1 1

1IJFS 435-09

2CONFIDENTIAL
3This paper is under evaluation by the Italian Journal of Food Science. No part of it may be
4reproduced or used in any way.
5
6

7 EFFECT OF DRYING METHOD ON THE ADSORPTION ISOTHERMS AND

8 ISOSTERIC HEAT OF PERSIMMON PULP POWDER

10ABSTRACT

11

12Moisture equilibrium data of persimmon pulp powders with 50% of maltodextrin obtained by

13different drying methods were determined at 20, 30, 40 and 50 oC. The spray dryer provides a

14dry product with higher adsorption capacity than the other methods. The vacuum and freeze

15dried products presented the same adsorption capacity. The highest isosteric heat of sorption

16was observed for powders produced by spray drying. The isokinetic temperature (TB)

17calculated for persimmon pulp powder obtained by vacuum drying, spray and freeze drying

18were 541.4 K, 616.3 K, 513.2 K, respectively. The sorption process showed to be spontaneous

19and enthalpy controlled.

20

21Keywords: Freeze drying, Maltodextrin, Persimmon pulp powders, Spray drying,

22Thermodynamic properties, Vaccum drying, Water activity.

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11. INTRODUCTION

2 Persimmon was introduced into the Brazilian state of São Paulo in 1890 but only

3expanded its cultivation around 1920 with Japanese immigration. The persimmon growing

4area in Brazil is now around 8,309 ha, with a production of 164,849 t. São Paulo has the

5largest production areas followed by the state of Rio Grande do Sul. In recent years the

6persimmon area has increased approximately 10% and the trend is to continue crop

7expansion. The main cultivars are “Fuyu”, “Rama Forte”, “Giombo” and “Taubaté”. The

8market price for persimmon depends on the cultivar and can vary up to 60% with fruit size

9and up to 30% in fruit quality. In Brazil, most persimmon production is sold fresh in local

10markets, and in some growing regions persimmon is commercialized as dried fruit or vinegar.

11However, recently part of the production has been exported to Germany, Canada, Spain, The

12Netherlands and Portugal. The future challenges are to improve postharvest and storage

13techniques together with development of an adequate distribution system to meet the

14increased market demand. Although persimmon is highly perishable, the fruit can be stored

15for up to two months in regular air storage and three months in controlled atmosphere, but a

16rapid loss of fruit quality occurs during shelf life (NEUWALD et al., 2009).

17 A number of persimmon varieties present a marked astringency due to their highly

18soluble tannin contents, but this undesirable attribute can be removed by several methods,

19such as exposing the fruit to anaerobic conditions or to products of anaerobic respiration, or

20even by immersion in water at moderate temperatures (40 to 60°C). The relatively high

21temperatures commonly applied during convective drying also lead to tannin degradation,

22whereas sugars present in the fruit exude to the surface where they crystallize. The result is a

23sweet, tasteful, and non-astringent dried product, which is already traditionally consumed in

24oriental countries (NICOLETI et al., 2007)

25 Persimmons contain many health benefiting phyto-nutrients flavonoid poly-phenolic

26anti-oxidants like catechins and gallocatechins as well as important anti-tumor compound

 1 3

1betulinic acid. Catechins are known to have anti-infective, anti-inflammatory and anti-

2hemorrhagic (prevents bleeding from small blood vessels) properties.

3 Fresh permissions contain anti-oxidant compounds like vitamin-A, beta carotene,

4lycopene, lutein, zeaxanthin and cryptoxanthin. These compounds function as protective

5scavengers against oxygen-derived free radicals and reactive oxygen species (ROS) that play

6a role in aging and various disease processes, zeaxanthin, an important dietary carotenoid,

7selectively absorbed into the retinal macula lutea in the eyes where it is thought to provide

8antioxidant and protective light-filtering functions; thus, helps prevent "Age related macular

9disease"(ARMD) in the elderly.

10 The fruits are also very good source of vitamin-C, another powerful antioxidant

11(especially native Chinese and American persimmons; provide 80% of DRI). Regular

12consumption of foods rich in vitamin C helps body develop resistance against infectious

13agents and scavenge harmful, pro-inflammatory free radicals (NUTRITION AND YOU,

142009).

