Journal of Food Engineering 80 (2007) 12931301 www.elsevier.

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Water desorption thermodynamic properties of pineapple

Susana Simal *, Antoni Femenia, Africa Castell-Palou, Carmen Rossello
Department of Chemistry, University of Illes Balears, Ctra. Valldemossa km. 7.5, 07122 Palma de Mallorca, Spain Received 6 April 2006; received in revised form 3 October 2006; accepted 4 October 2006 Available online 17 November 2006

Abstract The water desorption isotherms of pineapple were determined at 5, 15, 25, 35 and 45 C by using a gravimetric technique within the water activity range of 0.10.9. The eect of the temperature showed a cross-over of the desorption isotherms at water activity of 0.75. The experimental data was tted to the GAB model taking into account the eect of the temperature. The obtained simulation could be considered satisfactory (mean relative error <5.0% and percentage of explained variance >99.8%). The net isosteric heat of sorption (Qst ) n and the dierential entropy (Sd) were estimated as functions of the moisture content, the enthalpyentropy compensation theory was applied to sorption isotherms and plots of Qst vs. Sd provided the isokinetic temperature, suggesting an enthalpy controlled sorption process. 2006 Elsevier Ltd. All rights reserved.
Keywords: Isotherm; Pineapple; GAB model; Isosteric heat; Entropy; Compensation theory

1. Introduction In every food product there is an inherent relationship between water content and the relative humidity of the atmosphere in equilibrium with it, which is equivalent to water activity (aw) (Mulet, Garca-Pascual, Sanjuan, & GarcaReverter, 2002). The thermodynamic concept of water activity (Lewicki, 2004) is used in drying applications through the sorption isotherms, which represent the change in water activity versus the change in moisture content of a sample at equilibrium and at a specied temperature. Furthermore, the knowledge of the temperature dependence of sorption phenomenon is important for modelling the thermodynamics of the system (Kumar, Singh, Patil, & Patel, 2005). Engineering design is an important application of sorption isotherms for separation process, where interface water transport is involved. Knowledge of the sorption isotherms is considered important for the design and optimization of the drying equipment, for the evaluation of

Corresponding author. E-mail address: susana.simal@uib.es (S. Simal).

airfood interface state in drying process simulation and, also, to determine the drying limit at given air conditions. Several models have been proposed in the literature to mathematically describe the sorption isotherms of hygroscopic food products using isotherm equations (ASAE, 2004). Some of these models are based on theories of the mechanism of sorption; others are purely empirical or semi-empirical (Kaymak-Ertekin & Gedik, 2004). However, experience has shown that no single equation gives accurate t for sorption isotherm data over the entire range of aw and for dierent types of foods (Singh, Rao, Anjaneyulu, & Patil, 2001). In general, the widely accepted criteria to select the most appropriate model are the degree of t to the experimental data and the simplicity of the model (Kaymak-Ertekin & Gedik, 2004). Thermodynamic functions calculated from sorption isotherms allow the interpretation of the experimental results in accordance with the statement of the theory (Arslan & Togrul, 2006). The knowledge of sorption isotherms at different temperatures enables an evaluation of the heat of sorption which determines the interaction between an adsorbent and an adsorbate. A rapid computational procedure, commonly used for its determination, is the

0260-8774/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.jfoodeng.2006.10.001

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Nomenclature aw Cg C0 Kg K0 hm hn Lv MRE ni nw p p0 Qst Qst n water activity Guggenheim constant entropic accommodation factor (Eq. (2)) (dimensionless) constant in the GAB model entropic accommodation factor (Eq. (3)) heat of sorption of the monolayer (kJ/mol) heat of sorption of the multilayer (kJ/mol) latent heat of vaporisation of pure water (kJ/ mol) mean relative error (%) total number of isotherms water moles (mol) partial pressure of water vapour saturation pressure isosteric heat of sorption (kJ/mol) net isosteric heat of sorption (kJ/mol) R Sy Syx T Ta Tb Vc Ve % var W Wm W0 DG DH universal gas constant (kJ/mol K) standard deviation (sample) standard deviation (estimation) temperature (C) absolute temperature (K) isokinetic temperature (K) calculated value experimental value percentage of explained variance (%) moisture content (kg water/100 kg dm) monolayer moisture content (kg water/100 kg dm) constant adjusted to the temperature eect (Eq. (6)) (kg water/100 kg dm) free energy (kJ/mol) enthalpy (kJ/mol)

