Journal of Food Engineering 104 (2011) 134–142

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Journal of Food Engineering

journal homepage: www.elsevier.com/locate/jfoodeng

Fitting Fick’s model to analyze water diffusion into chickpeas during soaking
with ultrasound treatment
Ali Yildirim a, Mehmet Durdu Öner b,⇑, Mustafa Bayram b
a
Department of Food Technology, Vocational School of Higher Education in Nizip, Gaziantep University, 27700 Nizip, Gaziantep, Turkey
b
Department of Food Engineering, Faculty of Engineering, Gaziantep University, 27310 Gaziantep, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: Fick’s model together with Arrhenius relationship were successfully used to evaluate water absorption of
Received 15 September 2010 chickpea during soaking at a temperature range of 20–97 °C with 25 kHz 100 W, 40 kHz 100 W and
Received in revised form 27 November 2010 25 kHz 300 W ultrasound treatments. Use of ultrasound, increase in ultrasound power and soaking tem-
Accepted 4 December 2010
perature significantly (P < 0.05) increased the water diffusion coefficient (Deff) of chickpea during soaking.
Available online 15 December 2010
Average gelatinization temperature of chickpea was found as 61.47 °C. Activation energy (Ea) values of
chickpea for below and above gelatinization temperature were found to be 28.69 and 9.34 kJ mol1,
Keywords:
respectively. Ultrasound treatments significantly decreased the soaking time of chickpea.
Chickpea
Fitting
Ó 2010 Elsevier Ltd. All rights reserved.
Fick’s model
Ultrasound
Water diffusion

1. Introduction legumes during soaking is of practical importance since it affects

Chickpea (Cicer arietinum L.) is one of the oldest and most
widely consumed legumes in the world, particularly in tropical
and subtropical areas. Major chickpea producer and exporter
countries are India, Turkey, Pakistan, Iran Islamic Republic, and
Australia. Chickpea is an important source of proteins, carbohy-
drates, B-group vitamins and certain minerals (Chavan et al.,
1986; Christodoulou et al., 2006). Food legumes decreased inci-
dence of several diseases, such as cancer, cardiovascular diseases,
obesity and diabetes (Bhathena and Velasquez, 2002). Legumes
are usually cooked before being used in the human diet to improve
the protein quality by destruction or inactivation of the heat labile
anti-nutritional factors (Wang et al., 1997). Recently, there has
been increasing demand for research to improve cooking of chick-
peas in developed countries where chickpeas are mainly consumed
to improve overall nutritional status by replacing animal foods
with legumes (Guillon and Champ, 1996). The most common
process of pre-soaking usually is not sufficient to decrease overall
cooking time of chickpea. Understanding water absorption in
Abbreviations: AOAC, official methods of analysis of AOAC International; EAD,
acoustic energy density in W cm3; Deff, water diffusion coefficient in m2 s1; d.b.,
moisture content in dry basis (%); inci, a special type of chickpea produced by
Çukurova Agricultural Research Institute (Adana, Turkey).
⇑ Corresponding author. Tel.: +90 342 3172305; fax: +90 342 3172362.
E-mail address: oner@gantep.edu.tr (M.D. Öner).
subsequent processing operations and the quality of the final
product.
Ultrasound is a form of energy generated by sound waves of fre-
quencies that are too high to be detected by human ear, i.e. above
16 kHz (Jayasooriya et al., 2004). Ultrasound cavitations could re-
sult in the occurrence of micro streaming which is able to enhance
heat and mass transfer. Ultrasonic is a rapidly growing field of
research, which is finding increasing use in the food industry
(Jayasooriya et al., 2004; Zheng and Sun, 2006). Ultrasound has
been used to enhance mass transfer in solid/liquid food systems
(Fuente et al., 2004; Riera et al., 2004). Ultrasound applications
were reported to promote the leaching of oligosaccharides in
legumes (Han and Baik, 2006) and to reduce cooking time of rice
(Wambura et al., 2008).
In the food industry, chickpea is pre-processed in the factories to
produce humus (as Arabic food), canned products, blended powder
products. To produce these products, chickpea is soaked and cooked.
Therefore, this study supplies important information and ultrasonic
technique to process it easily. In addition, it is known that chickpea
is a hard legume to cook. Therefore, ultrasonic technique supplies a
new solution to decrease soaking and cooking time.
These studies show that thermosonication can be used to in-
crease the water absorption during soaking operation. The objec-
tive of this study was to determine the applicability of Fick’s
second law of diffusion in modeling the water diffusion character-

