1 Fitting Fick’s Model to Analyze Water Diffusion into Chickpeas During Soaking with

2 Ultrasound Treatment

4 Ali YILDIRIMa, Mehmet Durdu ÖNERb*, Mustafa BAYRAMb

5
a
6 Department of Food Technology, Vocational School of Higher Education in Nizip, Gaziantep University,

7 27700, Nizip, Gaziantep, TURKEY

8
b
9 Department of Food Engineering, Faculty of Engineering, Gaziantep University, 27310, Gaziantep,

10 TURKEY

11

12 Running title: Fitting Fick Mdl to ultrs trtd Chickpea

13
*
14 Corresponding author:

15 Prof.Dr. Mehmet Durdu Öner

16 Department of Food Engineering, Faculty of Engineering, Gaziantep University, 27310, Gaziantep, TURKEY

17 Phone number: +90(342)3172305

18 Fax number: +90(342)3172362

19 E-mail address: oner@gantep.edu.tr

20

21 Abstract

22 Fick’s model together with Arrhenius relationship were successfully used to evaluate

23 water absorption of chickpea during soaking at a temperature range of 20-97 oC with 25 kHz

24 100 W, 40 kHz 100 W and 25 kHz 300 W ultrasound treatments. Use of ultrasound, increase

25 in ultrasound power and soaking temperature significantly (P<0.05) increased the water

26 diffusion coefficient (Deff) of chickpea during soaking. Average gelatinization temperature of

1
27 chickpea was found as 61.47 oC. Activation energy (Ea) values of chickpea for below and

28 above gelatinization temperature were found to be 28.69 and 9.34 kJ mol-1, respectively.

29 Ultrasound treatments significantly decreased the soaking time of chickpea.

30

31 Keywords: Chickpea, fitting, Fick’s model, ultrasound, water diffusion

32

33 ABBREVIATIONS

34 AOAC: Official methods of analysis of AOAC International

35 EAD: Acoustic energy density in W cm-3

36 Deff : Water diffusion coefficient in m2 s-1

37 d.b.: Moisture content in dry basis (%)

38 inci: A special type of chickpea produced by Çukurova Agricultural Research Institute

39 (Adana, Turkey)

40

41 1. Introduction

42 Chickpea (Cicer arietinum L.) is one of the oldest and most widely consumed legumes in

43 the world, particularly in tropical and subtropical areas. Major chickpea producer and exporter

44 countries are India, Turkey, Pakistan, Iran Islamic Republic, and Australia. Chickpea is an

45 important source of proteins, carbohydrates, B-group vitamins and certain minerals (Chavan

46 et al., 1986; Christodoulou et al., 2006a). Food legumes decreased incidence of several

47 diseases, such as cancer, cardiovascular diseases, obesity and diabetes (Bhathena &

48 Velasquez, 2002). Legumes are usually cooked before being used in the human diet to

49 improve the protein quality by destruction or inactivation of the heat labile anti-nutritional

50 factors (Wang et al., 1997). Recently, there has been increasing demand for research to

51 improve cooking of chickpeas in developed countries where chickpeas are mainly consumed

2
52 to improve overall nutritional status by replacing animal foods with legumes (Guillon &

53 Champ, 1996). The most common process of pre-soaking usually is not sufficient to decrease

54 overall cooking time of chickpea. Understanding water absorption in legumes during soaking

55 is of practical importance since it affects subsequent processing operations and the quality of

56 the final product.

57 Ultrasound is a form of energy generated by sound waves of frequencies that are too high

58 to be detected by human ear, i.e. above 16 kHz (Jayasooriya et al., 2004). Ultrasound

59 cavitations could result in the occurrence of micro streaming which is able to enhance heat

60 and mass transfer. Ultrasonic is a rapidly growing field of research, which is finding

61 increasing use in the food industry (Jayasooriya et al., 2004; Zheng & Sun, 2006). Ultrasound

62 has been used to enhance mass transfer in solid/liquid food systems (Fuente et al., 2004; Riera

63 et al., 2004). Ultrasound applications were reported to promote the leaching of

64 oligosaccharides in legumes (Han & Baik (2006) and to reduce cooking time of rice

65 (Wambura et al., 2008).

66 In the food industry, chickpea is pre-processed in the factories to produce humus (as

67 arabic food), canned products, blended powder products. To produce these products, chickpea

68 is soaked and cooked. Therefore, this study supplies important information and ultrasonic

69 technique to process it easily. In addition, it is known that chickpea is a hard legume to cook.

70 Therefore, ultrasonic technique supply a new solution to decrease soaking and cooking time.

71 These studies show that thermosonication can be used to increase the water absorption

72 during soaking operation. The objective of this study was to determine the applicability of

73 Fick’s second law of diffusion in modeling the water diffusion characteristics of ultrasound

74 treated chickpea in an attempt to determine suitable processing conditions for rehydration.