application of the ClausiusClayperon equation to the sorption isotherms, at constant moisture contents. The heat of sorption of water in dried foods is essential for modelling of various food processes and food storage. It can be used to estimate the energy requirements of food drying and it also provides important information on the state of water in food products (Kaya & Kahyaoglu, 2005). In general, the isosteric heat of sorption is greater than the latent heat of vaporisation of pure water at a particular temperature and can be considered as indicative of the intermolecular attraction forces between sorptive sites and water. The change in the isosteric heat of sorption with the moisture content of the sample indicates the availability of polar sites to water vapour as the desorption/adsorption proceeds (Kumar et al., 2005). The sorption processes in systems exhibiting hysteresis involve thermodynamically irreversible phenomena. Thus, the entropy production arises from this irreversibility. The changes in the entropy could be used in energy balance giving valuable information about energy utilization in food processing (Kaya & Kahyaoglu, 2005). The dierential entropy of a material may be related to the number of available sorption sites at a specic energy level (McMinn & Magee, 2003). Physical phenomena, such as sorption reactions, are often evaluated on the basis of the isokinetic, or enthalpyentropy compensation, theory. This theory (McMinn, Al-Muhtaseb, & Magee, 2005) states that compensation arises from changes in the nature of the interaction between the solute and the solvent causing the reaction, and that the relationship between enthalpy and entropy for a specic reaction is linear. When this theory is applied to a sorption process, the enthalpy corresponds to the net isosteric heat of sorption.

The concept has been successfully applied to the sorption phenomena of dierent foods. McMinn and Magee (2003) determined the water adsorption and desorption isotherms of potato at dierent temperatures (30, 45 and 60 C) and concluded that the isosteric heat versus the entropy satisfy the enthalpyentropy compensation theory. Similarly, this theory could be successfully applied to water sorption for potatoes, macadamia nuts, apricots, gs, currants, prunes and raisins (Beristain, Garcia, & Azuara, 1996), for persimmon skin and pulp (Telis, Gabas, Menegalli, & Telis-Romero, 2000), for starch-rich materials (McMinn et al., 2005), for tea (Arslan & Togrul, 2006), among others. The objectives of this study were (i) to determine the water desorption for pineapple at dierent temperatures, 5, 15, 25, 35 and 45 C, (ii) model the eect of the temperature on the water desorption, (iii) determine thermodynamic functions as the isosteric heat of sorption and the dierential entropy, and (iv) evaluate the applicability of the enthalpyentropy compensation theory to the desorption phenomenon for pineapple. 2. Materials and methods 2.1. Experimental procedure Ripe pineapple fruits (Ananas comosus L. Merr) were purchased from local supermarkets, washed, peeled, and the cores removed. The total soluble solids measured as o Brix were of 13.6 0.2 g/100 g. The moisture desorption isotherms for pineapple samples were determined gravimetrically using the static method of saturated salt solutions recommended by the COST 90 project (Spiess & Wolf, 1983; Rockland & Beu-

