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This article presents basic concepts related to the thermodynamics of sorption of water and measurement of sorption isotherm
for food materials. A comprehensive review of the widely used sorption models is presented. Various statistical techniques used to
ascertain the effectiveness of a model to describe the sorption data
are discussed. It is anticipated that this article will provide useful
information to researchers pursuing work on sorption behavior of
food materials as well as modeling of drying processes.
Keywords Heat of sorption; Isosteric heat; Model; Sorption isotherm; Statistical analysis
INTRODUCTION
The state of water plays a crucial role in food preservation. The quality of preserved foods depends upon the
moisture content, moisture migration, or moisture uptake
by the food material during storage. Extent of sorption
of water by or desorption from a food product depends
on vapor pressure of water present in the food sample
and that in the surroundings. Moisture content at which
vapor pressure of water present in the food equals that of
the surroundings is referred to as equilibrium moisture content (EMC).[1] Relationship between EMC and corresponding relative humidity at constant temperature yields
the so-called moisture sorption isotherm. For a given
material the EMC increases with relative humidity but
decreases with increase in temperature. The phenomenon
where the EMC during the adsorption and that during
the desorption process is different is called hysterisis.
Water activity is commonly used to characterize the food
quality and is defined as
aw
P
ERH
P0
100
917
918
d1=T M
R
aw1
R T1 T2
where aw1 and aw2 represent water activities at temperatures T1 and T2, respectively, and R is the universal gas
law constant (8.314 kJ=molK)
Several assumptions are made implicitly in applying the
Clausius-Clapeyron equation. First, the heat of vaporization of pure water (DHvap ) and the excess heat of sorption
DHS are assumed not to change with temperature. Secondly, the equation applies only when the moisture content
of the system remains constant with respect to time.[14]
From the isotherms determined at least at 10C apart, aw
at any other temperature should be predictable from
Eq. (3) if the assumptions are correct. Plotting the experimental sorption isotherm in the form ln(aw) vs. 1=T for a
specific moisture content, DHS is determined from the
slope DHs =R.
An empirical relationship between the net isosteric heat
of sorption (DHS ) and the moisture content (M, dry basis)
is expressed as[14]
where DH0 is the net isosteric heat of sorption when moisture content (M) 0. The constant MC is a characteristic
moisture content (kg water per kg dry matter) of a food
material at which the net isosteric heat of sorption (DHS )
has been reduced by 63%. Due to the exponential decay,
the net isosteric heat of sorption becomes very small at high
moisture content; e.g., at M 3 MC, DHS is less than 5%
of DH0 .
The net heat of sorption of water Q (kJ per kg dry matter) from dryness (M 0) to moisture content M is
expressed as:[14]
Z M
Q
DHS dM
5
0
Substituting DHS from Eq. (4) into Eq. (5) and integrating
yields
Q DH0 MC 1 expbM=MC c
For very high moisture content (M ! 1), Eq. (6) gives the
total net isosteric heat in terms of heat of sorption of water
(QT).
QT DH0 MC
10
11
919
M M0
CM0
where M0 is monolayer sorbate constant and C is a constant.
The relation described by Eq. (12) yields the type I isotherm.
BRUNAUER-EMMETT-TELLER (BET) EQUATION
The BET isotherm equation[3] is one of the most widely
used models and gives good fit for a variety of foods over
the region 0.05 < aw < 0.45.[22] It provides an estimate of
920
M0 1 aw 1 C 1aw
13
or
aw
1
C1
aw
1 aw M M0 C M0 C
14
aw
1 aw
N
15
"
aw
M
A BT
#1
C
1
17
with C 1=N.
