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1
Fitting Ficks Model to Analyze Water Diffusion into Chickpeas During Soaking with1
Ultrasound Treatment2
3
Ali YILDIRIMa, Mehmet Durdu NERb*, Mustafa BAYRAMb4
5
aDepartment of Food Technology, Vocational School of Higher Education in Nizip, Gaziantep University,6
27700, Nizip, Gaziantep, TURKEY7
8
bDepartment of Food Engineering, Faculty of Engineering, Gaziantep University, 27310, Gaziantep,9
TURKEY10
11
Running title: Fitting Fick Mdl to ultrs trtd Chickpea12
13
*Corresponding author:14
Prof.Dr. Mehmet Durdu ner15
Department of Food Engineering, Faculty of Engineering, Gaziantep University, 27310, Gaziantep, TURKEY16
Phone number:+90(342)317230517
Fax number: +90(342)317236218
E-mail address:[email protected]
20
Abstract21
Ficks model together with Arrhenius relationship were successfully used to evaluate22
water absorption of chickpea during soaking at a temperature range of 20-97 oC with 25 kHz23
100 W, 40 kHz 100 W and 25 kHz 300 W ultrasound treatments. Use of ultrasound, increase24
in ultrasound power and soaking temperature significantly (P
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chickpea was found as 61.47 oC. Activation energy (Ea) values of chickpea for below and27
above gelatinization temperature were found to be 28.69 and 9.34 kJ mol-1, respectively.28
Ultrasound treatments significantly decreased the soaking time of chickpea.29
30
Keywords:Chickpea, fitting, Ficks model, ultrasound, water diffusion31
32
ABBREVIATIONS33
AOAC: Official methods of analysis of AOAC International34
EAD: Acoustic energy density in W cm-335
Deff : Water diffusion coefficient in m2 s-136
d.b.: Moisture content in dry basis (%)37
inci: A special type of chickpea produced by ukurova Agricultural Research Institute38
(Adana, Turkey)39
40
1. Introduction41
Chickpea (Cicer arietinum L.) is one of the oldest and most widely consumed legumes in42
the world, particularly in tropical and subtropical areas. Major chickpea producer and exporter43
countries are India, Turkey, Pakistan, Iran Islamic Republic, and Australia. Chickpea is an44
important source of proteins, carbohydrates, B-group vitamins and certain minerals (Chavan45
et al., 1986; Christodoulou et al., 2006a). Food legumes decreased incidence of several46
diseases, such as cancer, cardiovascular diseases, obesity and diabetes (Bhathena &47
Velasquez, 2002). Legumes are usually cooked before being used in the human diet to48
improve the protein quality by destruction or inactivation of the heat labile anti-nutritional49
factors (Wang et al., 1997). Recently, there has been increasing demand for research to50
improve cooking of chickpeas in developed countries where chickpeas are mainly consumed51
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to improve overall nutritional status by replacing animal foods with legumes (Guillon &52
Champ, 1996). The most common process of pre-soaking usually is not sufficient to decrease53
overall cooking time of chickpea. Understanding water absorption in legumes during soaking54
is of practical importance since it affects subsequent processing operations and the quality of55
the final product.56
Ultrasound is a form of energy generated by sound waves of frequencies that are too high57
to be detected by human ear, i.e. above 16 kHz (Jayasooriya et al., 2004). Ultrasound58
cavitations could result in the occurrence of micro streaming which is able to enhance heat59
and mass transfer. Ultrasonic is a rapidly growing field of research, which is finding60
increasing use in the food industry (Jayasooriya et al., 2004; Zheng & Sun, 2006). Ultrasound61
has been used to enhance mass transfer in solid/liquid food systems (Fuente et al., 2004; Riera62
et al., 2004). Ultrasound applications were reported to promote the leaching of63
oligosaccharides in legumes (Han & Baik (2006) and to reduce cooking time of rice64
(Wambura et al., 2008).65
In the food industry, chickpea is pre-processed in the factories to produce humus (as66
arabic food), canned products, blended powder products. To produce these products, chickpea67
is soaked and cooked. Therefore, this study supplies important information and ultrasonic68
technique to process it easily. In addition, it is known that chickpea is a hard legume to cook.69