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chat, 1987). Ten saturated salt solutions selected to give different relative humidities ranging from 10% to 90% (LiCl, CH3COOK, MgCl2, K2CO3, Mg(NO3)2, NaBr, SrCl2, NaCl, KCl and BaCl2) were prepared from analytical reagent grade salts in twist-o glass containers. The glass sorption containers were placed in temperature controlled cabinet with an accuracy of 1 C at the selected temperatures of 5, 15, 25, 35 and 45 C. Pineapple samples were exposed in the presence of the dierent saturated salts to give constant water activity values. After equilibrium was reached, the moisture content of the samples was determined according to the AOAC Method no. 934.06 (1990). All measurements were carried out in triplicate. The corresponding relative humidity of the salt solutions at the dierent temperatures was taken either from the literature (KCl, NaCl, Mg(NO3)2, K2CO3, MgCl2, CH3COOK and LiCl) (Rizvi, 1995) or experimentally measured by using an electric hygrometer NOVASINA thermoconstanter TH200 (BaCl2, SrCl2 and NaBr). The later values were in agreement with the results reported by Kiranoudis, Maroulis, Tsami, and Marinos-Kouris (1993) for the relative humidity of these saturated salt solutions at 30, 45 and 60 C. 2.2. The GAB model The most widely accepted and representative model for sorption isotherms of foods is the GAB model (Eq. (1)) (McMinn & Magee, 2003; ASAE, 2004), which according to the COST 90 study (Wolf, Spiess, & Jung, 1985) could be used to describe most food isotherms over a wide water activity range. The parameters of the GAB isotherm model have a physical meaning. In the GAB model, W is the equilibrium moisture content, the Wm parameter is the water content corresponding to saturation of all primary sites by one water molecule (namely monolayer moisture content), and Cg and Kg are energy constants. The Guggenheim constant (Cg) is related to the dierence of the chemical potential in the upper layers and in the monolayer while Kg is related to this dierence in the sorbates pure liquid state and in the upper layers. Thus, the Kg GAB parameter is, practically without exception, near but less than unity. This fact constitutes a denitive characteristic of this isotherm (Timmermann, Chirife, & Iglesias, 2001). W W m C g K g aw 1 K g aw 1 C g 1K g aw 1

The C0 and K0 parameters stand for entropic accommodation factors for the temperature eect, DH1 is the dierence between the heats of sorption of the monolayer (hm) and the multilayer (hn) of water (Eq. (4)) and DH2, the difference between the heat of vaporisation of water (Lv) and the heat of sorption of the multilayer of water (hn) (Eq. (5)). DH 1 hm hn DH 2 Lv hn 4 5

Some authors obtained for dierent foods that the monolayer moisture content parameter (Wm) is constant and independent of the temperature: in grapes, apricots, apples and potatoes, from 30 to 60 C (Kaymak-Ertekin & Gedik, 2004); in bitter orange leaves from 30 to 50 C (Mohamed, Kouhila, Jamali, Lahsasni, & Mahrouz, 2005); in nejayote from 25 to 60 C (Nogueira-Terrones, Herman-Lara, Garca-Alvardo, & Monroy-Rivera, 2004) whereas, other authors observed that the Wm depends on the temperature according to the following relationship (Eq. (6)) where W0 is an adjusted constant (Sanchez, Sanj uan, Simal, & Rossello (1997) & McLaughlin & Magee (1998) in potato, from 4 to 50 C and from 30 to 60 C, respectively; Rahman, Perera, & Thebaud (1997) in peas from 20 to 60 C; Vazquez, Chenlo, & Moreira (2001) in chestnut from 5 to 50 C).   DH W m W 0 exp 6 RT a In the literature, some methods are recommended to determine the GAB constants. One of them is the linearization of the Eq. (1) as it is shown in Eq. (7). Thus, the representation of experimental aw/[W(1 Kgaw)] vs. aw should be linear if the correct Kg value is used (Timmermann et al., 2001) and the GAB model conforms to experimental data (Nguyen, Verboven, Daudin, & Nicola, 2004). From the two linear regression coecients of this straight-line, the Wm and Cg constants can be obtained. aw 1 Cg 1 aw W 1 K g aw C g K g W m C g W m 7

The GAB equation can describe water activity variation with temperature since Cg and Kg are exponential functions of the inverse absolute temperature (Eqs. (2) and (3))   DH 1 C g C 0 exp RT a   DH 2 K g K 0 exp RT a 2 3

Usually, the linearization of the experimental data according to Eq. (7) is possible within the range 0.05 < aw < 0.8. At higher water activities, this representation presents a downward deviation due to the appearance of the third sorption stage being the limit of application of the GAB isotherm (Timmermann et al., 2001). However, Nguyen et al. (2004) observed in Conference pears sorption that these graphs were linear up to a certain value of aw about 0.95 and concluded that the GAB model could predict well the experimental data for aw up to 0.95. Sanchez et al. (1997) recommended the so-called direct method. In this method, Eqs. (2), (3) and (6) are substituted in the GAB model (Eq. (1)) and the six parameters (W0, DH, C0, DH1, K0 and DH2) are simultaneously estimated. To carry out the estimation, experimental results of water