15 For preservation of the fruits and of their original components, special attention has

16been given to the development of adequate drying techniques. In addition to aggregating

17commercial value to the fruits, drying reduces wastes and post-harvest losses, and might

18allow their commercialization for extended periods of time, with minor dependence on

19seasonal conditions (MARQUES et al., 2007).

20 Powders obtained from pulp fruit represent an interesting market. This physical form

21provides a stable, natural and easily dosable ingredient which may used to impart color and

22taste to food products (BHANDARI et al., 1993).

23 Several types of dryers exist that may be used in drying of foods and they are selected

24in agreement with some characteristics of the process, such as: characteristics of the food, the

25easiness of the processing, the processed volume, the state and the conditions of the raw

26material, factors of economical origin and, mainly, the form that one want to give to the final
 1 4

1product. Particularly for drying of pastes, the diversity of physical characteristics of the

2materials takes to the inexistence of a pattern of recommended dryer (FREIRE, 1992). In

3accordance with Tsami et al. (1999), the final products characteristics such as water sorption,

4porosity and color depend on the drying method used. Several changes can occur during

5drying of a food, including changes in solubility, rehydration, and shrinkage, alteration in

6shape, size, porosity and density reduction, which can influence the adsorption capacity of the

7dried products.

8 The spray dryers are used in drying of solutions, suspensions, emulsions, pulps and

9pastes. When well driven, the dehydration by atomization of suspensions and nutritious pastes

10generates a product of larger nutritional value, stable and also versatile in its use (MASTERS,

111991). Spray-dried powders usually have a small particle size, 10–100 μm, with poor

12handling and reconstitution properties (FUCHS et al., 2006). The residence time of particles

13in the spray dryer does not usually exceed 30 seconds. Microstructure analyses reported by

14Cano-Chauca et al. (2005) showed that the powders of mango juices obtained through spray

15drying using maltodextrin, gum arabic, and waxy starch presented characteristics of

16amorphous particles.

17 Vacuum drying has been successfully applied to many fruits and vegetables. Vacuum-

18dried products are characterized by their better quality retention in relation to hot air drying at

19atmospheric pressure.

20 Freeze-drying is a technique that results in high-quality dehydrated products due to the

21absence of liquid water and the low temperatures required in the process. The solid state of

22water during freeze-drying protects the primary structure and minimizes changes in the

23product shape, with minimal reduction of volume, providing a dry product with porous

24structure (RATTI, 2001). During the freeze-dehydration of fruit juices and pulp, products with

25a high degree of amorphous sugars are obtained. This state favors the high hygroscopicity and

26higher adsorption capacity (CARLOS et al., 2005).

 1 5

1 Depending on the nature of food powder (crystalline or amorphous), the isotherms

2shape is different. Most food powders have complex structures, including potentially

3crystallisable solutes such as sugars, which show changes in crystallinity during the

4adsorption of water (MATHLOUTHI AND ROGÉ, 2003). Carlos et al. (2005) confirm this

5behavior relating that the sorption characteristics were correlated with the degree of sugar

6crystallization.

7 The plot of equilibrium moisture content of materials versus water activity at a given

8temperature is referred as a sorption isotherm. Water sorption isotherms are useful

9thermodynamic tools for predicting the interaction between food components and water.

10Sorption isotherms can also be used to investigate structural features of a food product, such

11as specific surface area, pore volume, pore size distribution and crystallinity. Such data can be

12used for selecting appropriate storage conditions and packaging systems that optimize or

13maximize retention of aroma, color, texture, nutrients and biological stability, and optimizes

14the drying or rehydration conditions of a product (RIZVI, 1995).

15 Determination of the heat of sorption was the aim of several previous studies. ItS

16knowledge is essential for modeling of various food processes and food storage. In addition, it

17can be used to estimate the energy requirements of food drying and also provides important

18information about the state of water in food products (KAYA AND KAHYAOGLU, 2005).

