Kinetics of the Dehydration of Onion by Immersion Cintica da Desidratao por Imerso de Cebola

AUTORES AUTHORS
Alessandra Faria BARONI Mriam Dupas HUBINGER
Departamento de Engenharia de Alimentos - Faculdade de Engenharia de Alimentos - Universidade Estadual de Campinas - Brazil - Box. 6121 - CP 13083-970 e-mails: baroni@ceres.fea.unicamp.br mhub@ceres.fea.unicamp.br

SUMMARY
In this work, small squares of onion (Allium cepa L., var. Baia Piriforme) were submitted to dehydration by an immersion process in salt solutions. Different concentrations of sodium chloride (5, 10 and 15% w/w) and temperatures (22, 30 and 40oC) were tested to evaluate the kinetics, and the profiles of moisture content and salt penetration were constructed. After 1 hour of dehydration, few changes in moisture removal and solid gain were observed. The minimum water content obtained in a 4h process was 76% for the sample immersed in 15% NaCl at 40oC, with a solid uptake of 9%. Effective diffusion coefficients were obtained using Cranks solution to Ficks diffusion law, using plane sheet geometry bidimensional mass transfer, considering the skin of the product. The results showed that the higher the temperature and salt concentration, the higher the effective diffusion coefficient. The Deff values obtained varied from 0.9 to 3.73 .10-9m2/s for water and from 0.38 to 1.42 .10-9m2/s for salt. It was also observed that the concentration of the salt solution was more important than the temperature in the process mass transfers.

RESUMO
Neste trabalho, pedaos de cebola (Allium cepa L., var. Baia Piriforme) no formato de pequenos quadrados foram submetidos desidratao osmtica, em solues salinas de diversas concentraes (5, 10 and 15% p/p) e temperaturas (22, 30 e 40oC). Curvas da cintica da desidratao, bem como da impregnao de sal foram construdas. No incio do processo, a sada de gua ocorre mais rapidamente que a entrada de sal, porm aps 1 hora, poucas alteraes no teor de umidade e de sal foram observadas. O menor teor de umidade obtido, 76%, foi para a amostra imersa na soluo 15% NaCl a 40oC, com o ganho de sal total de aproximadamente 9%. Coeficientes de difuso aparentes foram obtidos por meio da soluo obtida por CRANK (1975) para a Lei de Fick da difuso, usando geometria de placa plana bidimensional, considerando a pele que cobre o pedao da cebola como resistncia transferncia de massa. Os resultados mostraram que quanto maior a concentrao e a temperatura, maior foi o coeficiente de difuso aparente. Os valores da difusividade mssica variaram de 0,9 a 3,73.10-9m2/s para a gua e de 0,38 a 1,42.10-9m2/s para o sal. Observou-se tambm que a concentrao parece exercer uma influncia maior que a temperatura nas trocas de massa durante o processo.

PALAVRAS-CHAVE KEY WORDS

Cebola; Desidratao osmtica; Coeficiente de difuso mssica / Onion; Osmotic dehydration; Mass diffusion coefficient.

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Recebido / Received: 04/11/1998. Aprovado / Approved: 14/06/1999.