75

76

3
 77 2. Materials and Methods

78 2.1. Raw materials

79 Certified chickpeas (inci-2003) with initial moisture content of 11.58 % (d.b.) and an

80 average diameter of 8.00 (±0.27) mm (measured with Mutitoyo No. 505–633, Japan, digital

81 micrometer) obtained from Çukurova Agricultural Research Institute (Adana, Turkey), were

82 used throughout this study. After removing foreign materials and damaged seeds, they were

83 sieved to standardize the sizes, 7.5 mm to 9 mm.

84

85 2.2. Water absorption determination during soaking operation

86 The soaking of chickpea was performed at 20, 30, 40, 50, 60, 70, 87, 92 and 97
o
87 C without, and with 25 kHz 100 W (acoustic energy density (EAD) of 0.025 W cm-3), 40

88 kHz 100 W (EAD of 0.025 W cm-3) and 25 kHz 300 W (EAD of 0.017 W cm-3) ultrasound

89 treatments. One hundred grams of chickpea seeds were immersed in 2000 ml deionized water

90 (1:20); conventional and ultrasonic soaking were both performed in ultrasonic (US) tanks

91 (Intersonik Co., Turkey) until seeds were fully hydrated. Four grams of chickpea and 80 ml

92 soaking water (1:20) were quickly removed from the tanks for the moisture content

93 determination within 30 minutes intervals. Chickpea seeds were gently wiped with clean

94 paper towel to remove excess water and ground for the moisture content determination. The

95 moisture contents of randomly selected grains (5 g) were determined in dry basis at 105 oC for

96 48 h using oven drying method (AOAC, 2002) and used for Fick’s modeling of water

97 diffusion. The experiments were replicated twice and measurements were duplicated.

98

99 2.3. Determination of soluble solids loss during soaking of chickpeas

100 Four grams of chickpea and 80 mL of soaking water (1:20 ratio) were removed from the

101 soaking chamber after 3.5 h of soaking operation at 97 oC. Soluble solids content (Brix, g/g%)

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102 of the soaking water was measured at 25 oC by using Abbe-refractometer (Opton-F.G. Bode

103 and Co., Germany) and was reported as maximum soluble solids loss.

104

105 2.4. Determination of gelatinization temperature of chickpeas

106 Birefringence images of the chickpea samples at soaking temperatures of 40, 50, 60 and

107 70 oC were captured in a PC using a polarized light microscope (OLYPOS TX51, Euromex

108 Microscopen, Ed Arnhem, Netherlands) equipped with a video camera (VC 3031, Euromex

109 Microscopen, Ed Arnhem, Netherlands) connected to the PC (Figure 6). A solution of 1 %

110 (cooked chickpea flour/water) samples was prepared. After 30 minutes of mixing, 20 µL of

111 sample solution was spread on lamella, and the birefringence images were captured through

112 the microscope. The gelatinization temperature of the grains is defined as the temperature at

113 which the birefringence of starch start to diminish (Hoseney, 1994).

114
115 2.5. Statistical analysis

116 SIGMA PLOT 10 (Jandel Scientific, San Francisco, USA) were used to fit the models

117 and to plot the data. ANOVA and DUNCAN Multiple Range Tests, using SPSS version 16, at

118 P < 0.05 were performed to determine effect of processing parameters.

119

120 3. Results and Discussion

121 3.1. Water diffusion characteristics of chickpea during soaking

122 Food legumes are usually soaked before cooking to provide sufficient amount of moisture

123 for gelatinization of starch and/or gelation of protein. The most important property for

124 soaking of chickpea is the moisture content to achieve the proper cooking operation. It could

125 be achieved either through conditioning below the gelatinization temperature and then

126 cooking above the gelatinization temperature, or through direct cooking above the

127 gelatinization temperature. Mass transfer plays a key role in food processing, like

5
128 humidification and dehumidification, dehydration, distillation, absorption, etc. The driving

129 force for mass diffusion is the concentration difference. In solids, there can obviously be no

130 convection and all movements are by molecular diffusion due to random molecular

131 movements.

132 The water absorption characteristics of chickpea were analyzed using moisture content

133 (%, d.b.) values in this study. The mean moisture contents and the statistical analysis of

134 soaked chickpeas at 20-97 oC without ultrasound, and with 25 kHz 100 W, 40 kHz 100 W and

135 25 kHz 300 W ultrasounds treatment were illustrated in Figures 1-4 and tabulated in Tables 1-

136 4. The moisture contents (%, d.b.) of chickpea during soaking were significantly (P<0.05)

137 increased as the temperature, time and power of ultrasounds increased (Figures 1-4 and

138 Tables 1-4). Chickpea water absorption curves are characterized by an initial phase of rapid

139 water pickup followed by an equilibrium phase, during which the chickpea approaches its full

140 soaking capacity. The rate of water absorption increased with increasing temperature as

141 suggested by the slopes of the absorption curves getting steeper with increased temperature

142 (Figures 1-4).