19 The adsorption isotherms of fruits and vegetables have been studied. Debnath et al.

20(2002) reported the moisture sorption of onion powders obtained by freeze dryer and vacuum

21shelf drying. Costa et al. (2003) determined adsorption isotherms for beetroot, pumpkin and

22carrot, which were obtained in powder form by using a spouted bed dryer. Alexandre et al.

23(2007) showed the moisture adsorption isotherms of red Brazilian cherry powder produced

24using the foam-mat drying process. Gabas et al. (2007) and Martinelli et al. (2007)

25determined the adsorption isotherms of vacuum dried pineapple pulp powder and lemon pulp

26powder, respectively.
 1 6

1 The enthalpy-entropy compensation or isokinetic theory was originally applied by Bell

2(Bell, 1937) and investigates physical and chemical phenomena involved in water sorption

3(Aguerre et al., 1986; Madamba et al., 1996). Changes in enthalpy (H) may provide a

4measure of the energy changes occurring upon mixing water molecules with sorbent during

5sorption processes. Entropy changes (S) may also be associated with the binding or

6repulsive forces in the system. Gibbs free energy (G) may be indicative of the affinity of

7sorbents for water and provides a criterion as to whether water sorption occurs as a

8spontaneous (-G) or non-spontaneous process (+G). Aguerre et al. (1986) applied

9enthalpy-entropy compensation to derive a two parameter sorption equation which takes into

10account the effect of temperature on water sorption isotherms of some food products.

11 Liu and Guo (2001) found that, for compounds undergoing a defined chemical

12reaction, parallel changes in enthalpy and entropy are usually found, i.e. the stronger the

13intermolecular interaction, or bonding (enthalpy related), the greater the reduction in the

14configurational freedom and hence, the greater order in the system (entropy related). This is

15the enthalpy-entropy compensation effect.

16 Since adsorption isotherms are generally affected by drying methods, it is also useful

17to determine and compare adsorption isotherms and thermodynamics properties of persimmon

18pulp powder processed by different drying methods. The objective of this study is to analyze

19the effects of different drying methods on sorption properties of persimmon pulp powder.

201.1 MATHEMATICAL DEVELOPMENT

21 The Guggenheim, Anderson and de Boer (GAB) isotherm equation has been widely

22used to describe the sorption behavior of foods (MAROULIS et al., 1988; IGLESIAS AND

23CHIRIFE, 1995). It is recommended to describe isotherms and it has been extensively used

24for foodstuffs, especially for fruits (LOMAURO et al., 1985; GABAS et al., 2000; TELIS et

25al., 2000).
 1 7

1 Having a reasonable small number of parameters (three), the GAB equation has been

2found to represent adequately the experimental data in the range of water activity of most

3practical interest in foods, i.e., 0.10±0.90 and is a relatively simple model with parameters

4that have a physical meaning.

5 IT IS MATHEMATICALLY EXPRESSED AS (RIZVI, 1995):

 C  1 K a w X m K aw X m
X   (1)
1   C  1 K a w 1  K aw
6where: aw is the water activity, Xm is the moisture content (dry basis) corresponding to an

7adsorbed monolayer (BET) and C and K are the GAB model constants related to the

8temperature effect.

9 The isosteric heat of sorption (q st) is defined as the difference between the total heat of

10sorption (Qst) and the heat of vaporization of water. It can be determined from the following

11equation, which is derived from the Clausius-Clapeyron equation (RIZVI, 1995):

 ln  a w  Q st   q
   st (2)
 1 T  X
R R
12where: qst is the isosteric heat of sorption (kJ/mol), Q st is the total heat of sorption (kJ/mol), 

13is the heat of condensation of pure water (kJ/mol), R is the universal gas constant (8.314

14J/mol K) and T is the absolute temperature (K).

15 The isosteric heat of sorption is a differential molar quantity derived from the

16temperature dependence of the isotherms. This approach assumes that the isosteric heat is

17invariant with temperature and the application of this method requires the measurement of

18sorption isotherms at two or more temperatures (MCLAUGHLIN AND MAGEE, 1998).

