4m) + NaOH (0.5m) 66.45 73.83 81.71 15.26 6.09 10.9
(± 0.51) (± 0.41) (± 0.52) (± 0.73) (± 0.69) (± 0.65)
NaCl (2m) + NaOH (0.25m) 73.45 80.17 87.51 14.06 13.09 13.89
(± 0.37) (± 0.5) (± 0.41) (± 0.55) (± 0.60) (± 0.61)
NaCl (2m) + NaOH (0.5m) 70.81 77.83 88.68 17.87 10.45 11.16
(± 0.31) (± 0.46) (± 0.4) (± 0.51) (± 0.56) (± 0.71)
NaCl (4m) + NaOH (0.25m) 76.41 83.67 92.58 16.17 16.05 12.93
(± 0.56) (± 0.46) (± 0.46) (± 0.72) (± 0.73) (± 0.69)
NaCl (4m) + NaOH (0.5m) 81.65 89 97.05 15.40 21.29 11.7
(± 0.55) (± 0.55) (± 0.49) (± 0.74) (± 0.72) (± 0.52)
KCl (2m) + NaOH (0.25m) 85.11 93.83 108.66 23.55 24.75 16.44
(± 0.57) (± 0.53) (± 0.52) (± 0.77) (± 0.74) (± 0.27)
KCl (2m) + NaOH (0.5m) 92.82 99.17 107.25 14.43 32.46 14.17
(± 0.5) (± 0.47) (± 0.53) (± 0.73) (± 0.69) (± 0.39)
KCl (4m) + NaOH (0.25m) 88.4 100.7 113.83 25.43 28.04 14.35
(± 0.48) (± 0.47) (± 0.41) (± 0.63) (± 0.67) (± 0.44)
KCl (4m) + NaOH (0.5m) 108.4 114.33 118.33 9.93 48.04 8.23
(± 0.5) (± 0.45) (± 0.41) (± 0.65) (± 0.69) (± 0.51)
e
a
To = onset temperature; bTp = peak temperature; cTe = end temperature; dΔTgr = gelatinization range; ΔTgel =
rise of gelatinization compared with CCS-Water system; fΔH = gelatinization enthalpy; g Mean of two observations.

migrate from the granules to the water, reducing the pH of the water from 7 to 6.25. This
migration takes place because outside the granules the pH is influenced by the dissociation
of the water molecules, which have a pK = 14. At this point, there will be a potential differ-
ence between the starch granules and the water phase, called Donnan potential.
When salts such as LiCl, NaCl, or KCl are added to starch suspensions, some alco-
holic groups in the starch granule are converted to alcoholate, as shown in Eq. 1. The alco-
holate form is better dissociated and some H+ are replaced by the cations into the granules,
increasing therefore the Donnan potential. The released H+ produce a pH reduction
and the absorbed cations cause the rise in the gelatinization temperature of the starch-
salt-water systems. Because these salts are highly dissociated in the solution, they are not
a good binding agent for the released H+, and consequently both the absorption of cations
and the increase in the Donnan potential are rather limited. The Donnan potential
excludes anions (Cl− and OH−) from the granules and so the rise in the gelatinization tem-
perature is rather limited.
When the salt concentration is increased, H+ are no longer replaced by cations
because the solution is still not a good binding agent for the H+ and it can be released from
the granules. The Donnan potential decreases as a consequence of the increase of Cl− in
the solution. In this way, the decrease of the Donnan potential reduces its ability to
exclude anions from the granule, and consequently reduces the rise of the gelatinization
temperature. The H-bonds formed among inter- and intramolecular chains of starch are the
 (a ) (b)

60 60

CCS + KCl 4m + NaOH 0.5m

CCS + KCl 2m + NaOH 0.5m
50 50

CCS + KCl 4m + NaOH 0.25m

CCS + KCl 2m + NaOH 0.25m

CCS + KCl 4m
CCS + KCl 2m
40 40

CCS + NaCl 4m + NaOH 0.25m

CCS + NaCl 2m + NaOH 0.5m

CCS + NaCl 4m + NaOH 0.25m

CCS + NaCl 2m + NaOH 0.25m
30 30

CCS + NaCl 4m
CCS + NaCl 2m

894
Heat Flow, (mW)
Heat Flow, (mW)
20 20 CCS + LiCl 4m + NaOH 0.5m
CCS + LiCl 2m + NaOH 0.5m

CCS + LiCl 4m + NaOH 0.25m

CCS + LiCl 2m + NaOH 0.25m

10 10 CCS + LiCl 4m
CCS + LiCl 2m
10 mW
10 mW

CCS CCS

0 0
20 40 60 80 100 120 140 160 180 20 40 60 80 100 120 140 160 180
Temperature (C) Temperature (C)

Figure 1 Differential scanning calorimetry thermograms of CCS, CCS-water-salt, and CCS-water-salt-NaOH. 4(a) Systems with 2 molal salt concentration. (b) Systems with
4 molal salt concentration.
 GELATINIZATION TEMPERATURE OF STARCH 895

main forces responsible for maintaining the granule structure. Anion penetration into the
granules disrupts H-bonds facilitating gelatinization.[1] Limited absorption of cation and
limited exchange of H+ for cations in starch-salt systems at low salt concentration is con-
sistent with the current results of no significant change of ΔTgr and ΔH. When more salt is
added, more anion penetration occurs and the granules are weaker. This also appears con-
sistent with the smaller ΔTgel found in the present article.
After adding NaOH to starch-salt systems, the absorption of cations is very much
enhanced due to the consumption of H+ by the OH−. The increased number of cations
results in a higher Donnan potential, which more efficiently excludes the gelatinizing
anions, and therefore increases the gelatinization temperature. The current results suggest
that K+ rather than Na+, and Na+ rather than Li+ are absorbed by starch granules. This cat-
ion selectivity effect becomes more obvious when the rise of ΔTgel in starch-salt-NaOH
systems at the same levels of concentration is compared. An evidence of the lowest Li+
selectivity presented by the starch granules can be inferred by observing the decrease of
ΔTgel in starch-LiCl systems when the concentration of sodium hydroxide is increased. In
addition, the highest selectivity of K+ is manifested by the substantial rise of ΔTgel in all
starch-KCl systems when the concentration of NaOH is increased. The intermediate
selectivity of Na+ by the starch granules becomes evident due to the rise of ΔTgel in
starch-NaCl systems and this only occurs when sodium hydroxide is added at the highest
concentration of NaCl (see Table 2). The penetration of the cations into the granules in
starch-salt-NaOH systems seems to explain the reduction of the ΔH since no significant
variation of ΔH was observed in starch-water or starch-water-salt systems. All starch-salt-
NaOH-water systems showed an exotherm with a peak (Tp) located between 125 – 135°C,
as shown in Fig. 1. The presence of an exotherm peak located in the same range of temper-
atures was also detected in starch-NaOH-water systems. These results suggest that a
degradation reaction occurring between starch and NaOH.

CONCLUSIONS
The assumption that starch behaves as a weak cation exchanger governed by the
Donnan potential clearly explains the substantial rise of the gelatinization temperature of
common corn starch by adding univalent salts and hydroxide. However, more studies are
needed to determine the validity of the model in more complex systems and at a higher
salt-hydroxide concentration.

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