Journal of Food Engineering 67 (2005) 401405 www.elsevier.

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Eect of heating and cooling on rheological parameters of edible vegetable oils

J.C.O. Santos
a b

a,b,*

, I.M.G. Santos b, A.G. Souza

Departamento de Qumica, CCT, Universidade Estadual da Paraba, UEPB, Bodocongo, 58109-790, Campina Grande, Paraba, Brazil Laboratorio de Termoqumica e Materiais, Departamento de Qumica, CCEN, Universidade Federal da Paraba, Campus I, 58059-900, Joao Pessoa, Paraba, Brazil Received 14 October 2003; accepted 4 May 2004

Abstract In this work, the temperature-dependent rheological behavior of un-used and used vegetable cooking oils was evaluated. The unused edible oils (soybean, sunower, olive, rapeseed, corn, rice and the mixtures soybean + olive and sunower + olive) presented Newtonian behavior above 10 s1 shear rates; the values of viscosity during heating and cooling were similar, indicating that degradation of the oils did not happen at the temperature range studied (1080 C). After treatment at frying condition (190 C), there was an increase of the edible oils viscosity, depending on frying time, perhaps due to the increase of saturation of the oil constituents. The rheological behavior of used cooking oils remained Newtonian at shear rates greater than 10 s1. 2004 Elsevier Ltd. All rights reserved.
Keywords: Edible oils; Soybean oil; Sunower oil; Olive oil; Rapeseed oil; Corn oil; Rice oil; Rheology; Degradation

1. Introduction Rheology is a simple analysis that is being more and more applied to determine the behavior of solutions, suspensions and mixtures. The fundamental parameter, obtained in the rheological study of liquid foods, is viscosity, used to characterize the uid texture (Alonso, Garzon, Melcon, & Zapico, 1990; Rao, 1977). As an example of application, chemical exchanges in foods frequently occur with time and may be studied by rheological methods. Temperature is also an important parameter and frequently appears in rheological equations (Rosen & Forster, 1978).

Corresponding author. Address: Departamento de Qumica, ba, UEPB, Bodocongo, 58109 CCT, Universidade Estadual da Para ba, Brazil. Tel./fax: +55 83 2167441. 790, Campina Grande, Para E-mail addresses: zecarlosltm@bol.com.br, zecarlosuepb@ibest. com.br (J.C.O. Santos). 0260-8774/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.jfoodeng.2004.05.007

In vegetable oils, viscosity increases with chain lengths of triglyceride fatty acids and decreases with unsaturationin other words, increase with hydrogenation. So, viscosity is a function of molecules dimension and orientation (Moretto & Fett, 1998; Santos et al., 2004a). Physical properties (including viscosity) of pure triglycerides of short chain, have been evaluated in preceding studies (Eiteman & Goodrum, 1993; Eiteman & Goodrum, 1994; Goodrum & Eiteman, 1996). These studies have tried to develop models, to the use of oils with triglycerides to substitute as diesel fuel. Studies about rheological properties of binary mixtures of triglycerides have also been published (Eiteman & Goodrum, 1994; Goodrum, Geller, & Lee, 1998; Valeri & Meirelles, 1997). These investigations have been trying to understand how these compounds interact among them, and how triglyceride chain length aects physical properties of edible oils. Studies related to properties of short chain triglycerides, in pure state

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and simple mixtures, can be very useful in the development of biological fuels and other valuable products. On the other hand, natural vegetable oils are not composed of pure triglycerides or simple binary mixtures of triglycerides. They are complex mixtures of many triglycerides with dierent chain lengths. Recently, physical properties of short chain triglycerides, obtained from a natural source, were evaluated (Geller, Goodrum, & Knapp, 1999). Rheological properties of two complex mixtures of triglycerides of short chain were experimentally determined in a temperature range of 2580 C (Geller & Goodrum, 2000). The objective of this work was to evaluate the rheological properties of commercial edible oils (soybean, sunower, olive, rapeseed, corn, rice and the mixtures soybean + olive and sunower + olive) before and after simulated cooking under frying conditions.

analysis. Temperature was controlled using a water bath with precision of 2 C. Analysis was done in a temperature range of 1080 C and measurements were done in dierent shear rates, during heating and cooling. 2.3. Analysis of used cooking oils In the study of edible vegetable oils degradation as a function of frying time, samples were heated up to 190 C for 0.5, 1, 2, 4 and 8 h and, after natural cooling, viscosity was measured to evaluate the inuence of thermal degradation in oils viscosity. These oils were submitted to frying conditions in a 500 ml ask, with a surface of about 4 cm of diameter, exposed to air. Measurements were done at room temperature (25 C), in dierent shear rates, using the viscometer described above.