0260-8774/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2010.12.005
 A. Yildirim et al. / Journal of Food Engineering 104 (2011) 134–142
istics of ultrasound treated chickpea in an attempt to determine
suitable processing conditions for rehydration.
2. Materials and methods
2.1. Raw materials
Certified chickpeas (inci-2003) with initial moisture content of
11.58% (d.b.) and an average diameter of 8.00 (±0.27) mm (mea-
sured with Mutitoyo No. 505-633, Japan, digital micrometer) ob-
tained from Çukurova Agricultural Research Institute (Adana,
Turkey), were used throughout this study. After removing foreign
materials and damaged seeds, they were sieved to standardize
the sizes, 7.5 –9 mm.
2.2. Water absorption determination during soaking operation
The soaking of chickpea was performed at 20, 30, 40, 50, 60, 70,
87, 92, and 97 °C without, and with 25 kHz 100 W (acoustic energy
density (EAD) of 0.025 W cm3), 40 kHz 100 W (EAD of
0.025 W cm3) and 25 kHz 300 W (EAD of 0.017 W cm3) ultra-
sound treatments. One hundred grams of chickpea seeds were im-
mersed in 2000 ml deionized water (1:20); conventional and
ultrasonic soaking were both performed in ultrasonic (US) tanks
(Intersonik Co., Turkey) until seeds were fully hydrated. Four
grams of chickpea and 80 ml soaking water (1:20) were quickly re-
moved from the tanks for the moisture content determination
within 30 min intervals. Chickpea seeds were gently wiped with
clean paper towel to remove excess water and ground for the mois-
ture content determination. The moisture contents of randomly se-
lected grains (5 g) were determined in dry basis at 105 °C for 48 h
using oven drying method (AOAC, 2002) and used for Fick’s mod-
eling of water diffusion. The experiments were replicated twice
and measurements were duplicated.
2.3. Determination of soluble solids loss during soaking of chickpeas
Four grams of chickpea and 80 mL of soaking water (1:20 ratio)
were removed from the soaking chamber after 3.5 h of soaking
operation at 97 °C. Soluble solids content (Brix, g/g%) of the soaking
water was measured at 25 °C by using Abbe-refractometer (Opton-
F.G. Bode and Co., Germany) and was reported as maximum solu-
ble solids loss.
2.4. Determination of gelatinization temperature of chickpeas
Birefringence images of the chickpea samples at soaking tem-
peratures of 40, 50, 60, and 70 °C were captured in a PC using a
polarized light microscope (OLYPOS TX51, Euromex Microscopen,
Ed Arnhem, Netherlands) equipped with a video camera (VC
3031, Euromex Microscopen, Ed Arnhem, Netherlands) connected
to the PC (Fig. 6). A solution of 1% (cooked chickpea flour/water)
samples were prepared. After 30 min of mixing, 20 lL of sample
solution was spread on lamella, and the birefringence images were
captured through the microscope. The gelatinization temperature
of the grains is defined as the temperature at which the birefrin-
gence of starch starts to diminish (Hoseney, 1994).
2.5. Statistical analysis
SIGMA PLOT 10 (Jandel Scientific, San Francisco, USA) were used
to fit the models and to plot the data. ANOVA and DUNCAN Multi-
ple Range Tests, using SPSS version 16, at P < 0.05 were performed
to determine effect of processing parameters.
135
3. Results and discussion
3.1. Water diffusion characteristics of chickpea during soaking
Food legumes are usually soaked before cooking to provide suf-
ficient amount of moisture for gelatinization of starch and/or gela-
tion of protein. The most important property for soaking of
chickpea is the moisture content to achieve the proper cooking
operation. It could be achieved either through conditioning below
the gelatinization temperature and then cooking above the gelati-
nization temperature, or through direct cooking above the gelatini-
zation temperature. Mass transfer plays a key role in food
processing, like humidification and dehumidification, dehydration,
distillation, absorption, etc. The driving force for mass diffusion is
the concentration difference. In solids, there can obviously be no
convection and all movements are by molecular diffusion due to
random molecular movements.
The water absorption characteristics of chickpea were analyzed
using moisture content (%, d.b.) values in this study. The mean
moisture contents and the statistical analysis of soaked chickpeas
at 20–97 °C without ultrasound, and with 25 kHz 100 W, 40 kHz
100 W and 25 kHz 300 W ultrasounds treatment were illustrated
in Figs. 1–4 and tabulated in Tables 1–4. The moisture contents
(%, d.b.) of chickpea during soaking were significantly (P < 0.05) in-
creased as the temperature, time and power of ultrasounds in-
creased (Figs. 1–4 and Tables 1–4). Chickpea water absorption
curves are characterized by an initial phase of rapid water pickup
followed by an equilibrium phase, during which the chickpea ap-
proaches its full soaking capacity. The rate of water absorption in-
creased with increasing temperature as suggested by the slopes of
the absorption curves getting steeper with increased temperature
(Figs. 1–4).
3.2. Primary modeling of chickpea water diffusion as a function of time
Many theoretical, empirical, and semi-empirical models have
been employed for modeling, to relate experimental results with
physical laws, the water absorption behavior of agricultural prod-
ucts during soaking. The theoretical mechanisms for the kinetics of
the diffusion process have been proposed for the Fickian diffusion
model by some researchers before (Bello et al., 2004; Kashaninejad
et al., 2007; Sabapathy et al., 2005; Seyhan-Gürtasß et al., 2001;
Gowen et al., 2007).
Moisture diffusivity is an important transport property neces-
sary for the design and optimization of all the processes that in-
volve internal moisture movement. Diffusion coefficient is the
160
140 20 o C
Moisture content (% g/g, d.b.)
30 o C
120
40 o C
100 50 o C
60 o C
80
70 o C
60 87 o C
40 92 o C
97 o C
20 Fick's Model
0
0 100 200 300 400 500 600 700 800
Time (min)
Fig. 1. Means of experimental and predicted moisture contents (% g/g, d.b.) of
chickpeas during soaking at different temperatures.
136 A. Yildirim et al. / Journal of Food Engineering 104 (2011) 134–142