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activity and moisture content at dierent temperatures are needed. Thus, the eects of both temperature and moisture content are simultaneously considered. Furthermore, the limit of Kg < 1 should be used in order to accomplish with the thermodynamic (Lewicki, 2000). The identication of the parameters of the equilibrium moisture isotherm model through the direct method was performed by using NonLinearFit of the Statistic package of Mathematica 5.2 software (Wolfram Research, Inc.), which estimates the coecients of a nonlinear regression function, the standard errors associated to the parameters and the residuals using least squares. The percentage of variance explained by the mathemat ical model (% var) (Eq. (8)) (Simal, Femenia, Carcel, & Rossello, 2005) and the mean relative error (MRE) (Eq. (9)) (Nguyen et al., 2004) were used in order to evaluate the goodness of the simulation provided by the proposed model. " # S2 yx %var 1 2 100 8 Sy MRE
N 100 X jV ei V ci j N i1 Vei

Qst Qst Lv n

13

The dierential entropy (Sd) can be calculated from GibbsHelmholtz equation (Eq. (14)) where the free Gibbs energy is calculated through Eq. (15) (Beristain et al., 1996). By substituting Eq. (15) into Eq. (14) and rearranging results Eq. (16). Sd Qst DG n Ta DG RT a ln aw ln aw jnw Qst n RT a Sd R 14 15 16

By plotting ln(aw) vs. 1/Ta for dierent constant moisture contents, the Sd gure can be calculated from the y-intercept (Sd/R). According to the compensation theory, the linear relationship between enthalpy and entropy for a specic reaction is given by (Eq. (17)) Qst T b S d DGb n 17

These modules have been used in the literature to evaluate the goodness of the t for dierent mathematical models. It is generally accepted that MRE-values below 10% give good t (Mulet et al., 2002; Kaymak-Ertekin & Gedik, 2004). 2.3. Thermodynamic properties The isosteric heat of sorption is a dierential molar quantity derived from the temperature dependence of the isotherm at a constant amount of sorbed water moles (nw) (Eq. (10)):   o ln p Qst 10 oT nw RT 2 a ClausiusClayperon equation for pure water is (Eq. (11)):   o ln p0 Lv 11 oT RT 2 a where p0 is the saturation pressure. Subtracting Eq. (11) from Eq. (10) (Eq. (12)):   o lnp=p0 Qst o ln aw =oT nw n2 oT RT a nw 12

The isokinetic temperature, Tb, represents the temperature at which all reactions in the series proceed at the same rate, and the free energy at Tb, DGb, provides a criterion to evaluate if water sorption is a spontaneous (DGb) or nonspontaneous process (+DGb). To test the validity of the compensation theory, the isokinetic temperature should be compared with the harmonic mean temperature (Thm) (Eq. (18)). Thus, a linear compensation pattern only exists if Tb 5 Thm. T hm Pni ni i1 1=T i 18

where ni is the total number of isotherms. Moreover, if Tb > Thm the process is enthalpy driven, while if the opposite condition is observed (Tb < Thm), the process is considered to be entropy-controlled (Telis et al., 2000). 3. Results and discussion The experimental results for the equilibrium moisture content of pineapple at each water activity for the dierent temperatures (from 5 to 45 C) are shown in Table 1. The equilibrium moisture content at each water activity represents the mean of three replications being the standard deviation of each experimental point within the range of 0.005 and 0.09 kg/kg dry matter. As it can be observed in Table 1, for equilibrium water content ranging from ca. 0.1 to ca. 0.75, an increase in temperature promoted an increase in water activity. On the opposite, for water contents higher than ca. 0.8, an increase in temperature was followed by a decrease in water activity. These desorption isotherms which crosses as the temperature increases are typical of fruits with high sugar content (Myhara & Sablani, 2001; Nicoleti, Telis-Romero, & Telis, 2001). The solubility of sugars augments with the tempera-