2. Materials and methods 2.1. Materials Edible vegetable oils samples were acquired in local commerce. In this study, the following oils were studied: soybean oil, sunower (with and without antioxidants), olive, rapeseed (with and without antioxidants), corn (with and without antioxidants), rice and the mixtures soybean (70%) + olive (30%) and sunower (97%) + olive (3%). Composition of the oils is presented in Table 1. 2.2. Analysis of un-used cooking oils Rheological study of vegetable edible oils, before degradation, was done to verify the inuence of heating and cooling in the oils viscosity. Measurements were done in a viscometer (model LV DVIIBrookeld, Middleboro, MA, USA), with a small sample adapter, spindle 31, which permits the use of only 20 ml of oil in each

3. Results and discussion 3.1. Rheological behavior of un-used cooking oils Fig. 1 illustrates viscosity (g) variation as a function of shear rate (c). A similar behavior was observed during heating and cooling of the edible vegetable oils analyzed. It may be observed that rheological behavior was independent of the presence of articial antioxidants (Table 1). A decrease of viscosity as a function of temperature may also be observed. According to Fig. 1, it may also be observed that viscosity depends on shear rates, for values below $5 s1. This indicates a range of non-Newtonian behavior and oils may be classied as Bingham uids. Viscosity values measured during heating and cooling are presented in Tables 2 and 3. Generally, liquid food viscosity depends on its temperature and composition, as well as on the previous treatment applied to these samples (Rao, 1977).

Table 1 Fatty acids composition (%) in edible vegetable oils Edible oils Fatty acids (%) Monounsaturated Olive Rapeseed (A) Rapeseed Sunower (A) Sunower Corn (A) Corn Soybean Rice Soybean + olive Sunower + olive (A) presence of articial antioxidant. 71.3 65.2 65.0 22.8 23.0 33.5 34.0 24.3 40.8 29.2 41.3 Polyunsaturated 12.7 29.3 29.0 65.2 65.0 51.0 50.0 60.0 40.1 57.0 46.7 Saturated 16.0 5.5 5.0 12.0 12.0 15.5 16.0 15.7 19.1 13.8 12.0

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Fig. 1. Relation between viscosity and shear rate for sunower oil showing temperature dependence.

Edible vegetable oils viscosity decreases with temperature increase. This is due to a higher thermal movement among molecules, reducing intermolecular forces, making ow among them easier and reducing viscosity. This behavior was also veried by researches (Kahn, Stehli, Wei, Steinberg, & Yamashita, 1990; Forster & Ferrier,
Table 2 Viscosity at 68 s1 shear rate, measured during edible vegetable oils heating Edible oils Viscosity (mPa s) 10 C Rice Soybean Rapeseed (A) Rapeseed Sunower (A) Sunower Olive Corn (A) Corn Soybean + olive Sunower + olive 141.1 101.8 113.6 112.1 95.6 93.8 131.0 114.7 99.1 88.1 103.0 25 C 70.6 53.4 58.7 60.1 52.3 52.0 66.1 58.9 54.4 52.3 56.5

1979), who observed that ow behavior is changed by sample temperature. Fig. 2 illustrates viscosity (g) variation as a function of temperature, for rice oil. Viscosity values of non-degraded oils were similar, during heating or cooling, indicating that no degradation occurred in the temperature range studied (1080 C). Considering that vegetable oils viscosity depends on fatty acids composition, Fig. 3 illustrates viscosity (g) dependence in relation to edible vegetable oils composition, described in Table 1. Results indicated that viscosity is better related to the concentration of polyunsaturated chains (r = 0.94) than to monounsaturated chains (r = 0.88). This is probably due to the higher amount of p bonds, that makes bonding more rigid, decreasing rotation between CC bonds. A more extended chain makes ow easier and viscosity smaller. 3.2. Rheological behavior of used cooking oils Results of vegetable oils viscosity after degradation are presented in Fig. 4. It may be observed that