A. F BARONI . M. D. HUBINGER

Kinetics of the Dehydration of Onion by Immersion

1. INTRODUCTION
In tropical countries, many fruits and vegetables are lost, due mainly to a lack of technical support for the processing of these products to guarantee a longer shelf-life. The development of simple, low-cost technologies to preserve such foodstuffs is necessary to keep these countries in the competitive market. Onion constitutes one of the most consumed vegetables in Brazil. Fresh onions are mainly used for culinary purposes to improve the flavor of a large number of food products during cooking although dehydrated onions are also used as an ingredient in soups, sauces and meal mixes. In the past few years, the national production of onions has increased more than the consumption and efforts to guarantee prices and protect farmers from bankruptcy have led large amounts of bulbs to dumping grounds. Losses are heavy. Dehydration by immersion of cut onions could be employed in an attempt to preserve this supply of onions for later use. The major factor contributing to the deterioration of plant tissue products is water. This water controls many physicochemical reactions and biological changes, hence being responsible for the quality and durability of foodstuffs. The removal of water or making it unavailable for reactions, is a key factor in preservation. One technique which combines water removal and impregnation with a solute, causing a decrease in water activity, is the process of dehydration by immersion (DI), also known as osmotic dehydration. This consists of the removal of water from cellular bodies (such as fruits and vegetables), through immersion of these products in a concentrated aqueous solution. The water flow caused by differences in activity inside and outside the vegetable cell, results in two major changes: water leaving the cell and penetrating solute. A third flow of lower intensity is that of natural substances from inside the product, such as sugars, organic acids and minerals. Dehydration by the immersion process combines dewatering and a formulation effect, improving some nutricional, organoleptic and functional properties of the product. However it does not generally produce stable products, a second step being necessary, such as convective drying, freezing or pasteurization. (LENART, 1996, BARONI, HUBINGER, 1998). Many researchers have studied different aspects of the process of dehydration by immersion, including solute type concentration, time and temperature of contact as well as the final product quality (LERICI et al., 1985). There are also many comprehensive reviews (LE MAGUER, 1988, RAOULT-WACK, 1994, TORREGIANNI, 1993, LENART, 1996). The rate of water removal depends on various factors and processing parameters. In general, the greater the concentration of solute and the temperature of processing, the greater the loss of water; temperatures over 50oC, however, may cause undesirable browning and flavor reactions (PONTING et al., 1966, PONTING, 1973). Mathematical modeling of diffusion mass transfer of the dehydration process is based on Ficks law of diffusion and on analytical solutions developed by CRANK (1975). HAWKES, FLINK (1978) were the pioneers in describing the osmotic dehydration

of apples in salt and sugar solutions. They analyzed experimental data through an empirical equation which related the solute concentration with the square root of soaking time. The proportionality constant was considered to be a coefficient of mass transfer. This mathematical solution, also considered to be the first term in the series of Ficks law solution, was used by many authors (TOMASICCHIO et al., 1986, BISWAL et al., 1991). Studies on mathematical modeling of DI using other geometric shapes have also been presented in the literature (RASTOGI, RAGHAVARAO, 1994, MAURO, MENEGALLI, 1995). Many studies report values of effective diffusion coefficients, but most of them are performed using a sugar solution (BERISTAIN et al., 1990, AZUARA et al., 1992, HOUGH et al., 1993, LAZARIDES, MAVROUDIS, 1996). Few research workers have reported effective diffusion coefficient values from DI in salt-only solutions (WANG, SASTRY, 1993). The present paper investigates the use of such salt-only solutions for the dehydration of onion pieces and determines the kinetics of mass transfer as well as the influence of sodium chloride concentration and temperature on the water removal rate and final salt content; effective diffusion coefficients are also presented.

2. MATERIALS AND METHODS

2.1 Raw material In Brazil, onions of the variety Baia Piriforme are those most widely consumed by industry, moreover good quality ones are available for most of the year. Hence, onions of this variety were used for the present study. Mature bulbs were purchased at a local market of uniform size, appearance and hardness and kept under refrigeration (4oC) until used. The onions were peeled manually and the layers cut, transversally to the longitudinal axis of the onion, in pieces of approximately 0.8 x 0.8 x 0.2cm, for the dehydration tests.