MODIFIED HALSEY EQUATION
Halsey[25] developed an equation to describe condensation of multilayers, assuming that the potential energy
of a molecule varies inversely as the Cth power of its
distance from the surface. The equation is
AM C
aw exp
18
RT
Because the use of the term RT does not eliminate the temperature dependence of constants A and C, Iglesias and
Chirife[26] simplified it to the form
aw expA0 M C
19
21
22
25
921
26
M
C 1Kaw
Kaw
27
1
1
1 X 1 1 CX
30
2
dX 1 X
1 1 C X 2
31
1
p
1 C
for C 0:
32
KC
1 K1 K1 C
for X K
33
a=0 < K;
C>
34a
34b
922
4. Points of inflection: the point of inflection of the sorption isotherm is given by the zero point of the second
derivative of w X plot. The following equation is
obtained for the X coordinate (Xi) of such a point:
Xi3
3Xi
C2
0
C 1 C 1 2
35
where k1, k2, n1, and n2 are constants (n1 < 1) and n2 > 1).
The model expressed by Eq. (43) has no monolayer incorporated in it. However, plots of aw =M1 aw vs. aw used
to determine the monolayer value with the BET model are
still expected to be practically linear over a water activity
range of up to about 0.4. This is because at this range of
aw Eq. (43) can be approximated by
M k1 anw1
Z1
Xi
for C 2
36
Z2
p
where Z 3 C 1. The relative moisture content corresponding to the point of inflection wr is given by inserting Xi from Eq. (36) into Eq. (30)
wr
Z2 1
A
37
A Z2 Z 1
38
t
k1 k2 t
39
1
k2
40
dt
k1 k2 2
41
aw
aw
M1 aw k1 anw1 1 aw
42
43
44
45
The plot of aw = anw1 1 aw vs. aw (k1 1) is linear in this
water activity range and for a range of n1 values. The intercept is positive when n1 is greater than 0.3.
aw
aw =k1
n1
M1 aw aw 1 k1 =k2 anw1 n2 1 aw
where
[45]
and
n1 < 1
46
M0 1 Kaw 1 CH 1Kaw
47
48
49
For h ! 1, H; H 0 ! 1 and with this result Eq. (47) transforms into a GAB equation.
923
52
53
k
X
j1
lna0wj
54
Here, awj is the water activity of the binary mixture with the
j component.
The Ross equation has been applied by several researchers, e.g., Chirife et al.,[51] Herman et al.,[52] and Roman
et al.[34] The water activities of non-solute parts were also
evaluated with the Henderson equation based on literature
data for starch, protein, and fiber by Roman et al.[34]
ARTIFICIAL NEURAL NETWORK MODELING
Artificial neural network (ANN) modeling is a method
to describe relations between independent and dependent
variables when the explicit form of mapping is not known.
In recent years, the concept of ANN has gained wide
acceptance in food engineering for predictive modeling.
In case of sorption isotherm prediction, Myhara et al.,[53]
Myhara and Sablani,[54] and Kaminski and Tomczak[55]
used ANN modeling for different food materials. Myhara
et al.[53] demonstrated that when chemical composition
data is combined with physical data through an ANN
approach, significant improvements in the prediction of
water sorption behavior can be achieved.
COMPARISON OF BET AND GAB MODELS
The BET and the GAB isotherms are closely related as
they are derived from the same statistical model. The
GAB model represents a refinement over the BET model
and shares with it two original BET constants (M0, the
monolayer capacity, and C, the energy constant) and owes
its versatility due to the introduction of a third constant
(K). The regression of an experimental sorption data by
each of these two isotherms will give two sets of values of
M0 and C. The same type of differences between both sets
of values of M0 and C have always been observed:
M0B < M0G ;
CB > CG
55
CB aw M0B
1 aw 1 CB 1aw
56
To obtain the two characteristic constants, the BET equation is linearized by the following function
F BET
aw
1
CB 1
aw
1 aw M CB M0B CB M0B
57
924
CG Kaw M0G
1 Kaw 1 CG 1Kaw
where
1
CGG M0G
64a
CGG 1 21 K
CGG M0G
64b
1 KCGG 1 K
CGG M0G
64c
A
B
58
and
CG K CGG
59
aw
1
CG 1
aw
1 Kaw M CG KM0G CG M0G
60
F GAB
1 aw M
1 aw
A C B Caw
C
1 aw
65
F BETi a0 a1 awi
2
minimum
66
i1
1
CB M0B
CB 1
CB M0B
67a
67b
and hereafter
PBET a0 a1 awi
61
aw
CG KM0G CG M0G
1 aw
CGG 1 21 K
1
aw
CGG M0G
CGG M0G
1 KCGG 1 K
aw
62
CGG M0G
1 aw
F BET A Baw
63
M0B
CB
1
a00 a01
a00 a01
a00
68a
68b
925
minimum
69
A C Cd=d0
70a
a1 B C Cd1 =d
70b
71a
d1 aw =1 aw n 1=1 aw aw
71b
d na2w aw 2
71c
1
1=fA B C d0 d1 =d 2g 72a
a00 a01
and
CB
These functions are always greater than unity.[56] Therefore, Eqs. (73a) and (73b) reproduce the inequalities
(Eq. (55)) if K<1.