The net isosteric heat of sorption, at any value of nw, may be calculated from Eq. (12) by plotting the sorption isotherm as ln(aw) vs. 1/Ta and determining the slope which equals Qst =R. The isosteric heat of sorption (Qst) can be n calculated using Eq. (13), where Lv is the latent heat of vaporization of pure water

S. Simal et al. / Journal of Food Engineering 80 (2007) 12931301 Table 1 Equilibrium moisture contents (kg/100 kg dry matter) of pineapple at dierent temperatures T = 5 C aw 0.931 0.877 0.757 0.776 0.613 0.584 0.459 0.336 0.234 0.113 W (% dm) 102.86 72.15 42.92 44.46 27.34 24.96 20.34 16.92 14.52 10.90 T = 15 C aw 0.915 0.860 0.756 0.735 0.594 0.559 0.451 0.333 0.233 0.113 W (% dm) 100.60 69.21 42.45 39.09 25.74 23.88 19.96 15.98 13.27 10.56 T = 25 C aw 0.903 0.843 0.753 0.701 0.566 0.536 0.443 0.328 0.225 0.113 W (% dm) 98.95 63.63 41.28 34.90 21.94 21.02 17.34 13.33 11.22 9.58 T = 35 C aw 0.897 0.830 0.749 0.651 0.546 0.516 0.436 0.320 0.208 0.113 W (% dm) 95.49 61.12 41.40 29.45 20.99 18.27 14.81 12.18 10.22 8.97 T = 45 C aw 0.892 0.818 0.746 0.616 0.526 0.497 0.430 0.311 0.204 0.112

1297

W (% dm) 94.80 56.86 42.51 25.52 18.68 16.32 14.88 8.87 7.33 5.09

ture converting the crystalline sugar into sugar solution and thus, lowering the water activity. On the other hand, the case of water adsorption in pineapple at 20, 30, 40 and 50 C was studied by Hossain, Bala, Hossain, and Mondol (2001). These authors obtained isotherm curves which were sigmoid in shape and all curves following the same pattern, without crossings. 3.1. Fitting the GAB model to the experimental desorption data The experimental results for each temperature were tted to a straight-line according to Eq. (7), as aw/ [W(1 Kgaw)] vs. aw. The Kg value that best linearized this tting at every temperature (evaluated through the MRE of the predictions) was identied by using Mathematica software. Fig. 1 shows the representation of these results from 5 to 45 C and the obtained straight-lines. The other two constants, Wm and Cg, could be calculated from the slope and the y-intercept of each representation. Figures obtained for the three GAB parameters at each temperature, together with the correlation coecients and the mean relative errors, are shown in Table 2. Although the r2 and MRE values obtained could be considered adequate, these statistical parameters indicated that the linearity of the representations was better at lower temperatures. The constants variation with the temperature was the usual

0.10

for fruits with high sugar content, thus, the Kg parameter increased with the temperature meanwhile Wm and Cg decreased. The calculated monolayer moisture (Wm) (Table 2) decreased from 11.59 kg/100 kg dm at 5 C to 9.97 kg/ 100 kg dm at 45 C. Nicoleti et al. (2001) proposed a similar trend with the temperature despite their values being very dierent, from 81.79 kg/100 kg dm at 40 C to 6.37 kg/100 kg dm at 70 C. However, it should be pointed out that estimated Kg gures at 35 and 45 C were higher than 1, in opposition with the physical meaning of this parameter. Similar results were obtained when the aw range was restricted to 0.05 < aw < 0.8 (results not shown) and no solution could be obtained when the estimated Kg values were limited to be lower than 1. Kaymak-Ertekin and Gedik (2004) proposed Kg values for water sorption of grapes and apricots at 45 and 60 C higher than 1. Nicoleti et al. (2001) used the GAB equation to model the water sorption of pineapple at 40, 50, 60 and 70 C. The Kg values proposed by these authors at 60 and 70 C were also higher than 1 and the variation of Cg and Kg with the temperature could not be satisfactorily tted to the Eqs. (2) and (3), respectively. Using these results (Table 2), the Wo, DH, C0, DH1, K0 and DH2 parameters were calculated from the representation of the ln(Wm), ln(Cg) and ln(Kg) vs. the inverse of the absolute temperature. The correlations of the parameters with the temperature from 5 to 45 C are given by Eqs. (19)(21). The corresponding linear coecients of regression values could be considered acceptable, from