143

144 3.2. Primary modeling of chickpea water diffusion as a function of time

145 Many theoretical, empirical, and semi-empirical models have been employed for

146 modeling, to relate experimental results with physical laws, the water absorption behavior of

147 agricultural products during soaking. The theoretical mechanisms for the kinetics of the

148 diffusion process have been proposed for the Fickian diffusion model by some researchers

149 before (Bello et al., 2004; Kashaninejad et al., 2007; Sabapathy et al., 2005; Seyhan-Gürtaş et

150 al., 2001; Gowen et al., 2007).

151 Moisture diffusivity is an important transport property necessary for the design and

152 optimization of all the processes that involve internal moisture movement. Diffusion

6
153 coefficient is the factor of proportionality representing the quantity of substance diffusing

154 across a unit area through a unit concentration gradient in unit time. Total amounts of

155 diffusing substance entered a spherical grain of radius r can be obtained from the following

156 Fick’s series type equation (Crank, 1975):

M −Me ∞
6  D eff π 2 2 
157 =∑ exp − n t (1)
Mo −Me n =1 n 2π 2  r2 

158 Where M, Me, Mo are moisture contents (%, d.b.) at any time, equilibrium and initial,

159 respectively. Deff and r are effective diffusion constant (m2 s-1) and average radius of chickpea

160 (m), respectively. A fit of the experimental data for soaking times leads to the determination

161 of an average diffusion coefficient, Deff, via Eq. 1 which is Fick’s law of diffusion of water in

162 solids of spherical shape. The chickpea seeds may be approximated as spheres with a mean

163 diameter of 0.0040 m (±0.0001). Fick’s laws of diffusion (Eq. 1) and its derived equations

164 account for most of the models used in food science, as can be observed from publications

165 (Garcia-Pascual et al., 2006; Gowen et al., 2007; Sabapathy et al., 2005). Some of the

166 common assumptions and simplifications often made for solving Fick’s second law (Eq. 1)

167 include the following: 1) the moisture transfer is one dimensional, unsteady state in the radial

168 direction, 2) chickpea is considered to be an almost spherical object, 3) the initial temperature

169 and moisture distributions are uniform, 4) there is a moisture gradient in the chickpea with

170 respect to time, 5) the thermal properties are constant, 6) chickpea is considered as a

171 homogeneous isotropic solid, 7) moisture transfer to and from the seed is due to concentration

172 gradient, 8) the quantity of solid loss in the grains during cooking was neglected, 9) for long

173 soaking times, only the first term of series equation was significant.

174 In this study, the effect of loss of soluble solids from chickpea seeds was not taken into

175 account in calculating the moisture content because maximum loss of soluble solids from

176 chickpea at temperatures of 97 oC for 3.5 h soaking was about 2.06 % of the original mass

7
177 which in comparison with the water gain was assumed to be negligible. Other researchers

178 have also reported similar assumption for other seeds (Sayar et al., 2001; Sabapathy et al.,

179 2005). When these assumptions were applied on Fick’s second law, the following equation

180 was obtained.

6  Deff π 2 t 
181 M = M e + ( M o − M e ) 2 exp −  (2)
π  r 2 

182 The Fick’s law of diffusion function is related to diffusion of water and diffusion

183 coefficient (Deff). For mathematical modeling of the variation of moisture content of chickpea

184 during soaking at each temperature without, and with ultrasounds treatment, Fick’s law model

185 was tested. The parameters in this model such as Deff (main parameter), Me, were estimated by

186 using the non-linear regression analysis of equations (2) and presented on Table 5. The

187 performance parameters of the model, the coefficient of determination (R2) and percentage of

188 root mean square error (% RMSE) are given on Table 5. The course of the hydration,

189 adequately fitted by a nonlinear equation (Eq. 2), and reveals the fact that the seed moisture

190 content increases with soaking time, use of ultrasound treatments and increase in used

191 ultrasound power at all temperatures (Figures 1-4 and Tables 1-5). Water absorption ceases

192 when the seed attained the equilibrium water content (Sayar et al., 2001). The diffusion

193 process, which obeys the Fick’s law model, was found to be a thermally activated process and

194 sensitive to temperature, time, ultrasound treatment and its power.

195 When the temperature was raised from 20 to 97 oC, Deff values were increased from 1.40 x

196 10-10 to 7.72 x 10-10 (m2 s-1), also significant (P<0.05) increase was observed in

197 the equilibrium moisture content (Me) (from 119.82 to 150.05 (%, d.b.)) (Table 5). R2 and %

198 RMSE values were in the range of 0.9894-0.9960 and 2.51-8.03, respectively. The magnitude

199 of diffusion coefficient reported by Sayar et al. (2001) for temperatures ranging from 20 to

200 100 °C were 2.43 x 10-10 to 39.16 x 10-10 m2 s-1 for spring chickpea and 1.99 x 10-10 to 36.94 x

8
201 10-10 m2 s-1 for winter chickpea. The water diffusion coefficient of chickpea ranged from 9.71