Therefore, ultrasonic technique supply a new solution to decrease soaking and cooking time.70
These studies show that thermosonication can be used to increase the water absorption71
during soaking operation. The objective of this study was to determine the applicability of72
Ficks second law of diffusion in modeling the water diffusion characteristics of ultrasound73
treated chickpea in an attempt to determine suitable processing conditions for rehydration.74
75
76
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2. Materials and Methods77
2.1. Raw materials78
Certified chickpeas (inci-2003) with initial moisture content of 11.58 % (d.b.) and an79
average diameter of 8.00 (0.27) mm (measured with Mutitoyo No. 505633, Japan, digital80
micrometer) obtained from ukurova Agricultural Research Institute (Adana, Turkey), were81
used throughout this study. After removing foreign materials and damaged seeds, they were82
sieved to standardize the sizes, 7.5 mm to 9 mm.83
84
2.2. Water absorption determination during soaking operation85
The soaking of chickpea was performed at 20, 30, 40, 50, 60, 70, 87, 92 and 97 86
oC without, and with 25 kHz 100 W (acoustic energy density (EAD) of 0.025 W cm-3), 4087
kHz 100 W (EAD of 0.025 W cm-3) and 25 kHz 300 W (EAD of 0.017 W cm-3) ultrasound88
treatments. One hundred grams of chickpea seeds were immersed in 2000 ml deionized water89
(1:20); conventional and ultrasonic soaking were both performed in ultrasonic (US) tanks90
(Intersonik Co., Turkey) until seeds were fully hydrated. Four grams of chickpea and 80 ml91
soaking water (1:20) were quickly removed from the tanks for the moisture content92
determination within 30 minutes intervals. Chickpea seeds were gently wiped with clean93
paper towel to remove excess water and ground for themoisture content determination. The94
moisture contents of randomly selected grains (5 g) were determined in dry basis at 105 oC for95
48 h using oven drying method (AOAC, 2002) and used for Ficks modeling of water96
diffusion. The experiments were replicated twice and measurements were duplicated.97
98
2.3. Determination of soluble solids loss during soaking of chickpeas99
Four grams of chickpea and 80 mL of soaking water (1:20 ratio) were removed from the100
soaking chamber after 3.5 h of soaking operation at 97o
C. Soluble solids content (Brix, g/g%)101
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of the soaking water was measured at 25 oC by using Abbe-refractometer (Opton-F.G. Bode102
and Co., Germany) and was reported as maximum soluble solids loss.103
104
2.4. Determination of gelatinization temperature of chickpeas105
Birefringence images of the chickpea samples at soaking temperatures of 40, 50, 60 and106
70 oC were captured in a PC using a polarized light microscope (OLYPOS TX51, Euromex107
Microscopen, Ed Arnhem, Netherlands) equipped with a video camera (VC 3031, Euromex108
Microscopen, Ed Arnhem, Netherlands) connected to the PC (Figure 6). A solution of 1 %109
(cooked chickpea flour/water) samples was prepared. After 30 minutes of mixing, 20 L of110
sample solution was spread on lamella, and the birefringence images were captured through111
the microscope. The gelatinization temperature of the grains is defined as the temperature at112
which the birefringence of starch start to diminish (Hoseney, 1994).113
114
2.5. Statistical analysis115
SIGMA PLOT 10 (Jandel Scientific, San Francisco, USA) were used to fit the models116
and to plot the data. ANOVA and DUNCAN Multiple Range Tests, using SPSS version 16, at117
P < 0.05 were performed to determine effect of processing parameters.118
119
3. Results and Discussion120
3.1. Water diffusion characteristics of chickpea during soaking121
Food legumes are usually soaked before cooking to provide sufficient amount of moisture122
for gelatinization of starch and/or gelation of protein. The most important property for123
soaking of chickpea is the moisture content to achieve the proper cooking operation. It could124
be achieved either through conditioning below the gelatinization temperature and then125
cooking above the gelatinization temperature, or through direct cooking above the126
gelatinization temperature. Mass transfer plays a key role in food processing, like127
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humidification and dehumidification, dehydration, distillation, absorption, etc. The driving128
