Measurement of Water Activity

Instrumentation methods Hair or Polymer Hygrometer

The principle is based on the fact that a water-sorbing fiber will undergo a magnitude of longitudinal change in length. In particular, keratinaceous proteins in hair stretch under tension, when they absorb moisture. If the hair strand is fixed at one end and attached to an indicating lever arm at the other end, the RH within an enclosure can be read directly from the deflection of the hair. Modern hair hygrometers are of dial type having a polyamide thread. In the past, animal hairs were used.

Measurement takes about 3 h of equilibration at constant temperature. However, longer equilibration times may be necessary at higher aw values. Inexpensive and fairly accurate (0.02 to 0.01 aw) Presence of glycerol or other volatile substances impair the sensitivity of the instrument during long equilibration.

Hygrometer Chilled Mirror Dew Point Method

The vapor pressure is determined from the exact temperature at which condensation of water vapor occurs (dew point). The dew point of vapour pressure in air is determined by cooling the air, without a change in the water content until saturation. The dew point is the temperature at which the air reaches saturation, which is measured from the condensation on the chilled mirror. The sample is equilibrated within the headspace of a sealed chamber containing a mirror, optical sensor, internal fan and infrared thermometer. into a photodetector cell.

A beam of light is directed on to this mirror and reflected

The exact point at which condensation appears is detected using an optical reflectance sensor, which emits infrared light onto the mirror. When condensation occurs, a change in reflectance is observed. The sample temperature at the point of condensation also is measured using the infrared thermometer. The water activity is computed by

where Td is the dew point temperature, Ts is the temperature of the sample.

Accurate, fast and simple with a resolution of 0.001 aw. Measurement time is less than 5 min.

Isopiestic Method

This method is based on the measurement of ERH of any aqueous system in a closed container at a specified temperature. Food substances either sorb or desorb water and equilibrate to the exposed moisture or RH condition. A sample of known mass is stored in a closed chamber and allowed to reach equilibrium either with an atmosphere of known ERH or with a reference material of known sorption isotherm. Usually, a series of salt solutions or sulfuric acid solutions of different RH (from 0 to 100%) are used.

Equilibrium between the environment and the sample is determined by weighing at intervals until constant weight is established. Several days or weeks may be required for equilibration. equilibrium with the vapour pressure of the reference salt slush or sulfuric acid.

The vapour pressure of the food samples will be in

Multiple samples could be measured at different equilibrium conditions.

Upon equilibration, the EMC is computed and the sorption isotherm is plotted. The sorption isotherm provides the aw against the moisture content of the food. Most commonly used because it is easy to set up and is inexpensive.

The disadvantages are: lengthy equilibration times, microbial spoilage at high RH, loss of conditioned atmosphere each time the sample chamber is opened for weighing and differences in temperature between the sample and the standard.

Figure. Schematic diagram a simple isopiestic system for water activity measurement

Table. Water activity of saturated salt solutions

Electric Hygrometers

These instruments use calibrated aluminium oxide or lithium chloride humidity sensor, which were calibrated by a set of reference salt slushes. The water activity of the sample is measured by connecting the sensor to an airtight food sample container and equilibrated at a specified temperature. The measurement time is only a few hours as the sample takes a short time to approach equilibrium conditions. The accuracy and precision are quite high but these hygrometers are susceptible to contaminants such as SO2, H2S, chlorine and oil vapors. There are two types: capacitance and resistant based. They both work on the same principle that the electrical response is a function of RH.

Water adsorbs or desorbs within the sensor and alter its electrical properties. These instruments can measure the entire range of aw with an accuracy between 0.01 and 0.02 aw. However, the equilibration time required increases with at higher aw values. Equilibration time is 20 min. to 24 h, depending on the humidity range and the food material.

Figure. Schematic diagram for relative vapor pressure/ water activity measurement

Thermocouple Psychrometer

The measurement of wet bulb temperature is related to the vapor pressure using the following equation: p = po(Tw) Pa (Td-Tw) where, po is the saturated vapor pressure at the wet bulb temperature is the psychrometer constant Pa is the pressure of the air Td and Tw are the dry bulb and wet bulb temperature of the surface A thermocouple, which is positioned above the sample in a small container, is used to measure the temperature based on the voltage produced. A small droplet of water is placed or condensed on the thermocouple junction to measure the wet bulb temperature. This instrument gives very high accuracy at high aw.

Vapor Pressure Manometer

Manometers determine aw by directly measuring the vapor pressure above a food. The sample to be measured is ground and introduced into a flask, which is attached through a trap to a simple manometer. The manometer assembly is then evacuated. The fluid level in the sample arm is deflected by the increase in pressure caused by the vapor pressure of the sample. The aw of a sample is calculated using equation

where,

Pvw is the vapor pressure of pure water (in Pa) is the density (kg/m3) of manometric oil g is the acceleration due to gravity (m/sec2) h1 & h2 are height readings of manometric oil (m)

The accuracy of this method is 0.005 a for a < 0.85.

Freezing Point Depression

When an ice phase is present in the foods, the ice exerts a vapor pressure that depends only on the temperature of the ice. The point at which water freezes within a food product is based on the colligative property (Raoults Law) of the sample. The freezing point indicates the temperature at which the vapor pressure of the solid and liquid phases of water are the same. the freezing point temperature relative to pure water, using the following equation:

The aw of the product is determined from the depression in

where, Pice and Psupercooled water are the vapor pressures above the ice and supercooled water, respectively at the same temperature.

Although measurement is simple and precise, the measurement is limited to solutions and products with aw>0.8. Moreover, capturing the point where water freezes is difficult because of its supercooling property beyond the freezing point.

Chemical Method

Certain chemical compounds change in color as they absorb water from the atmosphere (Eg. Cobaltous bromide, chloride or thiocyanate). These compounds are impregnated in a strip of absorbent paper. The change in color, in relation to the amount of imbibed moisture, is compared to the reference chart. These methods are inexpensive but gives only rough approximations of water activity.