0.08 aw/[Kg(1-Kgaw)]

0.06
5C 15C 25C

0.04

Table 2 Figures obtained for the three GAB parameters at each temperature and the correlation coecients of the straight-lines T (C) 5 15 25 35 45 Kg 0.955 0.971 0.986 1.001 1.014 Wm (% dm) 11.59 11.32 10.83 10.17 9.97 Cg 61.57 37.86 14.30 12.72 5.46 r2 0.998 0.999 0.994 0.981 0.952 MRE (%) 2.2 1.2 4.3 6.8 6.1

0.02

35C 45C

0.00 0 0.2 0.4 aw 0.6 0.8 1

Fig. 1. Linear GAB plot (Eq. (7)) for pineapple at dierent temperatures.

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0.96 to 0.99, meanwhile the mean relative error in the case of the Cg parameter was considerably high.
C g 4:0 107 exp    43664:1 ; RT a r2 0:965; MRE 14:2%

 1105:7 K g 1:541 exp ; RT a  W m 3:204 exp

19
r2 0:999;  ; MRE 0:1%

20
r2 0:970; MRE 0:9%

2994:6 RT 273:16

21
These equations (Eqs. (19)(21)) were used together with the GAB equation (Eq. (1)) to simulate the moisture content for dierent water activities and temperatures and compared with the experimental ones. The mean relative error and the percentage of explained variance obtained through this comparison were of 4.3% and 99.6%, respectively. From these results it could be concluded that the GAB model could be adequately used to represent the water desorption of pineapple from 5 to 45 C. Nevertheless, the Kg values obtained by using this method are not in agreement with the theoretical basis. As it was mentioned above, the direct method to use the GAB model consists in the simultaneous identication of the six GAB parameters by using the experimental results of moisture contents at dierent water activity and temperatures. To carry out the identication, gures obtained through the linearization method were used as initial values of the parameters. The statistical analysis of the non-linear regression showed that the inuence of the temperature on the Wm parameter within the studied range was negligible (p < 0.05). The monolayer moisture content only varied from 11.99 kg/100 kg dm at 5 C to 11.91 kg/100 kg dm at 45 C. Thus, only ve GAB parameters were simultaneous identied (Wm, C0, DH1, K0 and DH2). Results are shown in Table 3 together with the standard error associated to the estimated parameters. The Kg values obtained through the direct method varied from 0.954 at 5 C to 0.989 at 45 C, which accomplishes with the thermodynamic theory. Furthermore, it can be observed that the mean relative error (5.0%) and the percentage of explained variance (99.8%) were similar

to those obtained with the method of estimating Kg by the linearization of the GAB model. From DH1 and DH2 gures showed in Table 3 and Eqs. (4) and (5), the heat of sorption of the monolayer was estimated, being of 97.0 kJ/mol (the latent heat of vaporisation of water used has been of 43.9 kJ/mol, the average value within the 545 C range of temperature). This value is of the same order to others proposed by dierent authors: 90.1 kJ/mol in chestnut (Vazquez et al., 2001); 50.6 kJ/ mol in morel (Mulet et al., 2002). Fig. 2 shows the representation of the experimental moisture content vs. the water activity for the dierent temperatures, from 5 to 45 C together with those simulated by using Eqs. (1)(3) and gures of Table 3 (direct method). It can be observed the satisfactory correlation between both experimental and simulated groups of data. In order to better evaluate the goodness of the model ts, Fig. 3 shows the representation of the residuals vs. the predicted variable. 3.2. Isosteric heat of sorption and dierential entropy The GAB isotherm and the parameters obtained through the direct method (Table 3) were used to estimate the net heat of sorption and the dierential entropy for