force for mass diffusion is the concentration difference. In solids, there can obviously be no129
convection and all movements are by molecular diffusion due to random molecular130
movements.131
The water absorption characteristics of chickpea were analyzed using moisture content132
(%, d.b.) values in this study. The mean moisture contents and the statistical analysis of133
soaked chickpeas at 20-97 oC without ultrasound, and with 25 kHz 100 W, 40 kHz 100 W and134
25 kHz 300 W ultrasounds treatment were illustrated in Figures 1-4 and tabulated in Tables 1-135
4. The moisture contents (%, d.b.) of chickpea during soaking were significantly (P
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coefficient is the factor of proportionality representing the quantity of substance diffusing153
across a unit area through a unit concentration gradient in unit time. Total amounts of154
diffusing substance entered a spherical grain of radius r can be obtained from the following155
Ficks series type equation (Crank, 1975):156
=
=
tnr
D
nMM
MMeff
neo
e 2
2
2
122
exp6
(1)157
Where M, Me, Mo are moisture contents (%, d.b.) at any time, equilibrium and initial,158
respectively. Deffand r are effective diffusion constant (m2 s-1) and average radius of chickpea159
(m), respectively. A fit of the experimental data for soaking times leads to the determination160
of an average diffusion coefficient, Deff, via Eq. 1 which is Ficks law of diffusion of water in161
solids of spherical shape. The chickpea seeds may be approximated as spheres with a mean162
diameter of 0.0040 m (0.0001). Ficks laws of diffusion (Eq. 1) and its derived equations163
account for most of the models used in food science, as can be observed from publications164
(Garcia-Pascual et al., 2006; Gowen et al., 2007; Sabapathy et al., 2005). Some of the165
common assumptions and simplifications often made for solving Ficks second law (Eq. 1)166
include the following: 1) the moisture transfer is one dimensional, unsteady state in the radial167
direction, 2) chickpea is considered to be an almost spherical object, 3) the initial temperature168
and moisture distributions are uniform, 4) there is a moisture gradient in the chickpea with169
respect to time, 5) the thermal properties are constant, 6) chickpea is considered as a170
homogeneous isotropic solid, 7) moisture transfer to and from the seed is due to concentration171
gradient, 8) the quantity of solid loss in the grains during cooking was neglected, 9) for long172
soaking times, only the first term of series equation was significant.173
In this study, the effect of loss of soluble solids from chickpea seeds was not taken into174
account in calculating the moisture content because maximum loss of soluble solids from175
chickpea at temperatures of 97
o
C for 3.5 h soaking was about 2.06 % of the original mass176
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which in comparison with the water gain was assumed to be negligible. Other researchers177
have also reported similar assumption for other seeds (Sayar et al., 2001; Sabapathy et al.,178
2005). When these assumptions were applied on Ficks second law, the following equation179
was obtained.180
+=
2
2
2exp
6)(
r
tDMMMM
eff
eoe
(2)181
The Ficks law of diffusion function is related to diffusion of water and diffusion182
coefficient (Deff). For mathematical modeling of the variation of moisture content of chickpea183
during soaking at each temperature without, and with ultrasounds treatment, Ficks law model184
was tested. The parameters in this model such as Deff(main parameter), Me, were estimated by185
using the non-linear regression analysis of equations (2) and presented on Table 5. The186
performance parameters of the model, the coefficient of determination (R2) and percentage of187
root mean square error (% RMSE) are given on Table 5. The course of the hydration,188
adequately fitted by a nonlinear equation (Eq. 2), and reveals the fact that the seed moisture189
content increases with soaking time, use of ultrasound treatments and increase in used190
ultrasound power at all temperatures (Figures 1-4 and Tables 1-5). Water absorption ceases191
when the seed attained the equilibrium water content (Sayar et al., 2001). The diffusion192