A 140 A 180

160
120
Moisture content (%g/g, d.b.)

Moisture content (%g/g, d.b.)

140
100
120
80 100
20 o C (control) 50 o C (control)
60 80
20 o C + 25 kHz 100 W US 50 o C + 25 kHz 100 W US
20 o C + 40 kHz 100 W US 60 50 o C + 40 kHz 100 W US
40
20 o C + 25 kHz 300 W US 40 50 o C + 25 kHz 300 W US
20 Fick 's model 20 Fick 's model
0 0
0 100 200 300 400 500 600
0 100 200 300 400
Time (min) Time (min)

B 140
B 140

120
120

Moisture content (%g/g, d.b.)

Moisture content (%g/g, d.b.)

100 100

80 80
60 o C (control)
60 30 o C (control) 60 60 o C + 25 kHz 100 W US
30 o C + 25 kHz 100 W US 60 o C + 40 kHz 100 W US
40 40
30 o C + 40 kHz 100 W US 60 o C + 25 kHz 300 W US
30 o C + 25 kHz 300 W US Fick ' s model
20 20
Fick 's model
0 0
0 100 200 300 400 500 0 100 200 300
Time (min) Time (min)

C 140 C 160

140
120
Moisture content (%g/g, d.b.)
Moisture content (%g/g, d.b.)

120
100
100
80
80 70 o C (control)
40 o C (control)
60 70 o C + 25 kHz 100 W US
40 o C + 25 kHz 100 W US 60
70 o C + 40 kHz 100 W US
40 o C + 40 kHz 100 W US
40 40 70 o C + 25 kHz 300 W US
40 o C + 25 kHz 300 W US
Fick's model
20 Fick 's model 20

0 0
0 100 200 300 400 500 0 100 200 300 400
Time (min) Time (min)

Fig. 2. Means of experimental and predicted moisture contents (% g/g, d.b.) of Fig. 3. Means of experimental and predicted moisture contents (% g/g, d.b.) of
chickpeas during soaking at 20 (A), 30 (B) and 40 (C) °C temperatures without and chickpeas during soaking at 50 (A), 60 (B) and 70 (C) °C temperatures without and
with ultrasound treatments. with ultrasound treatments.

factor of proportionality representing the quantity of substance The chickpea seeds may be approximated as spheres with a mean
diffusing across a unit area through a unit concentration gradient diameter of 0.0040 m (±0.0001). Fick’s laws of diffusion (Eq. (1))
in unit time. Total amounts of diffusing substance entered a spher- and its derived equations account for most of the models used in
ical grain of radius r can be obtained from the following Fick’s ser- food science, as can be observed from publications (Garcia-Pascual
ies type equation (Crank, 1975): et al., 2006; Gowen et al., 2007; Sabapathy et al., 2005). Some of
the common assumptions and simplifications often made for solv-
X  
M  Me 1
6 Deff p2 2 ing Fick’s second law (Eq. (1)) include the following: (1) the mois-
¼ exp n t ð1Þ ture transfer is one dimensional, unsteady state in the radial
M o  Me n¼1 n2 p2 r2
direction, (2) chickpea is considered to be an almost spherical ob-
where M, Me, Mo are moisture contents (%, d.b.) at any time, ject, (3) the initial temperature and moisture distributions are uni-
equilibrium and initial, respectively. Deff and r are effective diffu- form, (4) there is a moisture gradient in the chickpea with respect
sion constant (m2 s1) and average radius of chickpea (m), respec- to time, (5) the thermal properties are constant, (6) chickpea is
tively. A fit of the experimental data for soaking times leads to the considered as a homogeneous isotropic solid, (7) moisture transfer
determination of an average diffusion coefficient, Deff, via Eq. (1) to and from the seed is due to concentration gradient, (8) the quan-
which is Fick’s law of diffusion of water in solids of spherical shape. tity of solid loss in the grains during cooking was neglected, (9) for
 A. Yildirim et al. / Journal of Food Engineering 104 (2011) 134–142 137

A 160 long soaking times, only the first term of series equation was
significant.
140
Moisture content (%g/g, d.b.)

