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    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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    Pinto, G. & Esin, A. (2004). Kinetics of the osmotic hydration of chickpeas. Journal of375

    Chemical Education, 81, 532-536.376

    Riera, E., Golas, Y., Blanco, A., Gallego, J.A., Blasco, M. & Mulet, A. (2004). Mass transfer377

    enhancement in supercritical fluids extraction by means of power ultrasound. Ultrason378

    Sonochem., 11, 241244.379

    Sabapathy, N.D., Tabil, L.G. & Baik, O.D. (2005). Moisture Absorption in Kabuli Type380

    Chickpea During Soaking and Cooking.ASAE Annual International Meeting.381

    Saol, S., Turhan, M. & Sayar, S. (2006). A potential method for determining in situ382

    gelatinization temperature of starch using initial water transfer rate in whole cereals.383

    Journal of Food Engineering, 76, 427432.384

    Sayar, S., Turhan, M. & Gunasekaran, S. (2001). Analysis of chickpea soaking by385

    simultaneous water transfer and waterstarch reaction. Journal of Food Engineering, 50,386

    9198.387

    Seyhan-Grta, F., Mehmet, A.K. & Evranuz, .E. (2001). Water diffusion coefficients of388

    selected legumes grown in Turkey as affected by temperature and variety. Turkey Journal389

    of Agriculture, 25, 297304.390

    Sopade, P.A. & Obekpa, J.A. (1990). Modeling water absorption soybean, cowpea and391

    peanuts at three temperatures using Pelegs equation. Journal of Food Science, 55, 1084-392

    1087.393

    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