process, which obeys the Ficks law model, was found to be a thermally activated process and193
sensitive to temperature, time, ultrasound treatment and its power.194
When the temperature was raised from 20 to 97 oC, Deffvalues were increased from 1.40 x195
10-10 to 7.72 x 10-10 (m2 s-1), also significant (P
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10-10 m2 s-1 for winter chickpea. The water diffusion coefficient of chickpea ranged from 9.71201
x 10-11 to 5.98 x 10-10 m2 s-1 in the study of Seyhan-Grta et al. (2001). The diffusion202
coefficients of chickpeas for temperature range of 45 - 98.7 oC were found as 0.14 x 10-10 -203
5.51 x 10-10 m2 s-1 in another study (Sabapathy et al., 2005). Diffusivity values reported in this204
study were similar to the literature results. Moisture absorption at elevated temperatures may205
induce irreversible changes of the seeds, such as chemical and structural degradation. It was206
reported that the rate of water absorption by legumes increased with increase in time and207
temperature of the soaking water. As the process continued, water absorption rate decreased208
steadily due to water filling into the free capillary and intermicellar spaces, and increasing the209
extraction rates of soluble solids from grains (Quast & de Silva, 1977; Tang et al., 1994;210
Sopade & Obekpa, 1990; Abu-Ghannam & McKenna, 1997).211
212
3.3. A general model to describe the water diffusion as a function of soaking time and213
temperature214
Previous studies showed that temperature is one of the most important factors affecting215
the water diffusivity and water absorption of agricultural products (Kashaninejad et al., 2007;216
Turhan et al., 2002). An Arrhenius type equation (Eq. 3), which had been used previously to217
describe the temperature dependant hydration kinetics of legumes (Abu-Ghannam &218
McKenna, 1997; Turhan et al., 2002), were used to evaluate temperature dependency of219
diffusion coefficients (Deff) and gelatinization temperature:220
)1
)(()ln()ln(TR
EDD a
refeff= (3)221
Where Deff, T, Ea and R are effective diffusion coefficient of the Ficks model, soaking222
temperature (in K), activation energy for the hydration process in kJ mol-1 and ideal gas223
constant in 8.314 x10-3 kJ mol-1 K-1, respectively. Dref is reference diffusion rate constant for224
the Ficks model. The rate of water transfer and/or starch gelatinization in whole cereal and225
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legume grains were found to be changing linearly with temperature and every curve brake at226
a specific temperature which is close to gelatinization temperature (Bakshi & Singh, 1980;227
Sayar et al., 2001; Saol et al., 2006). Arrhenius plots of the natural logarithm of rate228
constants versus the inverse of T (K) for chickpeas are superposed in Figure 5. The activation229
energy, Ea,is related to the slope of this graph, and shows the temperature dependence of Deff.230
To locate the temperature at which the break in the Arrhenius curve for soaked chickpeas231
occurred, the estimated natural log of rate constants (Deff) was fitted to a linear model with232
break point and the break temperature was estimated to be 61.47 oC (R2= 0.9349-0.9954) for233
the model (Muggeo, 2003). Such a discontinuity in the Arrhenius curve has been observed234
during the soaking of rice (Bakshi & Singh, 1980) and chickpeas (Sayar et al., 2001), and it235
has been suggested that the break is linked to the early onset of starch gelatinization. The236
process of gelatinization is generally thought to occur between 63 and 70 oC for chickpeas237
(Fernandez & Berry, 1989). However, it has been suggested (Sayar et al., 2001; Turhan et al.,238
2002) that chickpea gelatinization may actually begin between the lower temperatures of 55239
and 60 oC. Starch granules of the chickpeas used in this study kept the integrity of Maltese240
crosses till 61 oC (Figure 6). They noticeably started to decrease in number and distort in241
shape between 60 and 70 oC (Figure 6) pointing that gelatinization temperature of chickpeas242
starts between 60 and 70 oC. This observed temperature range is fairly close to the reported243
gelatinization temperature of 63-70 oC for chickpea (Fernandez & Berry, 1989). It is possible244
that the break in the Arrhenius curve for soaked chickpeas was due to partial gelatinization245
