dry-weight basis (dwb), i.e., the mass of water per unit
mass of dry solids. The latter way of expressing mois-
ture content is usually used in drying formulae and
calculations; see section Theory of Air Drying.
0004 However, when the influence of moisture on the
stability of foods is being studied, it is not only
the total moisture content that is of importance but
also how much of that moisture is available to sup-
port the activity of microorganisms and enzymes and
enable chemical changes to occur. It is now widely
accepted that a fraction of the total moisture in food
is strongly bound to individual sites on the solid
components and is not available to support these
activities. An additional amount of moisture is less
firmly bound but is still not readily available as a
solvent for soluble components of the food. Such
‘bound’ moisture exerts a vapor pressure less than
the vapor pressure of pure water at the prevailing
temperature. A property known as water activity
(a
w
) is used to represent the availability of moisture
in foods thus:
a
w
¼
p
v
p
w
ð1Þ
where p
v
is the water vapor pressure exerted by a
solution or wet solid, and p
w
is the vapor pressure
of pure water at the same temperature. This
expression also represents the relative humidity of
an air–water vapor mixture ( 100 to give the per-
centage relative humidity). A graph of moisture con-
tent as a function of water activity, with which it is in
equilibrium, is known as a sorption isotherm.Such
plots may be constructed by adsorption or desorp-
tion, which, in the case of many foods, results in two
different curves, exhibiting hysterisis (Figure 1). Food
isotherms may be considered to be made up of three
regions. In region A, water is strongly bound to spe-
cific sites on the solid components, is not available as
a solvent, and so does not support, microbiological,
enzymic or chemical activity. The amount of moisture
held in this way is known as the monolayer or mono-
molecular moisture content. This type of moisture
usually exits below a
w
0.35, corresponding to a mois-
ture content range 0.05–0.11 (dwb). Above region A,
water is less strongly bound to the solids but still does
not exert its full vapor pressure. In some publications,
region B (Figure 1), is said to contain moisture that is
bound in multilayers to the solid, and in region C,
structural and solution effects lower the water vapor
pressure. However, it is more likely that all these
effects have an influence over the whole isotherm.
At moisture contents of 1.0 (dwb) and above, most
foods exert vapor pressures equal to that of pure
water. Temperature affects the sorption behavior of
foods according to the expression:
d ðlna
w
Þ
d
1
T
¼
Q
s
R
, ð2Þ
where T is the absolute temperature, Q
s
is the heat of
adsorption, and R is the gas constant. The amount
of adsorbed water at any given value of a
w
decreases
as the temperature increases.
0005Numerous mathematical models have been proposed
to represent sorption isotherms of foods. One of the
earliest was the Brunauer–Emmet–Teller isotherm:
a
w
ð1a
w
ÞW
¼
1
W
m
C
þ
a
w
ðC 1Þ
W
m
C
, ð3Þ
where W is the total moisture content (dwb), W
m
is
the monolayer moisture content (dwb), and C is con-
stant. This model is said to apply over the a
w
range
0.05–0.45. An extended version of eqn (3), which
takes into account multilayer adsorption and is said
to be applicable up to a
w
0.90, is the Guggenheim–
Anderson–DeBoer model:
W
W
m
¼
Cka
w
ð1 ka
w
Þð1 ka
w
þ Cka
w
Þ
, ð4Þ
where C is known as the ‘Guggenheim’ constant, and
k is a factor correcting properties of the multilayer
molecules with respect to the bulk liquid.
0006A knowledge of the sorption characteristics of
foods is useful in the prediction of drying times and
energy requirements for drying processes. When
0 0.2 0.4
A
B
Desorption
Adsorption
Moisture content
0.6
C
Water activity
0.8 1.0
fig0001Figure 1 Adsorption and desorption isotherms showing hys-
teresis. From Brennan JG, Butters JR, Cowell ND and Lilly AEV
(1990) Food Engineering Operations, 3rd edn. London: Elsevier
Applied Science, with permission.
1914 DRYING/Theory of Air-drying