202 x 10-11 to 5.98 x 10-10 m2 s-1 in the study of Seyhan-Gürtaş et al. (2001). The diffusion

203 coefficients of chickpeas for temperature range of 45 - 98.7 oC were found as 0.14 x 10-10 -

204 5.51 x 10-10 m2 s-1 in another study (Sabapathy et al., 2005). Diffusivity values reported in this

205 study were similar to the literature results. Moisture absorption at elevated temperatures may

206 induce irreversible changes of the seeds, such as chemical and structural degradation. It was

207 reported that the rate of water absorption by legumes increased with increase in time and

208 temperature of the soaking water. As the process continued, water absorption rate decreased

209 steadily due to water filling into the free capillary and intermicellar spaces, and increasing the

210 extraction rates of soluble solids from grains (Quast & de Silva, 1977; Tang et al., 1994;

211 Sopade & Obekpa, 1990; Abu-Ghannam & McKenna, 1997).

212

213 3.3. A general model to describe the water diffusion as a function of soaking time and

214 temperature

215 Previous studies showed that temperature is one of the most important factors affecting

216 the water diffusivity and water absorption of agricultural products (Kashaninejad et al., 2007;

217 Turhan et al., 2002). An Arrhenius type equation (Eq. 3), which had been used previously to

218 describe the temperature dependant hydration kinetics of legumes (Abu-Ghannam &

219 McKenna, 1997; Turhan et al., 2002), were used to evaluate temperature dependency of

220 diffusion coefficients (Deff) and gelatinization temperature:

Ea 1
221 ln( D eff ) = ln( D ref ) − ( )( ) (3)
R T

222 Where Deff, T, Ea and R are effective diffusion coefficient of the Fick’s model, soaking

223 temperature (in K), activation energy for the hydration process in kJ mol-1 and ideal gas

224 constant in 8.314 x10-3 kJ mol-1 K-1, respectively. Dref is reference diffusion rate constant for

225 the Fick’s model. The rate of water transfer and/or starch gelatinization in whole cereal and

9
226 legume grains were found to be changing linearly with temperature and every curve brake at

227 a specific temperature which is close to gelatinization temperature (Bakshi & Singh, 1980;

228 Sayar et al., 2001; Sağol et al., 2006). Arrhenius plots of the natural logarithm of rate

229 constants versus the inverse of T (K) for chickpeas are superposed in Figure 5. The activation

230 energy, Ea, is related to the slope of this graph, and shows the temperature dependence of Deff.

231 To locate the temperature at which the break in the Arrhenius curve for soaked chickpeas

232 occurred, the estimated natural log of rate constants (Deff) was fitted to a linear model with

233 break point and the break temperature was estimated to be 61.47 oC (R2= 0.9349-0.9954) for

234 the model (Muggeo, 2003). Such a discontinuity in the Arrhenius curve has been observed

235 during the soaking of rice (Bakshi & Singh, 1980) and chickpeas (Sayar et al., 2001), and it

236 has been suggested that the break is linked to the early onset of starch gelatinization. The

237 process of gelatinization is generally thought to occur between 63 and 70 oC for chickpeas

238 (Fernandez & Berry, 1989). However, it has been suggested (Sayar et al., 2001; Turhan et al.,

239 2002) that chickpea gelatinization may actually begin between the lower temperatures of 55

240 and 60 oC. Starch granules of the chickpeas used in this study kept the integrity of Maltese

241 crosses till 61 oC (Figure 6). They noticeably started to decrease in number and distort in

242 shape between 60 and 70 oC (Figure 6) pointing that gelatinization temperature of chickpeas

243 starts between 60 and 70 oC. This observed temperature range is fairly close to the reported

244 gelatinization temperature of 63-70 oC for chickpea (Fernandez & Berry, 1989). It is possible

245 that the break in the Arrhenius curve for soaked chickpeas was due to partial gelatinization

246 and/or structural changes, promoted soaking at temperatures above 60 oC.

247 Incorporating the temperature break at 61.47 oC for the Fick’s model, time and

248 temperature dependence of moisture content for soaked chickpeas, and dependence of initial

249 and equilibrium moisture contents, the following general models were derived to describe the

250 water absorption kinetics of chickpeas:

10
 6  π2 −5 − 3450.79 
251 M = M e + (M o − M e ) 2
exp− 2 1⋅ 696×10 exp( )t  (≤ 60 oC) (4)
π  r T 

6  π2 −1123.56 
252 M = M e + (M o − M e ) 2 exp− 2 1.613×10−8 exp( )t  ( > 60 oC) (5)
π  r T 

253 Equations 4 and 5 can be used to find the moisture content of chickpea during

254 soaking/cooking at any time (seconds) and temperature (K) providing that Mo and Me are

255 known.