and/or structural changes, promoted soaking at temperatures above 60 oC.246
Incorporating the temperature break at 61.47 oC for the Ficks model, time and247
temperature dependence of moisture content for soaked chickpeas, and dependence of initial248
and equilibrium moisture contents, the following general models were derived to describe the249
water absorption kinetics of chickpeas:250
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+=
tTr
MMMM eoe )79.3450
exp(106961exp6
)( 52
2
2
( 60 oC) (4)251
+=
tTrMMMM eoe )
56.1123
exp(10613.1exp
6
)(
8
2
2
2
( > 60o
C) (5)252
Equations 4 and 5 can be used to find the moisture content of chickpea during253
soaking/cooking at any time (seconds) and temperature (K) providing that Mo and Me are254
known.255
The Arrhenius equation has been previously used to describe the temperature dependent256
hydration kinetics of other grains and seeds (Maskan, 2002; Turhan et al., 2002). The D eff257
values decreased as temperature increased suggesting a corresponding increase in the initial258
water absorption rate. As it is evident from Figure 5, the linearity of the curves indicates an259
Arrhenius relationship for model.260
When the Arrhenius equation (3) was applied to the Deff values for temperatures below261
and above break point (61.47 oC) separately, the activation energy values of 28.69262
(R2=0.9756) and 9.34 (R2=0.9954) kJ mol-1 were calculated, respectively. This value agrees263
well with the literature value of 19.50 kJ mol-1 for the activation energy of osmotic hydration264
of chickpeas at 5-50 oC (Pinto and Esin, 2004). The activation energies of chickpea were265
found as 41.79 kJ mol-1 and 8 kJ mol-1 for 25-37 oC and 37-60 oC temperature ranges by266
Goven et al. (2007). In another study, the activation energy for chickpea was 48 and 18 kJ267
mol-1 for temperature bellow and above 55 oC, respectively (Sayar et al., 2001). The lower268
activation energy for the rate of water transfer above the gelatinization269
temperature implies that water travels faster in gelatinized chickpea than in ungelatinized270
chickpea.271
272
273
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3.4. Effect of ultrasounds on water diffusion during soaking of chickpeas274
One emergent application of power ultrasound in food industry is the enhancement of275
mass transfer in processes where diffusion takes place. Power ultrasound introduces that276
pressure variation at solid/liquid interfaces, and therefore increases the moisture absorption277
rate. Acoustic energy also causes oscillating velocities and micro streaming at the interfaces278
which may affect the diffusion boundary layer (Gallego-Juarez, 1998). Furthermore,279
ultrasonic waves also produce rapid series of alternative contractions and expansions (sponge280
effect) of the material in which they are traveling; this alternating stress creates microscopic281
channels which may make the moisture gain easier. In addition, acoustic waves may produce282
cavitations of water molecules inside the solid matrix, which may be beneficial for the gain of283
strongly attached moisture (Gallego-Juarez, 1998; Mulet et al., 2003).284
The effects of ultrasounds on water absorption of chickpeas were illustrated in Figures 2-285
4. The statistical analysis of moisture contents were tabulated in Tables 1-4. Application of 25286
kHz 100 W ultrasound significantly (P
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Deff of the Fick's law model was main parameter for the ultrasonic assisted process of298
diffusion which was compared with the conventional soaking.At all temperatures, Deffvalues299found from the Ficks model were significantly increased when 25 kHz 100 W ultrasound300
treatment applied and also when ultrasound power increased to 300 W (Table 5). For soaking301
at 20 oC, Deff values changed from 1.40x10-10 to 1.70x10-10 and to 2.01x10-10m2 s-1for non-302
ultrasound, 25 kHz 100 W and 25 kHz 300 W ultrasound treatments, respectively. D eff303
changes at all temperatures were significant (P0.05) affect or/and decreased the water307
absorption rate and the diffusion coefficient of chickpea (Tables 2-5 and Figures 2-4). Change308
of ultrasound frequency from 25 to 40 kHz decrease Deff value from 1.40x10-10 to 1.28 x10-10309
m2 s-1 (20 oC soaking).310
311
4. Conclusion312