2.2 Dehydration by Immersion (DI) Sodium chloride solutions were used as the osmotic agent because this provides a taste compatible with industrial vegetable applications, as well as great ability in lowering the water activity. The raw unblanched material was soaked in salt solutions of different concentrations (5, 10 e 15%w/w) at three different temperatures 22oC, 30oC and 40oC, maintaining in each case a solid to liquid ratio of 0.1g/kg. After various time periods, samples were removed and gently blotted with paper to remove surface moisture. The salt concentration in immersed samples was determined by Mohrs titration method (RANGANNA, 1986)

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A. F BARONI . M. D. HUBINGER

Kinetics of the Dehydration of Onion by Immersion

and the water content measured gravimetrically by vacuum oven drying (12h, 60oC, 25mmHg). Before each test, the moisture content and salt content of raw material was determined. Weight loss was determined by weighing both before and after the process. Mean values are presented for three replicates with a standard deviation of 0.5%. Experimental results are expressed in terms of water content (WC), salt content (SC), and water loss (WL):

To solve this equation, certain assumptions are made: The onion slices are homogenous. The external concentration remains constant. Resistance to mass transfer at the minor surfaces is negligible in comparison to internal diffusion resistance. Unsteady state. To solve equation 4 the solution suggested by Neumann (CRANK, 1975), product of the solutions of two plane sheets, is applied: f ( x , y , t )= ( x , t ). ( y , t ) (5)

WC = SC =

Mw MT Ms MT

(1)

(2)

The solution for a single plane sheet is given by CRANK (1975):

( x, t ) = ( y, t ) =
Deff ( 2n + 1) 2 2 t Mi 8 exp = 1 2 2 M eq 4 L2 n = 0 ( 2n + 1)

WL =

M T o .WCo M T t .WCt M T 0 .WCo

(3)

(6)

where Mw is the water mass in the onion slices, MT the total mass and Ms the salt mass. The subscripts o and t refer to initial and sampling times during the process, respectively. 2.3 Modeling QUADRI et al. (1996) studied the osmotic dehydration of onions and observed that the thin skin that covers onion layers acts as a barrier to mass transfer. Thus, the edges are the main way out of water and penetrating salt. Considering these squares of onion to have two parallel faces covered by a thin skin which prohibits mass movement, this results in a bidimensional problem with mass flux in directions x and y, as shown in Figure 1:

where Mi is the component mass (salt or water), n the number of terms of the series, Deff the effective diffusivity and 2L is the plane size in directions x and y, the subscript eq refering to the equilibrium. The software program Statistica 5.0 was used to fit experimental data, with six terms of the series considered.

3. RESULTS AND DISCUSSION

3.1 Dehydration by immersion kinetics Figure 2 shows typical experimental results of the dehydration by immersion process. Water removal and solute penetration rates are greater in the initial phase of the process, gradually decreasing over time. An analysis of the kinetic curves shows that the loss of water is faster than salt penetration, so it arrives more quickly at the point of equilibrium. It can also be observed that salt gain by the onion can be controlled by the length of contact time. Although this penetration is slower than the rate of solvent, it is very high in comparison to other sorts of solute described in the literature. This difference can be attributed to the low molar mass of the NaCl, which may facilitate salt penetration of the vegetable cell wall, thus quickly lowering the water activity of the product.
25 30 C
o

0.2 cm 0.8 cm

skin
x

0.8 cm

20 %

FIGURE 1. Schematic representation of on onion slice.

15 10

WL SC

The phenomenon of Fickian diffusion for rectangular geometry is described by the following equation:

5 0 0 2 Time (h) 4 6

2C 2C C = Deff 2 + 2 t y x

(4)

FIGURE 2. Water loss (WL) and salt content (SC) of dehydrated onion soaked in a 15% salt solution at 30oC.

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Kinetics of the Dehydration of Onion by Immersion

LAZARIDES et al. (1995) attributed this quick water loss of the beginning of the process to the driving force between the diluted solution within the onion and the hypertonic surrounding solution. Even in dilute solutions, however, the rapid water removal rate decreases after an hour of processing. This seems to be related to a solid barrier formed on the surface of the product by salt uptake. Studies of BOLIN et al. (1983) and LENART, FLINK (1984) have shown that during the osmotic dehydration process, the solute (sucrose, in this case) penetrates only 2-3mm deep. This solid barrier seems to prevent water to flow from the cell. Moreover, LENART, FLINK (1984) have shown that the reduction in rates of water loss and solute impregnation are also due to structural changes in the product, such as matrix surface shrinkage and cell membrane rupture causing a compaction of surface layers and an increase in mass transfer resistance. The results of experimental procedures conducted at 22, 30 and 40oC, in NaCl concentrations of 5, 10 and 15 % are presented in Figures 3 and 4.

