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Water Sorption IsothermsTypes and Hysteresis

Classification of water sorption isotherms

Based on shape, the sorption isotherms are classified into five types in the BDDT (Brunaeur-Deming-DemingTeller) classification: Type I Type II Type III Type IV Type V

The shape of the water sorption isotherm is characteristic


of the states of the food constituents.

The type I isotherm is typical of anti-caking agents as they can hold large amounts of water at low water activities. This type of ingredients absorbs water via chemisorption onto sorption sites.

The type II shape (sigmoidal) is caused by the additive effects of Raoults law, capillary effects and surface water interactions. This type of isotherm shows an asymptotic trend as water activity approaches the value of 1. Two bending regions are observed: one around 0.2-0.4 aw and another at 0.6-0.7 aw, due to the build-up of multilayers and filling of small pores in the lower region, followed by filling up of large pores and solute dissolution. (Barbosa-Cnovas et al 2007)

Foods rich in sugar and salt manifest the type III isotherm, wherein the moisture gain is very low up to the point where the crystals begin to dissolve in the absorbed water at the surface of the crystal. Type III also is known as the Flory-Huggins isotherm. It accounts for the adsorption of a solvent or plasticizer like glycerol above Tg. In the lower aw region, water is hydrogen-bonded to the OH groups that stick out on the crystal surface. The Type IV isotherm describes the adsorption by a swellable hydrophilic solid until a maximum of hydration of sites is reached.

Type V is the B.E.T. multilayer adsorption isotherm, observed for the adsorption of water vapour on charcoal, and it is related to type II and III isotherms. In types IV and V, the maximum moisture content is reached before the aw reaches 1. are Types II and IV isotherms.

The two isotherms most frequently found for food products

Hysteresis

It is a phenomenon wherein two different paths exist between the adsorption and desorption isotherms because, at a given water content, a substance can have two aw values. It is because at equal vapor pressure, the amount of adsorption and desorption for the same food may differ.

The desorption isotherm lies above the adsorption


isotherm.

Depending on the type of food and the isotherm temperature, a variety of hysteresis loop shapes are observed. Other factors affecting hysteresis are composition of product, storage time before isotherm measurement, drying time, etc.

(Adopted from Barbosa-Cnovas et al 2007)

In general, the total hysteresis decreases as sorption temperature increases. Thermodynamically, it is impossible because the chemical potential or aw should be the same when the composition and water content of a material remains same. Three types of foods were defined based on the composition of the food affecting hysteresis: a. high sugar foods b. high protein foods c. starchy foods In high sugar foods, hysteresis occurs mainly below the monolayer region. In high protein foods, the hysteresis phenomenon is extended up to an aw of 0.85. In starchy foods, a large hysteresis loop occurs, which closes at about 0.7 aw.

Theories of Sorption Hysteresis

The differences in water activities at the same content is due to the structural arrangement occurring during the removal of bound water, which reduces the accessibility of polar groups and the cavities in the protein matrix. For example, hydration of proteins allows water to bind before desorption, while dehydrated proteins have some polar sites unavailable for water binding prior to adsorption. Similarly, the polymeric materials swell during adsorption also are contributing factors to hysteresis. Another theory states that since hysteresis is more evident in Region III of the isotherm, it could be a consequence predominantly of capillary condensation.

Also, a commonly-accepted hypothesis is that during desorption, some solutes may supersaturate below their crystallization aw, and thus hold more water as aw is lowered. Lastly, the surface tension and the wetting angle, obtained from the Kelvin equation, differ between adsorption and desorption, resulting in a higher moisture content for desorption.

Ink-bottle Theory of Hysteresis Phenomenon

According to this theory, pores in a food material are of inkbottle shape, with a narrow neck and a broad base.

Only water present in the neck contributes to water activity of the material.

In the wet product, the base of the pores are full with water, which are emptied during desorption. During desorption, as the aw is lowered, the controlling factor for moisture transfer is the small radius, and the system reaches an aw in equilibrium with the radius, so that the pores remain filled. This indicates that the moisture content will be higher in desorption. Conversely, during adsorption, the vapour condenses into the necks and blocks the filling of bases. As a result, the food material possess less water content for the same aw as observed during desorption.

Significance of Hysteresis Phenomenon

Hysteresis phenomenon is of practical importance because at a given aw, a desorption-prepared food can have a considerably higher moisture content than an adsorption-prepared food. For example, an IMP pork prepared to 0.92 aw had a moisture content of 67.5% when prepared by desorption but only 55.9% when prepared by adsorption. S. aureus grew readily in the former but died in the latter. Hysteresis also may affect the rates of chemical deterioration and physical changes in stored food. It is important in predicting the stability of dehydrated products.