Water diffusion rates of chickpea significantly increased (P0.05) affect the water diffusion of315
chickpea during soaking. Ficks diffusion constant (Deff) for a temperature range of 20-97oC316
increased from 1.40 x 10-10 to 11.9 x 10-10 (m2 s-1) with ultrasound application.317
Ficks second law model where Arrhenius relationship inserted for Deff can be used to318
determine moisture content of chickpeas as a function of soaking time and temperature.319
Average gelatinization temperature of chickpea from the water absorption model was found320
as 61.47 oC. Activation energy (Ea) values of chickpea for below and above gelatinization321
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temperature of 61.47 oC were found to be 28.69 and 9.34 kJ mol-1, respectively. Ultrasound322
treatments decreased the soaking time of chickpea.323
324
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Tang, J., Sokhansanj, S. & Sosulski, F.W. (1994). Moisture-absorption characteristics of394
Laird lentils and hard shell seeds. Cereal Chemistry, 71, 423428.395
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17
Turhan, M., Sayar, S. & Gunasekaran, S. (2002). Application of Peleg model to study water396
absorption in chickpea during soaking.Journal of Food Engineering, 53, 153-159.397
Wambura, P., Yang, W. & Wang, Y. (2008). Power Ultrasound Enhanced One-Step Soaking398
and Gelatinization for Rough Rice Parboiling.International Journal of Food Engineering,399
4, 1-12.400
Wang, N., Lewis, M.J., Brennan, J.G. & Westby, A. (1997). Effect of processing methods on401
nutrients and anti-nutritional factors in cowpea. Food Chemistry, 58, 5968.402
Zheng, L. & Sun, D.W. (2006). Innovative applications of power ultrasound during food403
freezing processes-a review. Food Science and Technology, 17, 16-23.404
405
406
407
408
409
410
411
412
413
414
415
416
417
418
419
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18
Figure 1. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas420
during soaking at different temperatures.421
422
Figure 2. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas423
during soaking at 20 (A), 30 (B) and 40 (C) oC temperatures without and with ultrasound424
treatments.425
426
Figure 3. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas427
during soaking at 50 (A), 60 (B) and 70 (C) oC temperatures without and with ultrasound428
treatments.429
430
Figure 4. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas431
during soaking at 87 (A), 92 (B) and 97 (C) oC temperatures without and with ultrasound432
treatments.433
434
Figure 5. Arrhenius plot of Ficks law model of diffusion constant, Deff, of chickpea over the435
soaking temperature range of 20-97 oC.436
437
Figure 6.Effect of soaking temperature on the birefriengence of chickpea starch at 40, 50, 60438
and 70 oC.439
440
441
442
443
444
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19
Time (min)
0 100 200 300 400 500 600 700 800
Moisturecontent(%g/g,d.b.)
0
20
40
60
80
100
120
140
160
20 oC
30 oC
40 oC
50 oC
60 oC
70 oC
87 oC
92 oC
97 oC
Fick's Model
445
446
Figure 1. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas447
during soaking at different temperatures.448
449
450
451
452
453
454
455
456
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20
Time (min)
0 100 200 300 400 500 600
Moisturecon
tent(%g/g,d.b.)
0
20
40
60
80
100
120
140
20 oC (control)
20 oC + 25 kHz 100 W US
20 oC + 40 kHz 100 W US
20 oC + 25 kHz 300 W US
Fick's model
457
(A)458
Time (min)
0 100 200 300 400 500
Moisturecontent(%g/g,d.b
.)
0
20
40
60
80
100
120
140
30 oC (control)
30 oC + 25 kHz 100 W US
30 oC + 40 kHz 100 W US
30 oC + 25 kHz 300 W US
Fick's model
459
(B)460
Time (min)
0 100 200 300 400 500
Moisturecontent(%g/g,d.b.)
0
20
40
60
80
100
120
140
40 oC (control)
40 oC + 25 kHz 100 W US
40 oC + 40 kHz 100 W US
40 oC + 25 kHz 300 W US
Fick's model
461
(C)462
463
Figure 2. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas464
during soaking at 20 (A), 30 (B) and 40 (C) oC temperatures without and with ultrasound465
treatments.466
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21
Time (min)
0 100 200 300 400
Moisturecontent(%g/g,d.b.)
0
20
40
60
80
100
120
140
160
180
50 oC (control)
50 oC + 25 kHz 100 W US
50 oC + 40 kHz 100 W US
50 oC + 25 kHz 300 W US
Fick's model
467
(A)468
Time (min)
0 100 200 300
Moisturecontent(%g/g,d.b.)