In this study, the effect of loss of soluble solids from chickpea

120 seeds was not taken into account in calculating the moisture con-
tent because maximum loss of soluble solids from chickpea at tem-
100
peratures of 97 °C for 3.5 h soaking was about 2.06% of the original
80 87 o C (control) mass which in comparison with the water gain was assumed to be
87 o C + 25 kHz 100 W US negligible. Other researchers have also reported similar assump-
60
87 o C + 40 kHz 100 W US tion for other seeds (Sayar et al., 2001; Sabapathy et al., 2005).
40 87 o C + 25 kHz 300 W US When these assumptions were applied on Fick’s second law, the
Fick's model following equation was obtained.
20

0  
0 50 100 150 200 250 6 Deff p2 t
Time (min) M ¼ M e þ ðM o  Me Þ exp  ð2Þ
p2 r2

B 160 The Fick’s law of diffusion function is related to diffusion of

water and diffusion coefficient (Deff). For mathematical modeling
140
Moisture content (%g/g, d.b.)

of the variation of moisture content of chickpea during soaking

120 at each temperature without, and with ultrasounds treatment,
Fick’s law model was tested. The parameters in this model such
100
as Deff (main parameter), Me, were estimated by using the non-
80
92 oC (control) linear regression analysis of Eq. (2) and presented in Table 5. The
92 oC + 25 kHz 100 W US performance parameters of the model, the coefficient of determi-
60
92 oC + 40 kHz 100 W US nation (R2) and percentage of root mean square error (% RMSE)
40
92 oC + 25 kHz 300 W US
are given on Table 5. The course of the hydration, adequately fitted
20 Fick's model by a non-linear equation (Eq. (2)), and reveals the fact that the seed
moisture content increases with soaking time, use of ultrasound
0 treatments and increase in used ultrasound power at all tempera-
0 50 100 150 200 250
Time (min) tures (Figs. 1–4 and Tables 1–5). Water absorption ceases when the
seed attained the equilibrium water content (Sayar et al., 2001).
The diffusion process, which obeys the Fick’s law model, was found
C 160 to be a thermally activated process and sensitive to temperature,
time, ultrasound treatment and its power.
Moisture content (%g/g, d.b.)

140
When the temperature was raised from 20 to 97 °C, Deff values
120 were increased from 1.40  1010 to 7.72  1010 m2 s1, also sig-
nificant (P < 0.05) increase was observed in the equilibrium mois-
100
97 oC (control) ture content (Me) (from 119.82 to 150.05 (%, d.b.)) (Table 5). R2
80 97 oC + 25 kHz 100 W US and % RMSE values were in the range of 0.9894–0.9960 and
60 97 oC + 40 kHz 100 W US 2.51–8.03, respectively. The magnitude of diffusion coefficient re-
97 oC + 25 kHz 300 W US ported by Sayar et al. (2001) for temperatures ranging from 20 to
40 Fick's model 100 °C were 2.43  1010 to 39.16  1010 m2 s1 for spring chick-
20 pea and 1.99  1010 to 36.94  1010 m2 s1 for winter chickpea.
The water diffusion coefficient of chickpea ranged from
0
0 50 100 150 200 250 9.71  1011 to 5.98  1010 m2 s1 in the study of Seyhan-Gürtasß
Time (min) et al. (2001). The diffusion coefficients of chickpeas for tempera-
ture range of 45–98.7 °C were found as 0.14  1010–
Fig. 4. Means of experimental and predicted moisture contents (% g/g, d.b.) of
chickpeas during soaking at 87 (A), 92 (B) and 97 (C) °C temperatures without and
5.51  1010 m2 s1 in another study (Sabapathy et al., 2005). Dif-
with ultrasound treatments. fusivity values reported in this study were similar to the literature
results. Moisture absorption at elevated temperatures may induce

Table 1
Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of soaked chickpeas as a function of processing time and temperature.

Time (min) Moisture content (%, d.b.)

20 °C 30 °C 40 °C 50 °C 60 °C 70 °C 87 °C 92 °C 97 °C
0 11.58a,1 11.58a,1 11.58a,1 11.58a,1 11.58a,1 11.58a,1 11.58a,1 11.58a,1 11.58a,1
30 33.55b,1 37.40b,2 46.10b,3 62.36b,4 70.61b,5 76.09b,6 86.85b,7 91.54b,8 97.05b,9
60 43.88c,1 57.54c,2 62.58c,3 84.70c,4 97.89c,5 99.01c,6 108.58c,7 111.16c,8 121.06c,9
90 56.27d,1 66.99d,2 80.53d,3 95.43d,4 108.05d,5 110.19d,6 122.38d,7 125.43d,8 136.49d,9
120 65.50e,1 78.98e,2 88.24e,3 108.69e,4 115.63e,5 119.45e,6 129.30e,7 131.36e,8 144.71e,9
150 72.52f,1 82.27f,2 97.30f,3 115.84f,4 124.02f,5 126.35f,6 135.41f,7 137.76f,8 148.59f,9
180 76.91g,1 84.53g,2 101.90g,3 120.82g,4 126.57g,5 129.78g,6 138.37g,7 142.44g,8 150.72g,9
210 81.93h,1 93.76h,2 110.18h,3 122.71h,4 128.99h,5 130.68h,6 140.17h,7 142.67h,8 151.97h,9
a–h
Indicate statistical differences between each row at a = 0.05.
1–9
Indicate statistical differences between each column at constant temperatures, a = 0.05.
138 A. Yildirim et al. / Journal of Food Engineering 104 (2011) 134–142

Table 2
Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of soaked chickpeas at 20, 30, and 40 °C with and without ultrasound treatments.