19 The change in molar differential entropy of sorption can be calculated by means of

20Gibbs-Helmholtz equation as used by (RIZVI, 1995):

H  G
S  (3)
T
21where the free energy (G) is calculated as:
 1 8

G  RT ln a w (4)
1 The effect of a change in water sorption on free energy is usually accompanied by

2changes on both the enthalpy and the entropy. Substituting equation (4) in (3) and rearranging,

3it results in:

H S
ln a w   (5)
RT R
4 Thus, the differential enthalpy of sorption and entropy can be calculated from equation

5(5) by plotting ln (aw) versus 1/T, for specific moisture content, the slope of the regression line

6(- H R ) providing a measure of enthalpy of sorption. This procedure is repeated for many

7values of moisture content, in order to detect the dependence on the moisture content (Tsami,

81991). The differential entropy of sorption, at specific moisture content, was calculated from

9the intercept ( S R ) obtained from Equation 5. Several researchers have used the above

10procedure for the determination of qst. Tsami (1991) calculated the heat of sorption of water

11for dried fruits, Kiranoudis et al. (1993) for some vegetables, Madamba et al. (1996) for

12garlic, and McLaughlin and Magee (1998) for potatoes.

13 A plot of H versus S from the values of equation (5) for the persimmon pulp powder

14can be evaluated for each set of sorption data. These values can be correlated according to the

15following equation:

H  TB  S G B (6)

16

17 Isokinetic temperature (TB) has an important physical significance as it represents the

18temperature at which all reactions in the series proceed at the same rate. Since there is a high

19degree of linear correlation between enthalpy and entropy, the compensation theory was

20assumed to be valid for sorption (Madamba et al., 1996). Krug et al. (1976) recommended a

21statistical analysis test for the compensation theory, which involves comparing the isokinetic

22temperature with the harmonic mean temperature Thm as defined by:

 1 9

n
Thm  n (7)
 1 T 
i1
1

22. MATERIALS AND METHODS

32.1 Raw material

4 Samples of persimmon (Diospyros kaki) with moisture content of 83 to 87% (wet

5basis) were obtained at the local market (São José do Rio Preto, SP, Brazil) and stored at 7 oC

6prior to their use. A batch of persimmon pulp was prepared in a pilot plant finisher and sieved

7through a 1.6 mm-mesh.

8 An aqueous solution with 50% solids (mass basis) was prepared by dispersing

9commercial maltodextrin MOR-REX® 1910 (Corn Products Brazil) in distilled water at 40 oC,

10using a mechanical stirrer. This solution was added to persimmon pulp and the mass ratio

11between maltodextrin solution and pulp was 1.10 kg maltodextrin/1kg soluble solids (50%

12maltodextrin).

13

14

15

162.2 Drying methods

172.2.1 Spray dryer

18 The spray dryer (model SD 5.0, Labmaq do Brazil LTDA) operates concurrently and

19has a spray nozzle with an orifice of 2 mm in diameter. The inlet air temperature was about

20140 ºC and the outlet air temperature was about 102 ºC. The liquid feed to the dryer was

21between 1 and 1.5 L/h. The drying air flow was about 12 m3/h (MARTINELLI, 2008). The

22experiments were performed at constant process conditions. The dry powder separated from

23inert particles by attrition was carried out of the drying chamber along with the exhausted air,

24and collected in a cyclone.

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1 The material obtained was placed into plastic bags, which were stored in a desiccator

2containing silica gel until posterior utilization.

42.2.2 Freeze dryer

5 The persimmon pulp was put into three stainless steel trays and frozen before drying in

6a freezer (LIOTOP, FV500) at -40º C. Freeze-drying tests were performed in a freeze-dryer

7model L101 (LIOBRAS, Brazil) with vacuum chamber total pressure and temperature equal

8to 500 Hg and −45 ◦C, respectively, during 48 hours.

9 The freeze-dryer is constituted of a cylindrical drying chamber of transparent acrylic

10of 35 cm covered with a stainless steel top with eight silicone faucets to fit the glass bottles

11with round bottom (vacuum relief system). To connect the bottles to the faucets it has a silica

12adapter and a stainless steel pipe that makes the linking between faucets and bottle. Inside of

13the drying chamber it has a shelf that serves of support for four stainless steel trays. The

14samples can be placed in the trays or in the glass bottles. The vacuum is produced through a

15vacuum pump that is connected to the freeze-dryer through a hose. At the end of the process,

16the dried product was removed and ground in a hammer mill.