0
20
40
60
80
100
120
140
60 oC (control)
60 oC + 25 kHz 100 W US
60 oC + 40 kHz 100 W US
60 oC + 25 kHz 300 W US
Fick's model
469
(B)470
Time (min)
0 100 200 300 400
Moisturecontent(%g/g,d.b.)
0
20
40
60
80
100
120
140
160
70 oC (control)
70 oC + 25 kHz 100 W US
70 oC + 40 kHz 100 W US
70 oC + 25 kHz 300 W US
Fick's model
471
(C)472
473
Figure 3. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas474
during soaking at 50 (A), 60 (B) and 70 (C) oC temperatures without and with ultrasound475
treatments.476
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22
Time (min)
0 50 100 150 200 250
Moisturecon
tent(%g/g,d.b.)
0
20
40
60
80
100
120
140
160
87 oC (control)
87 oC + 25 kHz 100 W US
87 oC + 40 kHz 100 W US
87 oC + 25 kHz 300 W US
Fick's model
477
(A)478
Time (min)
0 50 100 150 200 250
Moisturecontent(%g/g,d.b.)
0
20
40
60
80
100
120
140
160
92 oC (control)
92 oC + 25 kHz 100 W US
92 oC + 40 kHz 100 W US
92 oC + 25 kHz 300 W US
Fick's model
479
(B)480
Time (min)
0 50 100 150 200 25
Moisturecontent(%g/g,d.b.)
0
20
40
60
80
100
120
140
160
97 oC (control)
97 oC + 25 kHz 100 W US
97 oC + 40 kHz 100 W US
97 oC + 25 kHz 300 W US
Fick's model
481
(C)482
483
Figure 4. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas484
during soaking at 87 (A), 92 (B) and 97 (C) oC temperatures without and with ultrasound485
treatments.486
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23
1/T (1/K)
0,0026 0,0028 0,0030 0,0032 0,0034 0,0036
ln(D
eff,
m2s-1)
-23,0
-22,5
-22,0
-21,5
-21,0
-20,5
Experimental (20-60oC)
Experimental (60-97oC)
y= -10.9844- 3450.7955*x (R2=0.9756) (20-60
oC)
y= -17.9424-1123.565*x (R2
=0.9954) (60- 97o
C)
487
488
Figure 5. Arrhenius plot of Ficks law model of diffusion constant, Deff, of chickpea over the489
soaking temperature range of 20-97 oC.490
491
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24
492
(40
o
C) (50
o
C)493
494
(60 oC) (70 oC)495
496
Figure 6.Effect of soaking temperature on the birefriengence of chickpea starch at 40, 50, 60497
and 70 oC.498
499
500
501
502
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25
Table 1. Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of503
soaked chickpeas as a function of processing time and temperature.504
505
Moisture content (%, d.b)Time(min) 20 oC 30 oC 40 oC 50 oC 60 oC 70 oC 87 oC 92 oC 97 oC
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,130 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,9a-h Indicate statistical differences between each row at =0.05,
5061-9 Indicate statistical differences between each column at constant temperatures, =0.05.507
508
509
510
511
512
513
514
515
516
517
518
519
520
521
522
523
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26
Table 2. Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of524
soaked chickpeas at 20, 30 and 40 oC with and without ultrasound treatments.525
526
Moisture content (%, d.b)Time(min) 20 oC 20 oC+40 kHz 100 W 20 oC+25 kHz 100 W 20 oC+25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a30 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 88.39
b
86.14
a
95.14
c
102.30
d
270 90.63a 92.05b 99.12c 106.56d
300 98.06b 97.69a 103.11c 111.56d
30 oC 30 oC+40 kHz 100 W 30 oC+25 kHz 100 W 30 oC+25 kHz 300 W0 11.58a 11.58a 11.58a 11.58a30 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 oC 40 oC+40 kHz 100 W 40 oC+25 kHz 100 W 40 oC+25 kHz 300 W0 11.58a 11.58a 11.58a 11.58a30 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 128.12da-d Indicate statistical differences between each column at constant temperatures, =0.05.527