10 8 6 4 2 0 0 5

22 C
5% NaCl 10% NaCl 15% NaCl 10 15 Time(h) 20 25

SC (%)

12 10 8 6 4 2 0 0 5 10

30 C
5% NaCl 10% NaCl 15% NaCl

SC (%)

15

20

25

Time (h)

90 WC (%) 85 80 75 0 1

22 C
5% NaCl
SC (%)

40 C
10% NaCl 15% NaCl
12 10 8 6 4 2 0 0 5 10 15 Time (h) 20 25 5% NaCl 10% NaCl 15% NaCl

2 3 Time (h)

90 WC(%) 85 80 75 0 1 2

30 C
5% NaCl 10% NaCl 15% NaCl 3 Time(h) 4 5

FIGURE 4. Salt content profile of onion osmotically dehydrated in salt solutions. The reduction of water content and salt penetration were strongly affected by the solution concentration and temperature. In general, the higher the concentration and temperature, the greater was the removal of water and the higher the salt content in the onion. Thus solute concentration seems to have a more pronounced effect on the processing parameters than does temperature. For example, the final water content obtained by this process in a 10% NaCl solution was about 81% for all temperatures investigated (Figure 3), however increasing the solution concentration to 15% NaCl, led to a lower final water content: 78%, 76.5% and 75.6% at 22oC, 30oC and 40oC, respectively. For salt content (SC) the same behaviour was observed (Figure 4). For the 5% NaCl solution, the final salt content was about 3% for all temperatures investigated but when the salt concentration was increased the salt content in the onion increased noticeably (10% NaCl: 6.5% and 15% NaCl: 9%, at 30oC, for example). 3.2 Effective diffusion coefficients

90 WC(%) 85 80 75 0 1 2

40 C
5% NaCl 10% NaCl 15% NaCl 3 Time(h) 4 5

FIGURE 3. Water content profiles of onions osmotically dehydrated in salt solutions.

Table 1 shows the effective diffusion coefficients of the water and salt. It also shows the correlation coefficient (r2).

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Kinetics of the Dehydration of Onion by Immersion

TABLE 1: Effective Diffusion Coefficients of the water and sodium chloride.

NaCl % 5 5 5 10 10 10 15 15 15 Temp
0

temperature, and 78.2% for maintaining the temperature and varying the concentration. Besides, the high effective diffusivity for salt at 30 o and 40oC for 15% NaCl(1.39 and 1.42.10-9 m2/s, respectively) this suggests that this temperature is probably too high for the product, as it seems to cause damage in the cell structure such as the softening of the cellulose complex present in the plant tissue wall, which may be related to an increase in solute permeability (BARONI, 1997). For other concentrations studied this effect was observed to a lesser extent.

Deff water m2/s .109 0.90 1.30 1.34 1.61 1.87 2.30 2.10 2.45 3.73

Deff salt m2/s .109

22 30 40 22 30 40 22 30 40

0.94 0.99 0.98 0.99 0.99 0.99 0.99 0.98 0.98

0.38 0.56 0.78 0.41 0.79 0.93 0.94 1.39 1.42

0.97 0.97 0.96 0.98 0.97 0.96 0.98 0.96 0.97

4. CONCLUSIONS
Square onion pieces can be partially dehydrated by soaking in sodium chloride solution. High moisture removal and salt impregnation rates were observed at the beginning of the process. In general, the higher the concentration and temperature, the greater the removal of water and the higher the salt content in the onions. Solute concentration thus seems to affect processing parameters more than temperature. Effective diffusion coefficients were obtained successfully using Cranks plane sheet geometry solution of Ficks diffusion law, bidimensional mass transfer because of the product skin. The results showed that the higher the temperature and salt concentration, the higher the effective diffusion coefficient.