172.2.3 Vacuum chamber dryer

18 The samples of pulp were dried on a stainless steel tray inserted in a vacuum chamber

19(MARCONI, MA 030) at 60ºC during 48 h (GABAS et al., 2007). The dried product was

20ground in a hammer mill.

21

222.3 Sorption isotherms

23 Equilibrium moisture contents of pulp powder at several water activities were

24determined by the static gravimetric method (JOWITT et al., 1983) at 20, 30, 40 and 50 ºC.

25Ten saturated salt solutions (NaOH, LiCl, KC H O , MgCl , K CO , MgNO , NaNO , NaCl, KCl
2 3 2 2 2 3 3 2
 1 11

1e BaCl ), were prepared corresponding to a range of water activities from 0.06 to 0.90. Each
2

2solution was transferred into separated jars in a sufficient quantity to occupy a space of about

31.5 cm depth at the jar bottom. Triplicate samples of around 1 g of persimmon powder were

4weighed into small plastic receptacles and placed on tripods in the jars, which were then

5tightly closed and placed in a temperature-controlled chamber. The required equilibration time

6was 4 to 5 weeks, based on the change in sample weight expressed on a dry basis, which did

7not exceed 0.1% (0.001 g/g dry solids). The equilibrium moisture content was determined by

8the gravimetric method, in a vacuum oven at 60oC for 48 h (AOAC, 1990).

103. RESULTS

113.1 Sorption Isotherms

12 The experimental moisture sorption data determined at 20, 30, 40 and 50 ºC for

13persimmon pulp powder with 50% of maltodextrin obtained using different dryers are shown

14in Table 1. The moisture content for each level of water activity represents the mean value of

15three replicates.

16 The results of the fitting procedure of the GAB model to the experimental data of

17equilibrium moisture content at different temperatures activities are presented in Table 2,

18which shows the values of the fitting parameters calculated by non-linear regression. The

19adequacy of GAB models was evaluated by the determination coefficient (R 2) and the

20magnitude of the Sum of Square of Residuals (SSR).

21 The obtained isotherms are of type III, according to Brunauer´s classification, for most

22of the examined temperatures and all drying methods. The sorption isotherms demonstrate an

23increase in equilibrium moisture content with increasing water activity (Figure 1).

24 The typical effect of the temperature during equilibration time on the isotherms is

25shown for powders produced in the spray dryer in Figure 1. This shape of the curves is

26characteristic of foods with high sugar contents, which sorbs small amounts of water at low
 1 12

1water activity and large amounts of water at high water activity. The explanation for the

2nature of the isotherms may be that at low water activities, physical sorption on strongly

3active sites occurs, since water can be sorbed only to surface – OH sites of crystalline sugar

4(GOULA et al., 2008).

5 The effect of the equilibration temperature on the sorption isotherms is of great

6importance given that foods are exposed to a range of temperatures during storage and

7processing, and water activity changes with temperature for the same moisture content

8(GOULA et al., 2008). The equilibrium moisture content tends to decrease with increasing

9temperature at constant water activity. The extent of the decrease depends on the nature or

10constitution of the food (RIZVI, 1995). For persimmon pulp powder this behavior was not so

11pronounced, independently of the dryer used to obtain the powder. This result was in

12accordance with results for passion fruit pulp obtains by different dryers (PEDRO, 2009).

13Goula et al. (2008) reported that for spray dried tomato pulp the temperature effect was not

14dependent on water activity and probably this might be due to the fact that tomato powder

15contains high levels of protein and insoluble solids. Gabas et al. (2007) compared isotherms

16of vacuum dried pineapple pulp powder and Martinelli et al. (2007) compared isotherms of

17vacuum dried lemon pulp powder, both determined between 20 and 50oC, and also detected

18only a small dependence of sorption data on temperature.