528
529
530
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27
Table 3. Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of531
soaked chickpeas at 50, 60 and 70 oC with and without ultrasound treatments.532
533
Moisture content (%, d.b)Time(min) 50 oC 50 oC+40 kHz 100 W 50 oC+25 kHz 100 W 50 oC+25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a30 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
60o
C 60o
C+40 kHz 100 W 60o
C+25 kHz 100 W 60o
C+25 kHz 300 W0 11.58a 11.58a 11.58a 11.58a30 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 oC 70 oC+40 kHz 100 W 70 oC+25 kHz 100 W 70 oC+25 kHz 300 W0 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 135.78da-d Indicate statistical differences between each column at constant temperatures, =0.05.534
535
536
537
538
539
540
541
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28
Table 4. Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of542
soaked chickpeas at 87, 92 and 97 oC with and without ultrasound treatments.543
544
Moisture content (%, d.b)Time(min) 87 oC 87 oC+40 kHz 100 W 87 oC+25 kHz 100 W 87 oC+25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a30 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 oC 92 oC+40 kHz 100 W 92 oC+25 kHz 100 W 92 oC+25 kHz 300 W0 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 oC 97 oC+40 kHz 100 W 97 oC+25 kHz 100 W 97 oC+25 kHz 300 W0 11.58a 11.58a 11.58a 11.58a30 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, =0.05.545
546
547
548
549
550
551
552
553
554
555
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Table 5. Predicted parameters of Ficks model during soaking of chickpeas at different556
temperatures withoutand with ultrasound application.557
558
ProcessMe
(%, d.b)Deff x10
10(m2 s-1) R2
RMSE(%)
20 oC 119.82 1.40 0.9960 8.0320 oC + 25 kHz 100 W 119.48 1.70 0.9907 13.8820 oC + 40 kHz 100 W 123.10 1.28 0.9943 10.7620 oC + 25 kHz 300 W 120.94 2.01 0.9925 11.29
30 oC 122.81 1.87 0.9894 9.7030 oC + 25 kHz 100 W 122.61 2.10 0.9910 10.9730 oC + 40 kHz 100 W 122.41 1.86 0.9885 12.0230 oC + 25 kHz 300 W 124.40 2.62 0.9904 8.78
40 oC 128.44 2.39 0.9944 8.9340 oC + 25 kHz 100 W 129.86 2.98 0.9914 9.8840 oC + 40 kHz 100 W 127.56 2.46 0.9952 8.0140 oC + 25 kHz 300 W 130.79 3.79 0.9951 6.59
50 oC 128.64 4.11 0.9942 2.7050 oC + 25 kHz 100 W 130.72 4.94 0.9988 2.7250 oC + 40 kHz 100 W 127.30 4.42 0.9981 2.5350 oC + 25 kHz 300 W 133.56 6.52 0.9944 2.91
60 oC 129.76 5.58 0.9957 4.7460 oC + 25 kHz 100 W 131.68 5.92 0.9978 3.4360 oC + 40 kHz 100 W 129.17 5.57 0.9966 4.1060 oC + 25 kHz 300 W 133.67 7.29 0.9978 1.87
70o
C 130.66 6.01 0.9944 5.8570 oC + 25 kHz 100 W 131.05 7.11 0.9924 5.4570 oC + 40 kHz 100 W 130.22 5.78 0.9935 6.1970 oC + 25 kHz 300 W 134.06 7.96 0.9993 1.29
87 oC 137.47 7.12 0.9938 5.5587 oC + 25 kHz 100 W 139.06 8.19 0.9944 4.1387 oC + 40 kHz 100 W 138.78 6.76 0.9942 5.7587 oC + 25 kHz 300 W 150.63 9.77 0.9937 4.18
92 oC 139.70 7.49 0.9908 6.3692 oC + 25 kHz 100 W 149.74 8.54 0.9935 5.0092 oC + 40 kHz 100 W 139.67 7.40 0.9925 5.7392 oC + 25 kHz 300 W 151.37 11.20 0.9948 9.85
97 oC 150.05 7.72 0.9959 2.5197 oC + 25 kHz 100 W 157.88 9.23 0.9974 2.0297 oC + 40 kHz 100 W 150.32 7.53 0.9954 5.2997 oC + 25 kHz 300 W 159.75 11.90 0.9960 2.55
RMSE (%) = Root mean square error: 100* [ ]2
1expexp /)(
1
n
pre MMMn
559