Time (min) Moisture content (%, d.b.)

20 °C 20 °C + 40 kHz 100 W 20 °C + 25 kHz 100 W 20 °C + 25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a
30 33.55a 34.82b 40.61c 43.18d
60 43.88a 44.97b 54.06c 55.93d
90 56.27b 56.24a 65.76c 69.60d
120 65.50b 64.60a 70.64c 74.85d
150 72.52b 70.24a 78.20c 86.92d
180 76.91b 76.55a 85.14c 91.89d
210 81.93b 80.54a 89.48c 95.66d
240 88.39b 86.14a 95.14c 102.30d
270 90.63a 92.05b 99.12c 106.56d
300 98.06b 97.69a 103.11c 111.56d
30 °C 30 °C + 40 kHz 100 W 30 °C + 25 kHz 100 W 30 °C + 25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a
30 37.40a 39.79b 41.04c 49.85d
60 57.54a 57.79b 60.40c 60.88d
90 66.99b 66.24a 73.77c 72.19d
120 78.98b 78.37a 79.63c 90.31d
150 82.27b 81.72a 86.40c 100.06d
180 84.53a 84.87b 92.52c 107.72d
210 93.76b 93.20a 98.00c 111.05d
240 104.78b 104.40a 106.25c 113.29d
270 107.75b 107.39a 108.23c 115.60d
300 109.96b 109.75a 112.03c 118.85d
40 °C 40 °C + 40 kHz 100 W 40 °C + 25 kHz 100 W 40 °C + 25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a
30 46.10b 45.55a 54.71c 59.86d
60 62.58a 63.92b 72.20c 77.41d
90 80.53b 78.70a 84.23c 97.25d
120 88.24a 89.43b 93.59c 107.08d
150 97.30a 100.21b 109.76c 115.29d
180 101.90b 100.62a 115.10c 121.19d
210 110.18b 109.70a 118.23c 128.12d
240 111.00a 112.58b 122.29c 127.27d
270 117.95b 116.90a 125.34c 128.00d
300 121.84b 120.49a 125.47c 128.12d
a-d
Indicate statistical differences between each column at constant temperatures, a = 0.05.

Table 3
Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of soaked chickpeas at 50, 60 and 70 °C with and without ultrasound treatments.

Time (min) Moisture content (%, d.b.)

50 °C 50 °C + 40 kHz 100 W 50 °C + 25 kHz 100 W 50 °C + 25 kHz 300 W
a a a
0 11.58 11.58 11.58 11.58a
30 62.36b 57.74a 64.74c 75.35d
60 84.70a 86.78b 91.31c 109.25d
90 95.43a 101.14b 106.73c 117.07d
120 108.69b 108.19a 115.86c 121.01d
150 115.84a 117.20b 123.87c 128.71d
180 120.82b 119.15a 126.11c 131.34d
210 122.71a 123.12b 127.22c 134.59d
60 °C 60 °C + 40 kHz 100 W 60 °C + 25 kHz 100 W 60 °C + 25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a
30 70.61b 69.73a 72.96c 80.35d
60 97.89b 96.90a 99.89c 111.50d
90 108.05a 108.36b 113.06c 120.27d
120 115.63b 114.91a 119.91c 126.34d
150 124.02b 124.00a 127.76c 130.71d
180 126.57b 126.51a 128.99c 132.14d
210 128.99b 127.93a 130.74c 134.92d
70 °C 70 °C + 40 kHz 100 W 70 °C + 25 kHz 100 W 70 °C + 25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a
30 76.09b 74.13a 82.82c 84.81d
60 99.01b 98.09a 105.95c 112.69d
90 110.19b 109.72a 114.24c 124.46d
120 119.45b 115.87a 122.16c 129.46d
150 126.35b 125.11a 129.20c 131.97d
180 129.78b 128.64a 131.50c 133.72d
210 130.68b 129.32a 132.30c 135.78d
a–d
Indicate statistical differences between each column at constant temperatures, a = 0.05.
 A. Yildirim et al. / Journal of Food Engineering 104 (2011) 134–142 139

Table 4
Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of soaked chickpeas at 87, 92 and 97 °C with and without ultrasound treatments.

Time (min) Moisture content (%, d.b.)