120 100 80 60 40 20 0 0 0.2 0.4 0.6 0.8 1

experiment al 5 C experiment al 15 C experiment al 25 C experiment al 35 C experiment al 45 C simulat ed 5 C simulat ed 15 C simulat ed 25 C simulat ed 35 C simulat ed 45 C

W (% dm)

aw

Fig. 2. Experimental equilibrium moisture data for pineapple at dierent temperatures (from 5 to 45 C) compared to predicted GAB isotherms using the direct method.

residuals

Table 3 Parameters values of the GAB model using the direct method Estimate Wm (kg/kg dm) C0 DH1 (J/mol) K0 DH2 (J/mol) MRE (%) = 5.0% 11.484 6.28 109 53820.6 1.276 672.1 Standard error 0.18 18.5 7761.9 0.02 37.2 % var = 99.8%

0
0 25 50 75 100

-2

-4

-6

simulat ed W

Fig. 3. Representation of the residuals vs. the predicted moistures using the direct method to estimate the GAB model parameters.

S. Simal et al. / Journal of Food Engineering 80 (2007) 12931301

0
experiment al predict ed

1299

differential entropy (kJ/mol K)

-1

ln(aw)

-2

5.0% 7.5% 10.0% 12.5% 15.0% 17.5% 20.0%

0.12

0.09

0.06

-3

0.03

-4

0.00 0 5 10 15 20 25 30 35

-5 0.0031

moist ure cont ent ( kg/ 100 kg dm)

0.0032 0.0033 0.0034 0.0035
-1

0.0036

0.0037

1/ Ta ( K )

Fig. 6. Dierential entropy for water desorption in pineapple as a function of the moisture content.

Fig. 4. Representation of the desorption isotherms as ln aw vs. 1/Ta for constant moisture contents. Data simulated using Eqs. (1)(3) and gures of Table 3.

pineapple. This method requires the measurement of sorption isotherms at more than two temperatures and assumes that the thermodynamic parameters are invariant with the temperature. The water activities for certain moisture contents were simulated at dierent temperatures. According to Eq. (16), simulated ln(aw) was plotted vs. 1/Ta. As it can be observed in Fig. 4, good linear correlations were obtained (r2 > 0.97). The net isosteric heat of desorption and the differential entropy were calculated from the slope and the yintercept of these straight lines, respectively. The obtained gures for these thermodynamic functions (Qst and Sd), n which have been represented vs. the pineapple moisture content in Figs. 5 and 6, respectively, are of the same order than those proposed by dierent authors for other food products (Mohamed et al. (2005), in bitter orange leaves; Falade, Adetunji, & Aworh (2003) in fresh and osmo-dried plantain slices; Kaymak-Ertekin & Gedik (2004), in grapes, apricots, apples and potatoes; McMinn et al. (2005), in starchy materials). Dierent equations have been proposed in the literature to describe the variations of the net isosteric heat of desorp-

tion of water and the dierential entropy with the moisture content. Hossain et al. (2001) for the adsorption of water in pineapple (only Qst ), and McMinn and Magee (2003) for n both the adsorption and desorption of water in potato, obtained good ts by using power-law equations meanwhile Kaya and Kahyaoglu (2005) expressed the relation of the Qst for pestil (grape leather) in the form of an expon nential function and a power-law equation in the case of Sd. The mathematical relationship which better represented the results obtained in this study is shown by Eqs. (22) and (23). This form of relationship, which derives from the Ratti model (Khallou, Giasson, & Ratti, 2000) has been previously used by dierent authors (Mulet et al., 2002) to represent the variation of Qst with the moisture content. n Qst 18:73 exp0:350W W 1:684 ; n S d 1:69 10
2

r2 0:997
2:804

22 23

exp0:493W W

r 0:998

50
desorpt ion, experiment al

desorpt ion, predict ed

40

30

20

10

0 0 5 10 15 20 25 30 35

moist ure cont ent ( kg/ 100 kg dm)

Fig. 5. Net isosteric heat of sorption for water desorption in pineapple as a function of the moisture content.