19 A marked intersection of the isotherms and the inverse temperature effect were

20observed for persimmon pulp powders above 0.8. Some studies have reported this inversion

21in the temperature effect at water activities above 0.7 for products with high sugar content,

22such as fruits (TELIS-ROMERO et al, 2005; TSAMI et al., 1990), which can be explained by

23an increase in sugar solubility in water caused by increasing temperature.

24 The parameters of GAB models are presented in Table 2. The value of the monolayer

25moisture content (Xm) is of particular interest, since it indicates the amount of water that is

26strongly adsorbed to specific sites at the food surface and it’s considered as the optimum
 1 13

1value to assure food stability. Below this water content level, rates of deteriorative reactions,

2except oxidation of unsaturated fats, are minimal (GOULA et al., 2008). Estimated values for

3Xm for persimmon pulp powders were found to be lesser than values available for other

4fruits, which vary between 10 and 15% (dry basis), reported by Kiranoudis et al. (1993).

5Values of Xm obtained by vacuum and freeze drying were smaller than for spray dried

6persimmon. The monolayer values for persimmon pulp powder obtained by different dryers

7showed no temperature dependence.

8 The parameter C showed distinct trends for different drying methods. For vacuum and

9freeze dried materials, values of C decreased as temperature increased. For spray dried

10products, values C showed no clear temperature dependence. In accordance with Goula et al.

11(2008) the values for K were smaller than 1 as dictated by the GAB equation. The parameter

12K was practically unaffected by the drying method.

13 The effect of dryer types on the sorption isotherms is shown in Figure 2, for 20 ºC, and

14in Figure 3, for 50ºC. For both temperatures the effect of drying method on isotherms

15behavior was the same.

16 The spray dryer provides a dry product with higher adsorption capacity than the other

17methods. Freeze and vacuum dried products showed the same adsorption capacity. These

18drying methods present some similarities. Both are based on drying in the absence of air,

19providing products with very porous structure. Nevertheless, the adsorption capacity might

20not be directly related with porosity, since in order to obtain powders, the products resulting

21from freeze and vacuum drying processes were ground. This factor could also be responsible

22for the similar adsorption capacity observed between the powders obtained by these two

23drying methods.

24 Tonon et al. (2008) related that the materials produced by spray drying showed

25spherical particles. The spherical particles provide a larger surface area than irregular shape
 1 14

1particles (for the same particle volume). Probably this is the reason for highest adsorption

2capacity of spray dried materials.

43.2. Sorption thermodynamic property

53.2.1 Isosteric heat of sorption

6 The dependence of the isosteric heat of sorption on moisture content for persimmon

7pulp powder with 50% of maltodextrin is shown in Figure 4. The results illustrate a

8progressive increase of the sorption heat in relation to the decreasing moisture content. Al-

9Muhtaseb et al. (2004) stated that this may be possibly due to the fact that, at the initial stages

10of sorption (low moisture content), there are highly active polar sites available on the surface

11of the food material, which are covered with water molecules to form a monomolecular layer.

12This results in stronger water-solid interactions. Goula et al. (2008) related that the main

13water-adsorbing constituents in foods are various polymers (proteins, starch, cellulose,

14hemicellulose, etc.) and sugars. The different polar groups of the polymers provide

15energetically different sites for sorption. As the water content increases, the covering of less

16active adsorption sites and the formation of multilayers is manifested by the decrease in the

17heat of sorption (PÉREZ-ALONSO et al, 2006).

18 In almost the whole range of moisture content the qst values corresponding to powders

19produced by spray drying were the highest ones. This suggests that the spray-dried product

20has more surface polar sites than products obtained by the other drying methods. These results

21are in accordance with results for passion fruit pulp powders obtain by different dryers

22(PEDRO, 2009). The elevated heats of sorption of water at low moisture contents are an

23indication of strong water-food component interactions in the fruit.

