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Water Activity: Definition & Applications

Definitions The moisture content of a product can be defined as the percentage weight of water in relation to the dry weight of the product.

Products in which moisture can be present can be classified in two categories: hygroscopic and non hygroscopic. Examples of hygroscopic materials are salts, vegetal fibers, most metal oxides, many polymers, etc. Examples of non hygroscopic products are metal powders, glass granules, etc.

Regarding the moisture content of a product, we define static equilibrium as a set of conditions under which the  product does not exchange any moisture with its environment. Under conditions of static equilibrium, the moisture content of a hygroscopic product depends on the nature of the product and also on the two following factors:

(a) the partial pressure of water vapor in the immediate environment of the product
(b) the temperature of the product

If the moisture content of a product is not dependent on both these factors, then the product is not hygroscopic.

Hygroscopic products may absorb water in different ways: sorption with formation of a hydrate, binding by surface energy, diffusion of water molecules in the material structure, capillary condensation, formation of a solution, etc. Depending on the absorption process, water is bound to the product with more or less strength. Moisture content can include both an immobilized part (e.g. water of hydration) and an active part.

Water activity Aw (or equilibrium relative humidity %ERH) measures the vapor pressure generated by the moisture present in a hygroscopic product.

aw = p / ps  and  %ERH = 100 x Aw, where:

p    : partial pressure of water vapor at the surface of the product
ps  : saturation pressure, or the partial pressure of water vapor above pure water at the
       product temperature

Water activity reflects the active part of moisture content or the part which, under normal circumstances, can be exchanged between the product and its environment.

Water activity is defined under static conditions of equilibrium. Under such conditions, the partial pressure of water vapor (p) at the surface of the product is equal to the partial pressure of water vapor in the immediate environment of the product. Any exchange of moisture between the product and its environment is driven by a difference between these two partial pressures.

Finally, water vapor can also be present in a gas or gas mixture. The relative humidity of a gas is defined as %RH = 100 x p/ps, where (p) is the partial pressure of the water vapor present in the gas mixture and (ps) is the saturation pressure, or the partial pressure of water vapor above pure water at the temperature of the gas.
Aw and Temperature

Both water activity (materials) and relative humidity (gases) are referred to the saturation pressure (ps) or partial pressure of water vapor above pure water:

aw = p / ps

%RH = 100 x p/ps

The saturation pressure (ps) is strongly dependent on temperature. At normal room temperature, ps increases by about 6.2% for a 1°C increase in temperature.

In an open environment that is not saturated with water vapor, the partial pressure of water vapor (p) does not change with temperature. In a closed environment, (p) changes proportionally to the °K temperature (°K temperature = °C temperature + 273.16). At normal room temperature, the change in (p) caused by a small change in temperature is practically negligible.

Because (p) does not change with temperature while (ps) does, the relative humidity of a gas (%RH = 100 x p/ps) is strongly temperature dependent. At 95 %RH and room temperature, an increase of 1°C results in a relative humidity decrease of about 6 %RH. At 50%RH, the same temperature increase causes relative humidity to decrease by about 3 %RH.

The water activity of most hygroscopic products is not as strongly dependent on temperature. At room conditions, research data typically shows that water activity varies only by roughly 0.0005 to 0.005 aw (0.05 to 0.5 %RH) when temperature changes by 1°C.

This is explained by the fact that the partial pressure (p) at the surface of a hygroscopic product does vary with temperature. Above most hygroscopic products, the magnitude of the change in the partial pressure of water vapor (p) with temperature is similar (but not exactly equal) to the magnitude of the change of the saturation pressure (ps) above pure water.

In summary, a change in temperature causes the partial pressure of water vapor above a hygroscopic product to change. At the same time, the partial pressure in the air above the product is practically unchanged. It follows that any change in the temperature of a hygroscopic product automatically causes the product to exchange moisture with the air (or gas) that surrounds it. Moisture is exchanged until the partial water vapor pressure at the surface of the product and in the air are equal. When measuring aw, it is important to keep temperature as constant as possible both at the product sample and in the air above it.

Applications The active part of moisture content and, therefore, water activity, provide better information than the total moisture content regarding the micro-biological, chemical and enzymatic stability of perishable products such as foods and seeds. For similar reasons, water activity is equally relevant in the pharmaceutical industry where it provides useful information regarding the cohesion of tablets and pills, or the adherence of coatings. Water activity can be directly compared with the relative humidity of the ambient air to prevent dimensional changes in a product (paper, photographic film), to prevent hygroscopic powders (powdered sugar, salt) from caking or turning into a solid block, etc

Water activity can be used with some products (mostly synthetic products) as a means of indirectly measuring the total moisture content. This requires developing sorption isotherms to this purpose. Sorption isotherms are graphs that provide the relationship between water activity and moisture content at constant temperature. For most natural products, repeatable sorption isotherms cannot be reliably developed and water activity should be regarded as separate from moisture content.