87 °C 87 °C + 40 kHz 100 W 87 °C + 25 kHz 100 W 87 °C + 25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a
30 86.85b 85.33a 92.25c 108.65d
60 108.58b 107.48a 115.49c 128.81d
90 122.38b 122.13a 128.16c 142.46d
120 129.30a 130.03b 132.48c 148.93d
150 135.41a 136.01b 138.23c 150.90d
92 °C 92 °C + 40 kHz 100 W 92 °C + 25 kHz 100 W 92 °C + 25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a
30 91.54b 89.91a 102.61c 115.27d
60 111.16a 112.34b 122.37c 132.71d
90 125.43b 124.29a 139.77c 147.79d
120 131.36b 131.23a 146.11c 151.24d
150 137.76b 137.75a 150.54b 154.23c
97 °C 97 °C + 40 kHz 100 W 97 °C + 25 kHz 100 W 97 °C + 25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a
30 97.05b 96.49a 106.98c 122.78d
60 121.06b 119.59a 139.07c 145.37d
90 136.49b 136.25a 148.67c 153.97d
120 144.71a 144.91b 151.23c 157.57d
150 148.59a 148.61b 158.93c 165.45d
a-d
Indicate statistical differences between each column at constant temperatures, a = 0.05.

Table 5
Predicted parameters of Fick’s model during soaking of chickpeas at different temperatures without and with ultrasound application.

Process Me (%, d.b.) Deff  1010 (m2 s1) R2 RMSE (%)

20 °C 119.82 1.40 0.9960 8.03
20 °C + 25 kHz
100 W 119.48 1.70 0.9907 13.88
20 °C + 40 kHz
100 W 123.10 1.28 0.9943 10.76
20 °C + 25 kHz
300 W 120.94 2.01 0.9925 11.29
30 °C 122.81 1.87 0.9894 9.70
30 °C + 25 kHz
100 W 122.61 2.10 0.9910 10.97
30 °C + 40 kHz
100 W 122.41 1.86 0.9885 12.02
30 °C + 25 kHz
300 W 124.40 2.62 0.9904 8.78
40 °C 128.44 2.39 0.9944 8.93
40 °C + 25 kHz
100 W 129.86 2.98 0.9914 9.88
40 °C + 40 kHz
100 W 127.56 2.46 0.9952 8.01
40 °C + 25 kHz
300 W 130.79 3.79 0.9951 6.59
50 °C 128.64 4.11 0.9942 2.70
50 °C + 25 kHz
100 W 130.72 4.94 0.9988 2.72
50 °C + 40 kHz
100 W 127.30 4.42 0.9981 2.53
50 °C + 25 kHz
300 W 133.56 6.52 0.9944 2.91
60 °C 129.76 5.58 0.9957 4.74
60 °C + 25 kHz
100 W 131.68 5.92 0.9978 3.43
60 °C + 40 kHz
100 W 129.17 5.57 0.9966 4.10
60 °C + 25 kHz
300 W 133.67 7.29 0.9978 1.87
70 °C 130.66 6.01 0.9944 5.85
70 °C + 25 kHz
100 W 131.05 7.11 0.9924 5.45
70 °C + 40 kHz
100 W 130.22 5.78 0.9935 6.19
70 °C + 25 kHz
300 W 134.06 7.96 0.9993 1.29
87 °C 137.47 7.12 0.9938 5.55
87 °C + 25 kHz
100 W 139.06 8.19 0.9944 4.13
87 °C + 40 kHz
100 W 138.78 6.76 0.9942 5.75
87 °C + 25 kHz
300 W 150.63 9.77 0.9937 4.18
92 °C 139.70 7.49 0.9908 6.36
92 °C + 25 kHz
100 W 149.74 8.54 0.9935 5.00
92 °C + 40 kHz
100 W 139.67 7.40 0.9925 5.73
92 °C + 25 kHz
300 W 151.37 11.20 0.9948 9.85
97 °C 150.05 7.72 0.9959 2.51
97 °C + 25 kHz
100 W 157.88 9.23 0.9974 2.02
97 °C + 40 kHz
100 W 150.32 7.53 0.9954 5.29
97 °C + 25 kHz
300 W 159.75 11.90 0.9960 2.55
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P
RMSE (%) = Root mean square error: 100  1n 1n ½ðM exp  Mpre =M exp Þ2 .

irreversible changes of the seeds, such as chemical and structural creased steadily due to water filling into the free capillary and
degradation. It was reported that the rate of water absorption by intermicellar spaces, and increasing the extraction rates of soluble
legumes increased with increase in time and temperature of the solids from grains (Quast and Silva, 1977; Tang et al., 1994; Sopade
soaking water. As the process continued, water absorption rate de- and Obekpa, 1990; Abu-Ghannam and McKenna, 1997).
140 A. Yildirim et al. / Journal of Food Engineering 104 (2011) 134–142
3.3. A general model to describe the water diffusion as a function of
soaking time and temperature
Previous studies showed that temperature is one of the most
important factors affecting the water diffusivity and water absorp-
tion of agricultural products (Kashaninejad et al., 2007; Turhan
et al., 2002). An Arrhenius type equation (Eq. (3)), which had been
used previously to describe the temperature dependant hydration
kinetics of legumes (Abu-Ghannam and McKenna, 1997; Turhan
et al., 2002), were used to evaluate temperature dependency of dif-
fusion coefficients (Deff) and gelatinization temperature:
  