24 Values of qst were correlated by Equation (8) (TSAMI et al., 1990), resulting in the

25constants q0 and X0, as well as in the values of the determination coefficient (R2), which are

26shown in Table 3. The fit determination coefficient was found to be satisfactory (R2 > 0.94).
 1 15

 X 
q st  qo * exp  (8)
 Xo 
1

23.2.2 Enthalpy-entropy compensation theory

3 The plots of differential enthalpy (H) and differential entropy (S) of sorption for

4persimmon pulp powder obtain by different dryers was shown in Figure 5. Linear

5relationships were exhibited. There is a high degree of linear correlation between enthalpy

6and entropy, and the compensation theory was assumed to be valid for adsorption of

7persimmon pulp powder.

8 The parameters TB and ΔGB were calculated by linear regression of equation (6). The

9isokinetic temperature for the sorption of persimmon pulp dehydrated is shown in Table 4.

10The isokinetic temperatures for persimmon pulp powder obtained by vacuum and freeze-

11drying are lower than persimmon pulp dried by spray drying. McMinn et al. (2005) related

12that isokinetic temperature is observed to vary with material composition, and is little to be

13dependent on whether the material is undergoing adsorption or desorption. There is not much

14information about the isokinetic temperature for fruit pulp powder in literature. Gabas et al.

15(2000) reported isokinetic temperatures for the desorption process of plum pulp of 473.1 K,

16and Telis et al. (2000) obtained approximately the same isokinetic temperature for persimmon

17pulp desorption 475 K. Pérez-Alonso et al. (2006) determined the isokinetic temperature for

18the adsorption and desorption of mango to be 463 K and 501 K, respectively.

19 The harmonic mean temperature (Thm) was calculated from equation 7. According to

20Krug et al. (1976), a linear chemical compensation pattern exists only if T B ¹ Thm. To test the

21validity of the compensation theory the isokinetic temperature was compared with the

22harmonic mean temperature (Thm) (MCMINN et al., 2005). The harmonic mean temperature

23was calculated as 307.74 K, a value significantly different from all values of T B described

24above, thus confirming the isokinetic theory for persimmon pulp powder sorption. According
 1 16

1to Leffler (1995), if TB > Thm the process is enthalpy driven and if the opposite condition is

2observed (TB < Thm), the process is considered to be entropy controlled. Thus the process of

3sorption for persimmon pulp powder obtains by vacuum, spray and freeze drying enthalpy-

4driven.

5 Telis et al. (2000) suggest that the process sorption for persimmon pulp may be

6enthalpy-controlled. Gabas et al. (1999) reported an enthalpy-controlled mechanism in the

7sorption isotherms of grapes and plums. McMinn et al. (2005) suggest that sorption behavior

8of starchy materials was enthalpy-controlled. Most sorption processes can therefore be

9considered to be enthalpy-controlled.

10 For persimmon pulp powder obtained by vacuum, spray and freeze dryer the process of

11sorption is spontaneous for determining whether water sorption occurs as a spontaneous

12(G<0).

13 McMinn et al. (2005) reported a spontaneous sorption isotherm for starch materials,

14however McMinn et al. (2007) suggest that sorption in oatmeal and oat flakes was non-

15spontaneous.

16

174. CONCLUSIONS

18 The adsorption isotherms for samples of persimmon pulp powders with 50% of

19maltodextrin obtained by vacuum, spray and freeze drying presented type III behavior,

20according to Brunauer’s classification. The drying method significantly affects the sorption

21capacity of the dry product. The spray dryer provides a dry product with higher adsorption

22capacity than the other studied methods.

23 The isosteric heat of sorption increased with decreasing of moisture content. In almost

24the whole range of moisture content, the values of the isosteric heat of sorption corresponding

25to powders produced by spray drying were the highest ones.

 1 17

1 The isokinetic temperature (TB) calculated for persimmon pulp powder obtained by

2spray drying was higher than for pulp powder obtained by vacuum and freeze drying. The

3enthalpy-entropy compensation theory was successfully applied to water sorption of

4persimmon pulp powder, suggesting that this process occurs by enthalpy-controlled

5mechanisms and is spontaneous.

75. REFERENCES

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4
5
6
7FIGURE LEGENDS
8
9 Figure 1: Influence of temperature on sorption isotherms of persimmon pulp powder with

1050% of maltodextrin 10 DE dried in spray dryer.

11Figure 2: Influence of different drying methods on the sorption isotherms of persimmon pulp

12powder determined at 20ºC.