The marked differences between the BET and GAB constants are noteworthy. The GAB isotherm, is an improved
version of the BET model, by the introduction of the third
parameter, K, characterizing the state of sorbed molecules
beyond the first layer.
RESEARCH RESULTS FOR SORPTION ISOTHERMS
OF FOOD MATERIALS
Modeling of sorption behavior of a variety of food
materials has been carried out by many researchers. A list
of recent research done after 2000 on different types
of food materials is presented in Table 1. This list is
not exhaustive; comprehensive information of sorption
isotherms for different food materials has been
published.[39,5860]
STATISTICAL TESTING OF SORPTION MODELS
Statistical analysis of an isotherm may be quantified
through five standards: the coefficient of determination
(R2), the residual sum of squares (RSS), the standard error
of the estimate (SE), the mean relative deviation (MRD),
and the plot of residuals. The coefficient of determination
is a statistical measure of how closely two variables are
related. The coefficient of determination is a dimensionless
index that ranges from 0 to 1 and reflects the extent of linear relationship between two data sets.
The residual sum of squares (RSS) is defined as
RSS
n
X
M MCal 2
75
i1
a00 a01
a00
72b
73a
73b
74a
74b
df
df
Here, df represents the degrees of freedom of the fitting
equation. If a large data set is available, Eq. (76) is simplified to
r
RSS
SE
77
n
The mean relative deviation (MRD) is an absolute value
because it gives the mean divergence of the estimated data
from the measured data
926
TABLE 1
Recent works on sorption isotherms of food materials
Temperature (C)
Food product
Berries
Mushroom
4, 13, 27
4, 13, 27
3070
25, 30, 35
Cocoa beans
Starch, potato
Pumpkin seed flour
Cured beef and pork
Chicken meat
Hazelnuts
Rough rice
3060
3060
10, 25, 40
10, 20, 25, 35, 49
430
25
0, 5, 10, 15, 20, 25, 30, 35
Yogurt powder
Gelatine gel
Crystalline lactose powder
35
20
12, 20, 30, 40
MRD
n
1X
jM MCal j
M
n i1
aw
Reference
0.110.87
0.120.75
0.200.80
0.080.94
GAB
GAB
Chung-Pfost
BET (aw < 0.5)
Harkins-Jura (aw > 0.5)
GAB, Halsey
GAB, Ferro-Fontan, Peleg
GAB
Peleg, GAB
Ferro-Fontan, GAB
GAB
Modified Chung-Pfost,
modified Henderson
Modified Chung-Pfost
Ferro-Fontan
Timmermann-GAB, GAB
63
63
64
65
0.110.83
0.050.95
0.110.85
0.100.94
0.250.94
0.110.90
0.2590.935
0.40.99
0.750.98
0.110.98
78
Plotting of the residuals (MMCal) against the independent variable is also used as a measure of the distribution of errors. If the model is correct, then the
residuals should be only random independent errors with
a zero mean, constant variance and arranged in a normal
15
66
67
68
69
70
71
72
20
73
TABLE 2
Data on goodness of fit of selected models for sardine sheet at selected temperatures (25, 40, and 50C) and water activity
(0.110.84)
Coefficients of linear regression
Isotherm
BET
Oswin
Smith
Hasley
Henderson
Chung and Pfost
Iglesias and Chirife
GAB
Peleg
Modified Oswin
Modified Henderson
Modified Chung-Pfost
0.9390.978
0.9630.984
0.9540.974
0.9590.994
0.9310.974
0.8850.906
0.9900.993
S.E.