Ea 1
lnðDeff Þ ¼ lnðDref Þ 
R T
where Deff, T, Ea and R are effective diffusion coefficient of the
Fick’s model, soaking temperature (in K), activation energy for
the hydration process in kJ mol1 and ideal gas constant in
8.314  103 kJ mol1 K1, respectively. Dref is reference diffusion
rate constant for the Fick’s model. The rate of water transfer and/
or starch gelatinization in whole cereal and legume grains were
found to be changing linearly with temperature and every curve
brake at a specific temperature which is close to gelatinization
temperature (Bakshi and Singh, 1980; Sayar et al., 2001; Sağol
et al., 2006). Arrhenius plots of the natural logarithm of rate con-
stants versus the inverse of T (K) for chickpeas are superposed in
Fig. 5. The activation energy, Ea, is related to the slope of this graph,
and shows the temperature dependence of Deff. To locate the tem-
perature at which the break in the Arrhenius curve for soaked
chickpeas occurred, the estimated natural log of rate constants
(Deff) was fitted to a linear model with break point and the break
temperature was estimated to be 61.47 °C (R2 = 0.9349–0.9954)
for the model (Muggeo, 2003). Such a discontinuity in the Arrhe-
nius curve has been observed during the soaking of rice (Bakshi
and Singh, 1980) and chickpeas (Sayar et al., 2001), and it has been
suggested that the break is linked to the early onset of starch gela-
tinization. The process of gelatinization is generally thought to oc-
cur between 63 and 70 °C for chickpeas (Fernandez and Berry,
1989). However, it has been suggested (Sayar et al., 2001; Turhan
et al., 2002) that chickpea gelatinization may actually begin be-
tween the lower temperatures of 55 and 60 °C. Starch granules of
the chickpeas used in this study kept the integrity of Maltese
crosses till 61 °C (Fig. 6). They noticeably started to decrease in
number and distort in shape between 60 and 70 °C (Fig. 6) pointing
that gelatinization temperature of chickpeas starts between 60 and
-20.5
Experimental (20-60 oC)
o
Experimental (60-97 C)
y= -10.9844- 3450.7955*x (R2 =0.9756) (20-60 o C)
-21.0
y= -17.9424-1123.565*x (R 2 =0.9954) (60- 97 o C)
ln (Deff , m s )
2 -1
-21.5
-22.0
-22.5
-23.0
0.0026 0.0028 0.0030 0.0032 0.0034
1/T (1/K)
Fig. 5. Arrhenius plot of Fick’s law model of diffusion constant, Deff, of chickpea over
the soaking temperature range of 20–97 °C.
70 °C. This observed temperature range is fairly close to the re-
ported gelatinization temperature of 63–70 °C for chickpea (Fer-
nandez and Berry, 1989). It is possible that the break in the
Arrhenius curve for soaked chickpeas was due to partial gelatiniza-
tion and/or structural changes, promoted soaking at temperatures
above 60 °C.
Incorporating the temperature break at 61.47 °C for the Fick’s
model, time and temperature dependence of moisture content
for soaked chickpeas, and dependence of initial and equilibrium
moisture contents, the following general models were derived to
describe the water absorption kinetics of chickpeas:
6
M ¼ M e þ ðMo  Me Þ 2
ð3Þ p
  