256 The Arrhenius equation has been previously used to describe the temperature dependent

257 hydration kinetics of other grains and seeds (Maskan, 2002; Turhan et al., 2002). The Deff

258 values decreased as temperature increased suggesting a corresponding increase in the initial

259 water absorption rate. As it is evident from Figure 5, the linearity of the curves indicates an

260 Arrhenius relationship for model.

261 When the Arrhenius equation (3) was applied to the Deff values for temperatures below

262 and above break point (61.47 oC) separately, the activation energy values of 28.69

263 (R2=0.9756) and 9.34 (R2=0.9954) kJ mol-1 were calculated, respectively. This value agrees

264 well with the literature value of 19.50 kJ mol-1 for the activation energy of osmotic hydration

265 of chickpeas at 5-50 oC (Pinto and Esin, 2004). The activation energies of chickpea were

266 found as 41.79 kJ mol-1 and 8 kJ mol-1 for 25-37 oC and 37-60 oC temperature ranges by

267 Goven et al. (2007). In another study, the activation energy for chickpea was 48 and 18 kJ

268 mol-1 for temperature bellow and above 55 oC, respectively (Sayar et al., 2001). The lower

269 activation energy for the rate of water transfer above the gelatinization

270 temperature implies that water travels faster in gelatinized chickpea than in ungelatinized

271 chickpea.

272

273

11
274 3.4. Effect of ultrasounds on water diffusion during soaking of chickpeas

275 One emergent application of power ultrasound in food industry is the enhancement of

276 mass transfer in processes where diffusion takes place. Power ultrasound introduces that

277 pressure variation at solid/liquid interfaces, and therefore increases the moisture absorption

278 rate. Acoustic energy also causes oscillating velocities and micro streaming at the interfaces

279 which may affect the diffusion boundary layer (Gallego-Juarez, 1998). Furthermore,

280 ultrasonic waves also produce rapid series of alternative contractions and expansions (sponge

281 effect) of the material in which they are traveling; this alternating stress creates microscopic

282 channels which may make the moisture gain easier. In addition, acoustic waves may produce

283 cavitations of water molecules inside the solid matrix, which may be beneficial for the gain of

284 strongly attached moisture (Gallego-Juarez, 1998; Mulet et al., 2003).

285 The effects of ultrasounds on water absorption of chickpeas were illustrated in Figures 2-

286 4. The statistical analysis of moisture contents were tabulated in Tables 1-4. Application of 25

287 kHz 100 W ultrasound significantly (P<0.05) increased the water absorption of chickpea for

288 all temperatures (20-97 oC). The moisture content (%, d.b.) values of chickpea were found to

289 be increased from 76.91 to 85.14 % (d.b), when the 25 kHz 100 W ultrasound was applied at

290 20 oC and 180 min soaking. Increase in power of ultrasounds (from 100 to 300 W) also

291 further significantly (P<0.05) increased the moisture content (from 85.14 to 91.89 %) of

292 chickpea during 20 oC and 180 min soaking. Similarly, increase in power (100 to 300 W)

293 increased the moisture content of soaked chickpea at all other temperatures for a given

294 soaking time. However, 40 kHz 100 W ultrasound applications resulted in slight changes

295 (mostly increases) in moisture values. Increase in ultrasound frequency from 25 to 40 kHz

296 insignificantly (P>0.05) decreased the moisture content (%, d.b.) from 76.91 to 76.55 % at the

297 same soaking temperature and time (Table 2).

12
298 Deff of the Fick's law model was main parameter for the ultrasonic assisted process of

299 diffusion which was compared with the conventional soaking. At all temperatures, Deff values

300 found from the Fick’s model were significantly increased when 25 kHz 100 W ultrasound

301 treatment applied and also when ultrasound power increased to 300 W (Table 5). For soaking

302 at 20 oC, Deff values changed from 1.40x10-10 to 1.70x10-10 and to 2.01x10-10 m2 s-1 for non-

303 ultrasound, 25 kHz 100 W and 25 kHz 300 W ultrasound treatments, respectively. Deff

304 changes at all temperatures were significant (P<0.05) (Table 5). The ultrasound treatment

305 increased the water diffusion of chickpea during soaking due to increasing of mass diffusion

306 rate (Fuente et al., 2004). However, application of high frequency ultrasonic (40 kHz) for all

307 soaking temperatures did not significantly (P>0.05) affect or/and decreased the water

308 absorption rate and the diffusion coefficient of chickpea (Tables 2-5 and Figures 2-4). Change

309 of ultrasound frequency from 25 to 40 kHz decrease Deff value from 1.40x10-10 to 1.28 x10-10

310 m2 s-1 (20 oC soaking).

311

312 4. Conclusion

313 Water diffusion rates of chickpea significantly increased (P<0.05) with increasing of

314 soaking time, temperature and power of ultrasound (100 - 300 W). High ultrasound

315 frequencies such as 40 kHz did not significantly (P>0.05) affect the water diffusion of

316 chickpea during soaking. Fick’s diffusion constant (Deff) for a temperature range of 20-97 oC

317 increased from 1.40 x 10-10 to 11.9 x 10-10 (m2 s-1) with ultrasound application.