R2
S.E.
0.6480.968
0.1010.139
0.0120.022
0.0650.164
0.1520.237
0.250.299
0.0060.008
0.9830.996
0.9860.997
0.9540.974
0.9700.994
0.9480.978
0.9310.953
0.990.993
0.9890.996
0.9360.968
0.8130.995
0.9480.978
0.9310.953
0.0040.009
0.0040.009
0.0120.021
0.0200.042
0.360.054
0.060.067
0.0060.008
0.0040.007
0.0140.026
0.0050.029
0.0360.054
0.0600.067
927
TABLE 3
Pattern of residual plots of selected models
Model
BET
Peleg
Oswin
Hasley
GAB
Modified Henderson
Modified Chung-Pfost
Iglesias and Chirife
Patterned
Patterned
Scattered
Patterned
Scattered
Scattered
Patterned
Patterned
FIG. 4. Residual plot of sorption data for sardine fish at 40C (GAB
isotherm).
AN EXAMPLE
Published sorption data[62] (water activity range 0.11
0.84) of freeze-dried sardine fish at 25, 40, and 50C
was selected for comparison of the different sorption isotherm models. Both linear and nonlinear approaches were
used to estimate the model coefficients. Standard error
and R2 values of different isotherm models for both linear
and nonlinear forms are given in Table 2. The R2 values
of the nonlinear models were always higher than that of
the linear equations. Similarly, standard error values were
also lower in nonlinear cases compared to the linearized
form, which suggests that nonlinear forms should be used
for estimation of model parameters. After choosing few
sorption models with higher R2 and lower SE values, their
residual plots were checked. Residual plot patterns of different models are presented in Table 3. Among all the
TABLE 4
Calculated GAB parameters at selected temperatures
Temperature
(C)
25
40
50
Monolayer moisture
content
(kg water=kg
dry matter)
2.0699
0.6834
7.3495
1.1172
1.0697
1.2121
0.0768
0.1857
0.1857
CONCLUSION
Theoretical aspects of sorption of water and commonly
used mathematical models to describe sorption isotherms
are discussed. Statistical criteria for selection of a model
have also been presented. Both the GAB and Oswin equations presented high R2 and low standard error values and
scattered residual pattern for freeze-dried sardine fish. But
because of lack of a temperature term in the Oswin equation, the GAB model is recommended for fitting the sorption data. From this discrimination approach based on
statistical measures, it is possible to select the best model
equation for describing experimental sorption data.
NOMENCLATURE
aw
A, A0 , B, r, k1, k2, n1, n2
C
FIG. 3. Sorption isotherm for sardine fish at 25, 40, and 50 C (GAB
isotherm).
df
ERH
Water activity
Constants
Dimensionless parameter
related to heat of sorption
of monolayer region
Degrees of freedom
Equilibrium relative
humidity
928
H and H0
K2
M, M1, M2
MC
MCal
MRD
M0
M0B(B), M0G(G), CB(B), CG(G)
P
P0
Q
Q12
R
RSS
SE
T
w
X
Greek Letters
a, a0
c
DHd
DHS
DHvap
d; d0 ; d1 ; a0 ; a1 ; a0 ; a1
Functions containing a
fourth dimensionless
parameter h
Dimensionless GAB
parameter related to heat of
sorption in multilayer
region
Dimensionless parameter
Moisture content
Characteristic moisture
content
Estimated value
Mean relative deviation
Monolayer moisture content on the internal surface
Constants
Water vapor pressure in the
food material at any given
temperature
Vapor pressure of pure
water at that temperature
Net heat of sorption of
water
Net heat of desorption
Universal gas constant
Residual sum of squares
Standard error of the
estimate
Absolute temperature
M=M0
Kaw
Constants
Parameter which accounts
for the structure of sorbed
water
Total heat of sorption in
the food
Net isosteric heat of sorption
Heat of vaporization of
water
Functions
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