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The isopiestic method is one of the most common techniques for establishing water absorption
isotherms or the relationship of water activity in a sample to gravimetric water content. The theory
behind it relatively simple. A sample is placed in a vacuum chamber along with an open container of
reference saly solution and is allowed to equilibrate. Over time the chamber air will come to the
relative humidity of the reference salt. As the system reaches equilibrium the sample will either lose
or take up water from the air to reach the same water activity of the reference salt solution. The
gravimetric water content of the sample is determined by drying in an vacuum oven or by Karl Fischer
titration. Combining the sample water activity with its gravimetric water content will provide one
point on its sorption isotherm. By repeating with several reference salt solutions (typically at least 8
points are necessary) across a range of water activities, the resulting set of points can be fit with any
one of the number of sorption isotherm equations.

Assuming the makeup of the sample does not change future values of water activity can be
interpolated from a measure of water content. Typical equilibration times are from 10 to 21 days
where equilibrations for samples with lower water activity. Will fall in the upper end of the range.
Often many chambers are set up at once to allow for simultaneous equilibration, but this method
considerable amount of space

The isopiestic method is attractive because it is free from contamination concerns and most
importantly inexpensive. In addition, it is a straight forward method that is not difficult to set up. Its
main disadvantages are space and time requirements.

There is another drawback to the isopiestic method that may not be apparent. Because of the long
equilibration times, samples can change during equilibration. These changes may take the form of
mould growth on the sample, or transitions from a good to rubbery or crystalline texture.
Water profoundly influences product attributes such as quality and safety. To completely
understandwater relations in a product requires an understanding of the amount of water (moisture
content) that can be held at a given energy state (water activity). Moisture sorption isotherms describe
the relationship between water activity and moisture content at a constant temperature. The nature
of this relationship depends on the interaction between water and other ingredients. The amount of
water vapor that can be absorbed by a product depends on its chemical composition, physical-
chemical state, and physical structure. Consequently, the isotherm shape is unique to each product
type due to differences in capillary, surface, and colligative effects (Figure 1). Products that lie in the
low water activity portion of the isotherm are often referred to as dry, those in the range of 0.60 aw
to 0.90 aw are intermediate moisture products, and those having water activities higher than 0.90 are
high water activity products.

For ease of interpretation, isotherms are often identified by Brunauer classifications (Brunauer, 1945).
Most food and pharmaceutical products fall under type I, II, or III. Type I isotherms are typical of very
hygroscopic materials, Type II (sigmoidal) isotherms are typical for intermediate moisture products,
and type III (J-shaped) isotherms are typical for crystalline and coated materials. These general
classifications proved useful when conducting isotherms on every product was not feasible due to
time and labor constraints. However, with automation and improved speed, isotherms can easily be
conducted on any product and the uniqueness of each isotherm often proves more valuable than
placing them in a common classification.


Constructing an isotherm consists of collecting water activity and moisture content values over a
range of water activities. The range of water activities used depends on the situation, but
normally is 0.10 aw up to 0.90 aw.

Traditional Desiccator Method

In the traditional isotherm method, each point on the isotherm is determined by equilibrating a
sample to a known water activity and then determining its equilibrium moisture content by weight.
Typically, the sample is placed in a sealed chamber over a saturated salt slurry in excess. Different
water activity levels are achieved by using different salts. Alternatively, varying concentrations of acid
or glycerol solutions, mechanical humidifiers, and adjusted mixtures of wet and dry air can be used.
Equilibrium is reached when the weight of the sample stops changing. This equilibration process can
take weeks. The temperature must be tightly controlled during equilibration and steps must be taken
to prevent microbial contamination at water activities higher than 0.60.

 A moisture sorption isotherm describes the relationship

between water activity and the equilibrium moisture
content of a food products at constant temperature. It is
also called the equilibrium moisture content curve.
 Desiccators can be used for preparation of sorption
isotherms. In the desiccator method, saturated salt
solutions, sulfuric acid or glycerol solutions are put into
the bottom of desiccators .
 Although the desiccator method is very commonly used
for water activity determination and preparation of
sorption isotherms, there are some errors arising from
this method. The error comes from the disturbance of
equilibrium caused by opening the desiccators, taking
the sample, and closing it again.
 These disturbances cause adsorption of water from the
surrounding air by samples with low water activities and
desorption of water from samples having high water
 If desorption occurs, the results are not affected
significantly since desorption occurs slowly. However, if
adsorption occurs, water activity is affected significantly
since adsorption is a fast process.
 Equilibrium moisture content (X*) is the moisture
content of a substance at equilibrium with a given partial
pressure of the vapor. It is used to describe the final
moisture content that will be reached during drying.
 Free moisture content is the moisture content in a
substance in excess of equilibrium moisture content (X −
X*). Free moisture can be removed by drying under the
given percent relative humidity.
 The moisture content data can be given in a dry or wet
basis. Moisture content is in a dry basis if it is expressed
as the ratio of the amount of moisture in the food to the
amount of dry solid (kg of moisture/kg of dry solid). If
the moisture content of a sample is described as the ratio
of the amount of water in the food to the total amount of
wet solid (kg of moisture/kg of wet solid), it is in a wet
 Moisture content is usually given in a wet basis to
describe the composition of the food material. It is
more common to use moisture content in a dry basis to
describe moisture changes during drying.
 The sorption isotherm is useful to determine the shelf life
and to assess the background of operations such as
drying, conditioning, mixing, packaging, and storage.
 The isotherm also gives information about the specific
interaction between water and the product since it
directly relates the thermodynamic potential (Gibbs free
energy) of water in the system to its mass fraction
 The two principal techniques used for the adjustment of
water activity are the integral and differential methods.
 In the integral method, several samples are prepared and
each is placed under a controlled relative humidity
environment simultaneously. The moisture contents of
the samples are measured after constant weight is
 In differential method, a single sample is placed under
successively increasing or decreasing relative humidity
environments. Moisture content is measured after each
equilibration. The differential method has the advantage
of using only a single sample. As a result, the error
coming from the sample variation is eliminated.
 However, since equilibration can take several days, the
sample may undergo various degenerative changes. The
integral method avoids this problem because each sample
is discarded after appropriate measurement is made.
Classification of
standard moisture
sorption isotherms

 Sorption isotherms of food materials are generally in sigmoid shape (type II). The effects of
Raoult’s law, capillary effects, and surface–water interactions are important in sorption curves
and they are additive.

 Type I isotherm is observed in pure crystalline sugar. It shows very little moisture gain up to
a water activity of 0.7 to 0.8 since the only effect of water is hydrogen bonding to the –OH
groups present on the surface of the crystal
 Thus, surface effect is important, which means grinding the sugar to smaller particles will
increase the moisture content at low water activity values. As the water activity is increased,
water begins to penetrate into the crystal, causing dissociation of sugar–sugar interactions
and a solution is obtained. At this stage, the effect of Raoult’s law is important.
 The type III isotherm is observed in the case of anticaking agents. In these types of materials,
binding energy is so large that water activity is depressed while water is absorbed. When all
the binding sites are filled, the increase in moisture content causes water activity to increase