40 C 39.2 30.6 33.4 33.3 30.1 30.3 35.7 33.4 31.3 30.2 33.0

60 C 21.1 16.9 17.8 18.1 16.8 17.1 19.1 18.4 17.1 16.5 18.0

80 C 12.7 10.5 10.7 11.2 10.4 10.6 11.5 11.4 10.4 10.0 11.2

Table 3 Viscosity at 68 s1 shear rate, measured during edible vegetable oils cooling Edible oils Viscosity (mPa s) 80 C Rice Soybean Rapeseed (A) Rapeseed Sunower (A) Sunower Olive Corn (A) Corn Soybean + olive Sunower + olive 12.7 10.5 10.7 11.2 10.4 10.6 11.5 11.4 10.4 10.0 11.2 60 C 20.5 16.8 17.9 18.1 16.5 17.0 18.7 18.3 16.7 16.3 17.6 40 C 38.5 30.2 33.1 33.1 30.2 30.3 35.3 33.3 30.5 29.9 31.8 25 C 69.3 51.9 58.1 58.3 52.0 51.5 64.2 58.8 53.5 51.3 55.1 10 C 142.7 101.6 115.2 117.5 101.2 97.6 130.0 115.1 105.7 100.5 107.3

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Fig. 2. Viscosity at 68 s1 shear rate as a function of temperature for rice oil.

Fig. 3. Relation between viscosity at 68 s1 shear rate and fatty acids concentration.

Fig. 4. Relation between viscosity at 68 s1 shear rate and frying time of the following oils: (a) rapeseed, rapeseed (A), corn, corn (A), sunower and sunower (A), (b) soybean, rice, olive, sunower + olive, soybean + olive.

the presence of antioxidants decreases degradation for rapeseed and sunower oils. For corn oil, viscosity is increased, indicating that the antioxidant is not ecient. Another important point is that addition of olive oil to soybean one decreases degradation. According to the results, it may be observed that vegetable oils viscosity increases with frying time. This may be due to oxidation and polymerization reactions (Moretto & Fett, 1998). Edible vegetable oils, repeatedly used in frying without immersion, are degraded by oxidative reactions with air (auto-oxidation) and with water (hydrolytic oxidation). In the present case, oxidation (accelerated by frying time and temperature) is the main agent responsible for modication in physical-chemical and organoleptic characteristics of the oils (Felsner & Matos, 1998; Santos, dos Santos, de Souza, Prasad, & dos Santos, 2002). During degradation, oils saturation increases, as well as formation hydroperoxide and other degradation products, leading to non-volatile compounds, as cyclic monomers, dimers, trimers and high molecular weight compounds (Kowalski, Ratusz, Miciula, & Krygier, 1997; Moretto & Fett, 1998; Sanhueza & Valenzuela Nieto, 2000; Santos, de Souza, Conceicao, Silva, & Prasad, 2004b).

Generally, oxidation reactions lead to the formation of carbonyl and/or hydroxyl groups bonded to carbon chain. Oxygen may lead to the formation of hydrogen bonds that increase intermolecular forces, making ux among molecules more dicult and increasing viscosity. In relation to polymerization, the increase in chain size leads to the increase in the electron number in the molecule, increasing London forces and, one more time, intermolecular forces. Besides this, longer chains are more dicult to move, leading to a higher viscosity. Rheological behavior of edible vegetable oils after frying is presented in Fig. 5, being observed that, in spite

Fig. 5. Rheological behavior of edible vegetable oils after being submitted to frying conditions.

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of the increase in frying time, a Newtonian behavior is still observed, above 10 s1 shear rate (Geller & Goodrum, 2000). Edible vegetable oils analyzed after thermal degradation became dark, viscous and developed a rancid unpleasant smell.

4. Conclusions Rheological properties of edible vegetable oils, not previously degraded, are similar in the temperature range 1080 C, even during heating or cooling, indicating that no thermal degradation occurs up to 80 C, at least during essay time. After being submitted to frying conditions, at 190 C, an increase in viscosity with frying time was observed, probably due to the formation of undesirable compounds, caused by oxidation and polymerization reactions. This way, it can be considered that viscosity may be used as a parameter to indicate edible vegetable oils degradation.

Acknowledgment The authors acknowledge CAPES and CNPq for scholarship and nancial support of this work.

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