Figs. 5 and 6 also show the representation of the Eqs. (22) and (23), respectively. According to the important dierences between the isosteric heat and the dierential entropy and from a practical point of view, the heat involved in irreversible processes is small compared with the overall energy changes. The decrease in the net isosteric heats with the amount of water sorbed can be quantitatively explained by considering that at low moisture contents, sorption occurs on the most active available sites given rise to great interaction energy. As the moisture increases, water occupies the less active sites giving lower heats of sorption. It can be observed in Fig. 5 that the net isosteric heats (Qst ) at low n moisture contents are high, which indicates that the heat of sorption (Qst Lv ) amounted twice the heat of vaporizan tion of pure water (Lv). These initial heats may result probably from the chemisorption on polar groups. The value of Qst was higher than zero at every moisture contents but n tending to zero as the moisture content increased. Hossain et al. (2001) calculated the net isosteric heat of sorption from the adsorption isotherm of pineapple by using the modied BET model and proposed a mathematical equation of exponential shape to calculate the heat of adsorption of pineapple. This equation has been also

net heat of sorption (kJ/mol)

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40

30

20

10

st n

= 342.77 Sd + 1.323 r2 = 1.000

0 0.00

0.02

0.04

0.06

0.08

0.10

0.12

dif f erent ial ent ropy ( kJ/ mol K)

Fig. 7. Net isosteric heat/entropy relation for desorption in pineapple.

represented in Fig. 5. In this case, the values of Qst n observed by these authors were low, being close to the heat of vaporization of pure water when the moisture content increase. From moisture contents of ca. 30% onwards, both curves, the proposed by Hossain et al. (2001), obtained from adsorption data, and the equation proposed in this study, obtained from desorption data, were very similar. Dierent authors have determined the net isosteric heat of both adsorption and desorption for some products (McLaughlin & Magee (1998) for potatoes; Kaymak-Ertekin & Gedik (2004) for grapes, apricots, apples and potatoes; Mohamed et al. (2005) for bitter orange leaves; among others). In most cases, the desorption heats were signicantly higher than the adsorption ones at low moisture contents. On increasing moisture content the dierence tends to disappear. This indicated that the energy required in the desorption is higher than that in the adsorption process (Kaymak-Ertekin & Gedik, 2004). Nevertheless, no denite conclusions could be drawn about the nature of the hysteresis phenomena and its relationship with the ad-desorption heat curves. The plot of Qst vs. Sd for pineapple is shown in Fig. 7. A n linear relationship was exhibited with a correlation coecient r2 of 0.999. Thus, the results conrm the compensation theory. The isokinetic temperature (Tb) and free energy (DG), determined by linear regression were of 342.0 K and 1.67 kJ/mol, respectively. Dierent authors proposed isokinetic temperature values between 327 and 427.8 K for starchy food products (McMinn et al., 2005) being the DG gures positive in some products and negative in others. The calculated harmonic mean temperature was 297.5 K, value dierent to the isokinetic temperature value, conrming the suitability of the isokinetic theory for water sorption of pineapple. Furthermore, Tb > Thm, indicating an enthalpy controlled sorption process. 4. Conclusions The GAB model has been used to adequately represent the desorption data of pineapple at dierent temperatures ranging from 5 to 45 C. The two methods used to identify the model parameters allowed an accurate simulation of the experimental data (MRE < 5.0% and %var > 99.8%).

Although the method that uses the estimation of Kg through the linearization of the GAB model resulted in Kg values higher than 1, this transformed equation is useful as a means of obtaining initial estimates of the dierent terms that may be used in the direct nonlinear method. By using the GAB model and the ClausiusClayperon equation, the net isosteric heat of sorption and the dierential entropy have been calculated for dierent moisture contents. It was observed that the desorption heats of water in pineapple were signicantly higher than the adsorption ones (Hossain et al., 2001) at low moisture contents and very similar at moisture contents higher than 30% (d.b.). These thermodynamic properties tted adequately to the three-parameter Ratti model. Finally, the enthalpyentropy compensation theory was applied to sorption isotherms and plots of Qst vs. Sd provided the n isokinetic temperature, indicating an enthalpy controlled sorption process. Acknowledgements The authors would like to acknowledge the nancial support of CICYT (AGL2003-03889) and the Ministery of Education and Science of the Spanish Government. References
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