13Figure 3: Influence of different drying methods on the sorption isotherms of persimmon pulp
14powder determined at 50ºC.
15Figure 4: Influence of drying methods on sorption isosteric heat of persimmon pulp powders.
16
17Figure 5: Enthalpy-entropy relationship for water sorption in persimmon pulp dried by
18vacuum, spray and freeze drying.
1 24

1Table 1: Experimental equilibrium moisture contents (dry basis) for persimmon pulp powders with 50% of
2maltodextrin 10 DE.
Vacuum dryer Spray dryer Freeze dryer
Xeq Xeq Xeq
Temperature (ºC) aw
(% dry basis) (% dry basis) (% dry basis)
0.070 0.048 0.076 0.049
0.113 0.056 0.094 0.053
0.246 0.081 0.123 0.081
0.331 0.089 0.138 0.088
20 0.446 0.108 0.167 0.109
0.547 0.125 0.202 0.124
0.655 0.167 0.252 0.172
0.754 0.221 0.347 0.219
0.853 0.311 0.518 0.300
0.907 0.378 0.544 0.400
0.069 0.041 0.067 0.041
0.112 0.048 0.080 0.048
0.223 0.083 0.132 0.081
0.324 0.082 0.137 0.080
30 0.439 0.101 0.168 0.102
0.526 0.110 0.184 0.111
0.635 0.183 0.290 0.183
0.756 0.211 0.348 0.211
0.835 0.264 0.438 0.266
0.9 0.398 0.703 0.395
0.066 0.036 0.060 0.037
0.111 0.047 0.074 0.046
0.206 0.067 0.107 0.066
0.319 0.081 0.127 0.078
40 0.432 0.100 0.164 0.100
0.506 0.111 0.178 0.111
0.615 0.147 0.242 0.148
0.753 0.215 0.345 0.214
0.82 0.266 0.422 0.265
0.893 0.361 0.603 0.359
0.059 0.033 0.053 0.034
0.110 0.041 0.067 0.040
0.189 0.058 0.095 0.057
0.314 0.070 0.113 0.066
50 0.432 0.101 0.162 0.102
0.489 0.107 0.173 0.106
0.599 0.149 0.242 0.150
0.746 0.206 0.333 0.205
0.809 0.254 0.412 0.253
0.884 0.376 0.609 0.373
3
 1 25

1
2Table 2: Estimated GAB parameters at different temperatures for powders obtained by
3different drying methods.
Temperature
Parameter
20 ºC 30 ºC 40 ºC 50 ºC
Vacuum Dryer
C 22.326 23.709 14.710 13.609
K 0.900 0.927 0.913 0.941
Xm 0.070 0.064 0.067 0.063
R2 0.997 0.985 0.999 0.997
SSR 0.235E-03 0.169E-02 0.678E-04 0.256E-03
Spray Dryer
C 18.047 30.997 16.387 13.732
K 0.8787 0.949 0.925 0.941
Xm 0.118 0.100 0.105 0.102
2
R 0.982 0.987 0.999 0.997
SSR 0.467 E-02 0.446 E-02 0.259E-03 0.671E-03
Freeze Dryer
C 26.593 21.835 14.192 13.609
K 0.916 0.924 0.912 0.941
Xm 0.067 0.065 0.067 0.063
R2 0.998 0.986 0.999 0.997
SSR 0.193E-03 0.151 E-02 0.788E-04 0.256E-03
4
5
6
7Table 3: Estimated parameters of the empirical Equation 5 for samples dried by different
8methods.
Drying Method q0 (kJ/mol) X0 (dry basis) R2
Vacuum dryer 27.263 0.058 0.967
Spray dryer 18.755 0.113 0.940
Freeze dryer 33.429 0.049 0.973
9
10
11
12
13
14Table 4: Isokinetic temperatures and Gibbs free energy for persimmon pulp dried by vacuum,
15spray and freeze drying.
16
Drying Method TB (K) GB (kJ/mol)
Vacuum dryer 541.409 -0.796
Spray dryer 616.340 -1.631
Freeze dryer 513.215 -0.725
17