318 Fick’s second law model where Arrhenius relationship inserted for Deff can be used to

319 determine moisture content of chickpeas as a function of soaking time and temperature.

320 Average gelatinization temperature of chickpea from the water absorption model was found

321 as 61.47 oC. Activation energy (Ea) values of chickpea for below and above gelatinization

13
322 temperature of 61.47 oC were found to be 28.69 and 9.34 kJ mol-1, respectively. Ultrasound

323 treatments decreased the soaking time of chickpea.

324

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

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

382 Sağol, S., Turhan, M. & Sayar, S. (2006). A potential method for determining in situ

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

384 Journal of Food Engineering, 76, 427–432.

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

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

387 91–98.

388 Seyhan-Gürtaş, F., Mehmet, A.K. & Evranuz, Ö.E. (2001). Water diffusion coefficients of

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

390 of Agriculture, 25, 297–304.

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

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

393 1087.

394 Tang, J., Sokhansanj, S. & Sosulski, F.W. (1994). Moisture-absorption characteristics of

395 Laird lentils and hard shell seeds. Cereal Chemistry, 71, 423–428.

16
396 Turhan, M., Sayar, S. & Gunasekaran, S. (2002). Application of Peleg model to study water

397 absorption in chickpea during soaking. Journal of Food Engineering, 53, 153-159.

398 Wambura, P., Yang, W. & Wang, Y. (2008). Power Ultrasound Enhanced One-Step Soaking

399 and Gelatinization for Rough Rice Parboiling. International Journal of Food Engineering,

400 4, 1-12.

401 Wang, N., Lewis, M.J., Brennan, J.G. & Westby, A. (1997). Effect of processing methods on

402 nutrients and anti-nutritional factors in cowpea. Food Chemistry, 58, 59–68.

403 Zheng, L. & Sun, D.W. (2006). Innovative applications of power ultrasound during food

404 freezing processes-a review. Food Science and Technology, 17, 16-23.

405

406

407

408

409

410

411

412

413

414

415

416

417

418

419

17
420 Figure 1. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas

421 during soaking at different temperatures.

422

423 Figure 2. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas

424 during soaking at 20 (A), 30 (B) and 40 (C) oC temperatures without and with ultrasound

425 treatments.

426

427 Figure 3. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas

428 during soaking at 50 (A), 60 (B) and 70 (C) oC temperatures without and with ultrasound

429 treatments.

430

431 Figure 4. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas

432 during soaking at 87 (A), 92 (B) and 97 (C) oC temperatures without and with ultrasound

433 treatments.

434

435 Figure 5. Arrhenius plot of Fick’s law model of diffusion constant, Deff, of chickpea over the

436 soaking temperature range of 20-97 oC.

437

438 Figure 6. Effect of soaking temperature on the birefriengence of chickpea starch at 40, 50, 60

439 and 70 oC.

440

441

442

443

444

18
 160

140 20 oC

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

30 oC
120
40 oC
100 50 oC
60 oC
80
70 oC
60 87 oC
40 92 oC
97 oC
20 Fick's Model

0
0 100 200 300 400 500 600 700 800

Time (min)
445

446

447 Figure 1. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas

448 during soaking at different temperatures.

449

450

451

452

453

454

455

456

19
 140

120

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

100

80
20 oC (control)
60
20 oC + 25 kHz 100 W US
40 20 oC + 40 kHz 100 W US
20 oC + 25 kHz 300 W US
20 Fick's model

0
0 100 200 300 400 500 600

457 Time (min)

458 (A)

140

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

100

80

60 30 oC (control)
30 oC + 25 kHz 100 W US
40
30 oC + 40 kHz 100 W US

20 30 oC + 25 kHz 300 W US
Fick's model
0
0 100 200 300 400 500
Time (min)
459
460 (B)

140

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

100

80
40 oC (control)
60
40 oC + 25 kHz 100 W US
40 oC + 40 kHz 100 W US
40
40 oC + 25 kHz 300 W US
20 Fick's model

0
0 100 200 300 400 500
Time (min)
461
462 (C)

463

464 Figure 2. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas

465 during soaking at 20 (A), 30 (B) and 40 (C) oC temperatures without and with ultrasound

466 treatments.

20
 180

160

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

140

120

100
50 oC (control)
80
50 oC + 25 kHz 100 W US
60 50 oC + 40 kHz 100 W US
40 50 oC + 25 kHz 300 W US
20 Fick's model

0
0 100 200 300 400
Time (min)
467
468 (A)

140

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

100

80
60 oC (control)
60 60 oC + 25 kHz 100 W US
60 oC + 40 kHz 100 W US
40
60 oC + 25 kHz 300 W US
Fick's model
20

0
0 100 200 300
Time (min)
469
470 (B)

160

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

120

100

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

0
0 100 200 300 400
Time (min)
471
472 (C)

473

474 Figure 3. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas

475 during soaking at 50 (A), 60 (B) and 70 (C) oC temperatures without and with ultrasound

476 treatments.