The effective diffusion coefficients for water were slightly higher than those presented in the literature (see Table 2) mainly because a low molecular mass solute was used that could penetrate the cell wall more easily than other compounds such as sugar and alcohol. Moreover, a bidimensional geometrical approach to diffusion modeling was employed to account for the thin onion skin which acts as a barrier to mass transfer. However, WANG, SASTRY (1993) reported a similar effective diffusion coefficient for salt, 0.53.10-9m2/s in a 3% NaCl at 25oC, for cylindrical potato tissue. TABLE 2. Effective Diffusion Coefficients for water.
Product Pineapple Solution type Sucrose Concentration 50-70oB Temperature (oC) 30-50 Deff water m2/s .109 0.5-2.6 Authors BERISTAIN et al. 1990 HOUGH et al. 1993 LAZARIDES et al. 1997 RASTOGI et al. 1997

5. NOMENCLATURE
Deff C L M n r
2

effective diffusion coeffcient mass concentration plane size mass number of term series correlation coefficient salt content time temperature water content water loss water total time initial equilibrium salt component ( water or salt)

m2/s adim. m Kg adim. adim. % h/s

o

Apple

Glucose

55oB

45

0.19

Potato

Corn syrup 38DE CSS Sucrose

55%

50

0.22

Banana

40-70oB

25-35

0.85-2.43

SC In all cases, the higher the solution temperature and concentration, the higher the effective diffusion coefficients. To evaluate the influence of temperature and concentration on the effective diffusion coefficients, the ratios between the Deff values for the same variable, were calculated (e.g., 10% NaCl, the ratio between the Deff for water value for 22oC to 30oC is near 16%). This procedure was repeated for all conditions shown in Table 1, and the mean ratio between all Deff water values for the same concentration, varying the temperature, is about 36.1%, while the mean ratio changing the concentration resulted in 79.8%, indicating that the temperature has a lower effect than the concentration, as shown by kinetics curves. In the case of Deff salt values, the same behavior was found, but it was not so evident as for water. The mean ratio was 58.9% for the same concentration, changing the t T WC WL Subscripts w T t o eq s i

% %

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Kinetics of the Dehydration of Onion by Immersion

REFERENCES
AZUARA, E., CORTS, R., GARCIA, H.S., BERISTAIN, C.I. Kinetic Model for Osmotic Dehydration and Its Relationship with Ficks Second Law. International Journal of Food Science and Technology, 27:409-418, 1992. BARONI, A .F. Semi-Desidratao Congelamento e SemiDesidratao Secagem de Cebola. (Mestrado em Engenharia de Alimentos). Universidade Estadual de Campinas, Brazil, 1997. BARONI, A .F., HUBINGER, M.D. Dr ying of onion: Effects of Pretreatments on Moisture Transport. Drying Technology, 16:2083-2094, 1998. BERISTAIN, C.I., AZUARA, E., CORTS, R., GARCIA, H.S. Mass Transfer during Osmotic Dehydration of Pinneapple Rings. International Journal of Food Science and Technology, 25:409-418, 1990. BISWAL, R.N., BOZORGMEHR, K., TOMPKINS, F .D., LIU, X. Osmotic Concentration of Green Beans Prior to Freezing. Journal of Food Science, 56:1008-1012, 1991. BOLIN, H.R., HUXSOL, C.C., JACKSON, R., NG, K.C. Effect of Osmotic Agents and Concentration on Fruit Quality. Journal of Food Science, 48:202-205, 1983. CRANK, J. The Mathematics of Diffusion. Clarendon Press, Oxford, 1975. HAWKES, J., FLINK, J.M. Osmotic Concentration of Fruit Slices Prior to Freeze Dehydration. Journal of Food Process Engineering, 2:265-284, 1978. HOUGH, G., CHIRIFE, J., MARINI, C. A Simple Model for Osmotic Dehydration of Apples. Lebensmitteln-Wissenschaft undTechnologie, 26:151-156, 1993. L AZARIDES, H. N., GEKAS, V., MAVROUDIS, N.E. Apparent Mass Diffusivities in Fruit and Vegetable Tissues Undergoing Osmotic Processing. Journal of Food Engineering, 31:315-324, 1997. LAZARIDES, H.N., MAVROUDIS, N.E. Kinetics Of Osmotic Dehydration of a Highly Shrinking Vegetable Tissue in a Salt-free Medium. Journal of Food Engineering, 30:61-74, 1996. L AZARIDES, H.N., KATSANIDIS, E., NICKOL AIDIS, A. Mass Transfer Kinetics during Osmotic Preconcentration Aiming at Minimal Solid Uptake. Journal of Food Engineering, 25:151-166, 1995. LE MAGUER, M. Osmotic Dehydration: Review and Future Directions. Proceedings of Symposium on Progress in Food Preservation Process, 1, Brussels, Belgium, 183-309, 1988.