p2 345079
 exp  2 1:696  105 exp t ð6 60 CÞ ð4Þ
r T
6
M ¼ M e þ ðMo  Me Þ 2

p  
p2 112356
 exp  2 1:613  108 exp t ð6 60 CÞ ð5Þ
r T
Eqs. (4) and (5) can be used to find the moisture content of
chickpea during soaking/cooking at any time (seconds) and tem-
perature (K) providing that Mo and Me are known.
The Arrhenius equation has been previously used to describe
the temperature dependent hydration kinetics of other grains
and seeds (Maskan, 2002; Turhan et al., 2002). The Deff values de-
creased as temperature increased suggesting a corresponding in-
crease in the initial water absorption rate. As it is evident from
Fig. 5, the linearity of the curves indicates an Arrhenius relation-
ship for model.
When the Arrhenius equation (3) was applied to the Deff values
for temperatures below and above break point (61.47 °C) sepa-
rately, the activation energy values of 28.69 (R2 = 0.9756) and
9.34 (R2 = 0.9954) kJ mol1 were calculated, respectively. This va-
lue agrees well with the literature value of 19.50 kJ mol1 for the
activation energy of osmotic hydration of chickpeas at 5–50 °C
(Pinto and Esin, 2004). The activation energies of chickpea were
found as 41.79 and 8 kJ mol1 for 25–37 °C and 37–60 °C tempera-
ture ranges by Gowen et al. (2007). In another study, the activation
energy for chickpea was 48 and 18 kJ mol1 for temperature bel-
low and above 55 °C, respectively (Sayar et al., 2001). The lower
activation energy for the rate of water transfer above the gelatini-
zation temperature implies that water travels faster in gelatinized
chickpea than in ungelatinized chickpea.
3.4. Effect of ultrasounds on water diffusion during soaking of
chickpeas
One emergent application of power ultrasound in food industry
is the enhancement of mass transfer in processes where diffusion
takes place. Power ultrasound introduces that pressure variation
at solid/liquid interfaces, and therefore increases the moisture
absorption rate. Acoustic energy also causes oscillating velocities
and micro streaming at the interfaces which may affect the diffu-
sion boundary layer (Gallego-Juarez, 1998). Furthermore, ultra-
sonic waves also produce rapid series of alternative contractions
and expansions (sponge effect) of the material in which they are
traveling; this alternating stress creates microscopic channels
which may make the moisture gain easier. In addition, acoustic
waves may produce cavitations of water molecules inside the solid
0.0036
matrix, which may be beneficial for the gain of strongly attached
moisture (Gallego-Juarez, 1998; Mulet et al., 2003).
The effects of ultrasounds on water absorption of chickpeas
were illustrated in Figs. 2–4. The statistical analysis of moisture
 A. Yildirim et al. / Journal of Food Engineering 104 (2011) 134–142
Fig. 6. Effect of soaking temperature on the birefringence of chickpea starch at 40, 50, 60 and 70 °C.
contents were tabulated in Tables 1–4. Application of 25 kHz
100 W ultrasound significantly (P < 0.05) increased the water
absorption of chickpea for all temperatures (20–97 °C). The mois-
ture content (%, d.b.) values of chickpea were found to be increased
from 76.91% to 85.14% (d.b.), when the 25 kHz 100 W ultrasound
was applied at 20 °C and 180 min soaking. Increase in power of
ultrasounds (from 100 to 300 W) also further significantly (P <
0.05) increased the moisture content (from 85.14% to 91.89%) of
chickpea during 20 °C and 180 min soaking. Similarly, increase in
power (100–300 W) increased the moisture content of soaked
chickpea at all other temperatures for a given soaking time. How-
ever, 40 kHz 100 W ultrasound applications resulted in slight
changes (mostly increases) in moisture values. Increase in ultra-
sound frequency from 25 to 40 kHz insignificantly (P > 0.05) de-
creased the moisture content (%, d.b.) from 76.91% to 76.55% at
the same soaking temperature and time (Table 2).
Deff of the Fick’s law model was main parameter for the ultra-
sonic assisted process of diffusion which was compared with the
conventional soaking. At all temperatures, Deff values found from
the Fick’s model were significantly increased when 25 kHz 100 W
ultrasound treatment applied and also when ultrasound power in-
creased to 300 W (Table 5). For soaking at 20 °C, Deff values chan-
ged from 1.40  1010 to 1.70  1010 and to 2.01  1010 m2 s1
for non-ultrasound, 25 kHz 100 W and 25 kHz 300 W ultrasound
treatments, respectively. Deff changes at all temperatures were sig-
nificant (P < 0.05) (Table 5). The ultrasound treatment increased
141
the water diffusion of chickpea during soaking due to increasing
of mass diffusion rate (Fuente et al., 2004). However, application
of high frequency ultrasonic (40 kHz) for all soaking temperatures
did not significantly (P > 0.05) affect or/and decreased the
water absorption rate and the diffusion coefficient of chickpea
(Tables 2–5 and Figs. 2–4). Change of ultrasound frequency from
25 to 40 kHz decrease Deff value from 1.40  1010 to 1.28 
1010 m2 s1 (20 °C soaking).
4. Conclusion
Water diffusion rates of chickpea significantly increased
(P < 0.05) with increasing of soaking time, temperature and power
of ultrasound (100–300 W). High ultrasound frequencies such as
40 kHz did not significantly (P > 0.05) affect the water diffusion
of chickpea during soaking. Fick’s diffusion constant (Deff) for a
temperature range of 20–97 °C increased from 1.40  1010 to
11.9  1010 m2 s1 with ultrasound application.
Fick’s second law model where Arrhenius relationship inserted
for Deff can be used to determine moisture content of chickpeas as a
function of soaking time and temperature. Average gelatinization
temperature of chickpea from the water absorption model was
found as 61.47 °C. Activation energy (Ea) values of chickpea for be-
low and above gelatinization temperature of 61.47 °C were found
to be 28.69 and 9.34 kJ mol1, respectively. Ultrasound treatments
decreased the soaking time of chickpea.
142 A. Yildirim et al. / Journal of Food Engineering 104 (2011) 134–142

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