21
 160

140

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

120

100

80 87 oC (control)
87 oC + 25 kHz 100 W US
60
87 oC + 40 kHz 100 W US
40 87 oC + 25 kHz 300 W US
Fick's model
20

0
0 50 100 150 200 250
Time (min)
477
478 (A)

160

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

120

100

80
92 oC (control)
60 92 oC + 25 kHz 100 W US
92 oC + 40 kHz 100 W US
40
92 oC + 25 kHz 300 W US
20 Fick's model

0
0 50 100 150 200 250
Time (min)
479
480 (B)

160

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

120

100
97 oC (control)
80 97 oC + 25 kHz 100 W US
60 97 oC + 40 kHz 100 W US
97 oC + 25 kHz 300 W US
40 Fick's model
20

0
0 50 100 150 200 250
Time (min)
481
482 (C)

483

484 Figure 4. Means of experimental and predicted moisture contents (% g/g, d.b.) of chickpeas

485 during soaking at 87 (A), 92 (B) and 97 (C) oC temperatures without and with ultrasound

486 treatments.

22
 -20,5
Experimental (20-60 oC)
o
Experimental (60-97 C)
y= -10.9844- 3450.7955*x (R2=0.9756) (20-60 oC)
-21,0
y= -17.9424-1123.565*x (R2 =0.9954) (60- 97 oC)
ln (Deff, m s )
2 -1

-21,5

-22,0

-22,5

-23,0
0,0026 0,0028 0,0030 0,0032 0,0034 0,0036

1/T (1/K)
487

488

489 Figure 5. Arrhenius plot of Fick’s law model of diffusion constant, Deff, of chickpea over the

490 soaking temperature range of 20-97 oC.

491

23
492

493 (40 oC) (50 oC)

494

495 (60 oC) (70 oC)

496

497 Figure 6. Effect of soaking temperature on the birefriengence of chickpea starch at 40, 50, 60

498 and 70 oC.

499

500

501

502

24
503 Table 1. Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of

504 soaked chickpeas as a function of processing time and temperature.

505

Time Moisture content (%, d.b)

(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,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 43.88 c,1
57.54 c,2
62.58 c,3
84.70 c,4
97.89 c,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
108.05 d,5
110.19d,6 122.38d,7 125.43d,8 136.49d,9
120 65.50 e,1
78.98 e,2
88.24 e,3
108.69 e,4
115.63 e,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
506 a-h
Indicate statistical differences between each row at α=0.05,

507 1-9
Indicate statistical differences between each column at constant temperatures, α=0.05.

508

509

510

511

512

513

514

515

516

517

518

519

520

521

522

523

25
524 Table 2. Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of

525 soaked chickpeas at 20, 30 and 40 oC with and without ultrasound treatments.

526

Time Moisture content (%, d.b)

o
(min) 20 C 20 C+40 kHz 100 W 20 oC+25 kHz 100 W
o
20 oC+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 oC o o
30 C+40 kHz 100 W 30 C+25 kHz 100 W o
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 104.40 a
106.25c 113.29d
270 107.75b 107.39 a
108.23c 115.60d
300 109.96b 109.75a 112.03c 118.85d
40 oC o o
40 C+40 kHz 100 W 40 C+25 kHz 100 W o
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 100.21 b
109.76c 115.29d
180 101.90b 100.62a 115.10c 121.19d
210 110.18b 109.70 a
118.23c 128.12d
240 111.00a 112.58 b
122.29c 127.27d
270 117.95b 116.90 a
125.34c 128.00d
300 121.84b 120.49a 125.47c 128.12d
527 a-d
Indicate statistical differences between each column at constant temperatures, α=0.05.

528

529

530

26
531 Table 3. Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of

532 soaked chickpeas at 50, 60 and 70 oC with and without ultrasound treatments.

533

Time Moisture content (%, d.b)

o
(min) 50 C 50 C+40 kHz 100 W 50 oC+25 kHz 100 W
o
50 oC+25 kHz 300 W
0 11.58a 11.58a 11.58a 11.58a
30 62.36b 57.74a
64.74c 75.35d
60 84.70a 86.78 b
91.31c 109.25d
90 95.43a 101.14 b
106.73c 117.07d
120 108.69b 108.19a 115.86c 121.01d
150 115.84a 117.20 b
123.87c 128.71d
180 120.82b 119.15 a
126.11c 131.34d
210 122.71a 123.12 b
127.22c 134.59d
60 oC 60 oC+40 kHz 100 W 60 oC+25 kHz 100 W 60 oC+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 108.36 b
113.06c 120.27d
120 115.63b 114.91 a
119.91c 126.34d
150 124.02b 124.00a 127.76c 130.71d
180 126.57b 126.51 a
128.99c 132.14d
210 128.99b 127.93 a
130.74c 134.92d
70 oC 70 oC+40 kHz 100 W 70 oC+25 kHz 100 W 70 oC+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 109.72 a
114.24c 124.46d
120 119.45b 115.87a 122.16c 129.46d
150 126.35b 125.11 a
129.20c 131.97d
180 129.78b 128.64 a
131.50c 133.72d
210 130.68b 129.32a 132.30c 135.78d
534 a-d
Indicate statistical differences between each column at constant temperatures, α=0.05.