LENART, A. Osmo-convective Drying of Fruits and Vegetables: Technology and Application. Drying Technology, 14:391-413, 1996. LENART, A., FLINK, J.M. Osmotic Concentration of Potato. I. Journal of Food Technology, 19:45-63, 1984. LERICI, C.R., PINNAVAIA, G., DALL A ROSA, M., BARTOLUCCI, L. Osmotic Dehydration of Fruit: Influence of Osmotic Agents on Dr ying Behavior and Product Quality. Journal of Food Science, 50:1217-1226, 1985. MAURO, M.A., MENEGALLI, F.C. Evaluation of Diffusion Coefficients in Osmotic Concentration of Bananas. International Journal of Food Science and Technology, 30:199-213, 1995. PONTING, J.D. Osmotic Dehydration of Fruits - Recent Modification and Applications. Process Biochemistry, 8:18-20, 1973. PONTING, J.D., WATTERS, R.R., FORREY, R., JACKSON, R., STANLEY, W.L. Osmotic Dehydration of Fr uits. F o o d Technology, 20:1365-1368, 1966. QUADRI, M.G.N., QUAST, E., QUADRI, M.B. Secagem de Cebola em Bandejas Utilizando Desidratao Osmtica como Pr-tratamento. Anais do XXIV Congresso Brasileiro de Sistemas Particulados, 1, Uberlndia, MG, 313-317, 1996. RANGANNA, S. Handbook of Analysis and Quality Control for Fruit and Vegetable Products. Tata McGraw Hill, New Delhi, 1986. RAOULT-WACK, A.L. Recent Advances in the Osmotic Dehydration of Foods. Trends in Food Science and Technology, 5:255-260, 1994. RA STOGI, N.K., RAGHAVARAO, K.S.M.S. Effect of Temperature and Concentration on Osmotic Dehydration of Coconut. Lebensmitteln-Wissenschaft und-Technologie, 27:564-567, 1994. RASTOGI, N.K., RAGHAVARAO, K.S.M.S., NIRANJAN, K. Mass Transfer during Osmotic Dehydration of Banana: Fickian Diffusion in Cylindrical Configuration. Journal of Food Engineering, 31:423-432, 1997. TOMA SICCHIO, M., ANDREOTTI, R., DE GIORGI, A. Osmotic Dehydration of Fruits. II. Pineapples, Strawberries and Plums. Industrie Conserve, 61:108-114, 1986. TORREGGIANI, D. Osmotic Dehydration in Fruit and Vegetable Processing. Food Research International, 26:59-68, 1993. WANG, W.-C., SASTRY, S.K. Salt Diffusion into Vegetable Tissue as a Pretreament for Ohmic Heating: Determination of Parameters and Mathematical Model Verification. Journal of Food Engineering, 20:311-323, 1993.

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