535

536

537

538

539

540

541

27
542 Table 4. Summary of multiple range analysis (Duncan test) on moisture contents (%, d.b.) of

543 soaked chickpeas at 87, 92 and 97 oC with and without ultrasound treatments.

544

Time Moisture content (%, d.b)

o
(min) 87 C 87 C+40 kHz 100 W 87 oC+25 kHz 100 W
o
87 oC+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 107.48 a
115.49c 128.81d
90 122.38b 122.13 a
128.16c 142.46d
120 129.30a 130.03b 132.48c 148.93d
150 135.41a 136.01 b
138.23c 150.90d
92 oC o o
92 C+40 kHz 100 W 92 C+25 kHz 100 W o
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 124.29 a
139.77c 147.79d
120 131.36b 131.23 a
146.11c 151.24d
150 137.76b 137.75 a
150.54b 154.23c
97 oC 97 oC+40 kHz 100 W 97 oC+25 kHz 100 W 97 oC+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 119.59 a
139.07c 145.37d
90 136.49b 136.25 a
148.67c 153.97d
120 144.71a 144.91b 151.23c 157.57d
150 148.59a 148.61 b
158.93c 165.45d
545 a-d
Indicate statistical differences between each column at constant temperatures, α=0.05.

546

547

548

549

550

551

552

553

554

555

28
556 Table 5. Predicted parameters of Fick’s model during soaking of chickpeas at different

557 temperatures without and with ultrasound application.

558

Me Deff x 1010 RMSE

Process (%, d.b) (m2 s-1) R2 (%)
20 oC 119.82 1.40 0.9960 8.03
o
20 C + 25 kHz 100 W 119.48 1.70 0.9907 13.88
20 oC + 40 kHz 100 W 123.10 1.28 0.9943 10.76
20 oC + 25 kHz 300 W 120.94 2.01 0.9925 11.29
30 oC 122.81 1.87 0.9894 9.70
o
30 C + 25 kHz 100 W 122.61 2.10 0.9910 10.97
30 oC + 40 kHz 100 W 122.41 1.86 0.9885 12.02
30 oC + 25 kHz 300 W 124.40 2.62 0.9904 8.78
40 oC 128.44 2.39 0.9944 8.93
o
40 C + 25 kHz 100 W 129.86 2.98 0.9914 9.88
40 oC + 40 kHz 100 W 127.56 2.46 0.9952 8.01
40 oC + 25 kHz 300 W 130.79 3.79 0.9951 6.59
50 oC 128.64 4.11 0.9942 2.70
50 oC + 25 kHz 100 W 130.72 4.94 0.9988 2.72
50 oC + 40 kHz 100 W 127.30 4.42 0.9981 2.53
50 oC + 25 kHz 300 W 133.56 6.52 0.9944 2.91
60 oC 129.76 5.58 0.9957 4.74
o
60 C + 25 kHz 100 W 131.68 5.92 0.9978 3.43
60 oC + 40 kHz 100 W 129.17 5.57 0.9966 4.10
60 oC + 25 kHz 300 W 133.67 7.29 0.9978 1.87
70 oC 130.66 6.01 0.9944 5.85
o
70 C + 25 kHz 100 W 131.05 7.11 0.9924 5.45
70 oC + 40 kHz 100 W 130.22 5.78 0.9935 6.19
70 oC + 25 kHz 300 W 134.06 7.96 0.9993 1.29
87 oC 137.47 7.12 0.9938 5.55
o
87 C + 25 kHz 100 W 139.06 8.19 0.9944 4.13
87 oC + 40 kHz 100 W 138.78 6.76 0.9942 5.75
87 oC + 25 kHz 300 W 150.63 9.77 0.9937 4.18
92 oC 139.70 7.49 0.9908 6.36
92 oC + 25 kHz 100 W 149.74 8.54 0.9935 5.00
92 oC + 40 kHz 100 W 139.67 7.40 0.9925 5.73
92 oC + 25 kHz 300 W 151.37 11.20 0.9948 9.85
97 oC 150.05 7.72 0.9959 2.51
o
97 C + 25 kHz 100 W 157.88 9.23 0.9974 2.02
97 oC + 40 kHz 100 W 150.32 7.53 0.9954 5.29
97 oC + 25 kHz 300 W 159.75 11.90 0.9960 2.55
2
1 n
559 RMSE (%) = Root mean square error: 100*
n
∑ [( M
1
exp −M pre ) / M exp ]

29