Journal of Food Engineering 48 (2001) 1931

www.elsevier.com/locate/jfoodeng

Water sorption isotherms of foods and foodstus: BET or GAB

parameters?
E.O. Timmermann a, J. Chirife b,*, H.A. Iglesias b
a


Facultad de Ingeniera, Universidad de Buenos Aires, and PRograma de INvestigaciones en SOlidos
(PRINSO), CITEFA-CONICET,
Zufriategui 4380, 1603 Villa Martelli, Provincia de Buenos Aires, Argentina
b
Departamento de Industrias, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria,
1428 Buenos Aires, Argentina
Received 3 March 2000; accepted 8 August 2000

Abstract
The aim of the present work is to solve the dilemma about the dierences between the values of the monolayer and the energy
parameters obtained by the regression of water sorption data by foods and foodstus using the Brunauer, Emmett and Teller (BET)
two-parameter isotherm or the Guggenheim, Anderson and de Boer (GAB) three-parameter isotherm. It is shown that the GAB
values are more general and have more physical meaning, and that the two BET parameters can be calculated in terms of the three
GAB-parameters. Furthermore, the marked dependency of the BET constants on the regression range as well as the typical upswing
at higher water activities observed in the so-called BET plots are explained. It is also shown that the rough agreement early reported
by L. Pauling, J. Am. Chem. Soc. 67 (1945) 555557 between monolayer values and number of polar groups in the aminoacid side
chain in several proteins is enhanced if the former are evaluated by means of the GAB sorption equation. 2001 Elsevier Science
Ltd. All rights reserved.
Keywords: Sorption isotherms; Monolayer values; Energy constants; BET equation; GAB equation; Proteins

1. Introduction
In the past, the well-known Brunauer, Emmett and
Teller (BET) sorption isotherm was the model that had
the greatest application to water sorption by foods and
foodstus (Labuza, 1968; Iglesias & Chirife, 1976a),
although it was known to hold only for a limited range
of water activity (aw ), up to only 0.30.4. Two familiar
constants are obtained from the BET model, namely the
monolayer moisture content, xmB , and the energy constant, cB . Despite the theoretical limitations of the BET
adsorption analysis, the BET monolayer concept was
found to be a reasonable guide with respect to various
aspect of interest in dried foods (Karel, 1973; Iglesias &
Chirife, 1982).
In more recent years, the Guggenheim, Anderson and
de Boer (GAB) isotherm equation has been widely used
to describe the sorption behavior of foods (Bizot, 1983;

Corresponding author. Fax: +54-1-7943344.

E-mail addresses: etimmer@citefa.gov.ar (E.O. Timmermann),
jchirife@satlink.com (J. Chirife).

Weisser, 1985; Maroulis, Tsami, Marinos-Kouris, &

Saravacos, 1988; Iglesias & Chirife, 1995). Having a
reasonable small number of parameters (three), the
GAB equation has been found to represent adequately
the experimental data in the range of water activity of
most practical interest in foods, i.e., 0.100.90. The
GAB equation has been recommended by the European
Project Group COST 90 on Physical Properties of
Foods (Wolf, Spiess, & Jung, 1985) as the fundamental
equation for the characterisation of water sorption of
food materials.
Both isotherms (BET and GAB) are closely related as
they follow from the same statistical model (Timmermann, 1989). By postulating that the states of water
molecules in the second and higher layers are the same
as each other but dierent from that in the liquid state,
the GAB model introduced a second well-dierentiated
sorption stage for water molecules. This assumption
introduces an additional degree of freedom (an additional constant, k) by which the GAB model gains its
greater versatility. One of the three GAB constants is, as
in the BET equation, the monolayer capacity now denoted by xmG . The other two GAB constants, denoted

0260-8774/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
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20

E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

by cG and k, are energy constants as the BET constant

cB , but with slighly dierent physical meanings. The
BET constant cB is related logarithmically to the difference between the chemical potential of the sorbate
molecules in the pure liquid state and in the rst sorption layer. On the other hand, the GAB constant cG is
related to the dierence of this magnitude in the upper
layers and in the monolayer, while the constant k is
related to this dierence in the sorbate's pure liquid state
and in the upper layers, and the product of both
(cG k cBG ) represents the equivalent to cB of BET. It is
to be mentioned that the third GAB constant k is,
practically without exception, near to but less than unity
(Chirife, Timmermann, Iglesias, & Boquet, 1992), a fact
which constitutes a denitive characteristic of this isotherm (Timmermann, 1989).
Now, if both isotherms (BET and GAB) are used
for regression analysis of sorption data, two sets of
values of the monolayer capacity and of the energy
constant are obtained, which should be comparable.
However, it has been observed by several authors (van
den Berg, 1981; Kim, Song, & Yam, 1991; Duras &
Hiver, 1993; Lagoudaki, Demertzis, & Kontominas,
1993) that
xmB BET < xmG GAB;

cB BET > cB GAB:

That is, the monolayer capacity by BET is always less

than the GAB value, while the energy constant cB by BET
is always larger than the GAB value. These inequalities
set up the dilemma, about which values resemble a better
physical reality, a dilemma not solved so far.
Following a general approach given elsewhere by one
of us (Timmermann, 2000), it will be shown here that
there exits mathematical (and physical) reasons for the
inequalities set by Eq. (1) and that the GAB values are
the values of better physical reality. For this purpose,
several experimental data for water sorption in foods
and foodstus are analysed and in each case, the inequalities (Eq. (1)) are qualitatively and quantitatively
explained. Hydration of proteins, in terms of the attachment of one water molecule to each polar group of
the side chains of the aminoacids (Pauling, 1945), is also
discussed in terms of the BET and GAB monolayer
values.
2. BET regression vs GAB regression
2.1. The BET isotherm
The classical BET equation, giving the amount of
water x(aw ) sorbed by a unitary amount of sorbant in
terms of the water activity aw , is the following:
BET : xaw xmB cB aw =1 aw 1 cB 1aw :

It is well known that the two constants, the monolayer

value xmB and the energy constant cB , are obtained from
the so-called BET plots (Iglesias & Chirife, 1976a). In
synthesis, in these plots, the linearised form, F(BET), of
this isotherm
FBET  aw =1 aw xaw
1=cB xmB cB 1=cB xmB aw

is drawn in terms of aw . This function should be linear if

the BET assumptions apply, and within the linear range,
using a linear least-square analysis, F(BET) is adjusted
by a linear polynomial
PBETi a0 a1 xi

by minimising the squares sum over the n experimental

points (index i)
in
X
2

FBETi a0 a1 xi minimum;

i1

where xi stands for aw at the point i. The coecients a0

and a1 are given by the solutions of the system of normal
equations associated to the extremum condition (5).
According to Eqs. (3) and (4), the least-squares estimates of a0 and a1 , a^0 and a^1 , are related to the BET
constants by
a^0  1=cB xmB ;

a^1  cB 1=cB xmB

and herefrom


xmB 1= a^0 a^1 ;



cB a^0 a^1 =^
a0

6
7

relations by which the BET constants are calculated. It

should be noted that the energy constant cB is inversely proportional to the intercept a^0 of the linear
regression polynomial P(BET) of Eq. (3) and, therefore, cB is very sensitive to the value of a^0 , which is
usually very low.
Usually, and this was observed by many workers, the
BET plots give only an apparent linear plot at low
water activities (0.05 < aw < 0.30.4) and over this range
the BET regression is performed (Iglesias & Chirife,
1976a). For aw > 0.30.4, always deviation from linearity is observed with an upswing of F(BET) indicating
that at higher water activities less water is sorbed than
that predicted by the BET equation as shown in Fig. 1
for the BET plots of water sorption for various food
materials.
2.2. The GAB isotherm
On the other hand, the GAB equation is
GAB :
xaw xmG cG kaw =1 kaw 1 cG 1kaw ;

E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

where
cBG  cG k:

To determine the three constants of the GAB equation,

several methods can be employed. In the present context, a linearisation method of the GAB isotherm analogue to that of the BET model (Eq. (3)) is the most
adequate; the other methods will be examined latter. To
linearise the GAB isotherm, the following function
F(GAB) applies:
FGAB  aw =1 kaw xaw
1=cG kxmG cG 1=cG xmG aw :

10

Thus the so-called GAB plots i.e., F(GAB) vs aw

(Anderson, 1946; Gascoyne & Pethig, 1977; Timmermann, 1989) should be linear in aw , if the correct kvalue is used for the experimental F(GAB). In practice,
one looks for the k-value which best linearises F(GAB)
vs aw ; a too high k-value determines an upward curva-

21

ture in these plots as in the BET plots and a too low kvalue determines a downward curvature. Analytically,
the minimum of the sum of the least squares of the linear
regression of Eq. (10) in terms of variable k determines
the best k-value. Moreover, from the two linear regression coecients of F(GAB), the other constants xmG
and cG can be obtained.
The corresponding representation of F(GAB) vs aw is
also given in Fig. 1 (corresponding values of k have been
taken from Table 1). The linearisation of experimental
data through Eq. (10) is possible within the range
0.05 < aw < 0.8, which represents a much broader applicability range of the GAB isotherm compared with the
BET equation. Furthermore, at higher water activities,
these GAB plots present a downward deviation due to
the appearance of the third sorption stage (Timmermann & Chirife, 1991), an eect, which determines the
upper limit of application of the GAB isotherm.
2.3. The relation between F(BET) and F(GAB)
As already stated, the results of both regressions for
the same set of experimental data lead to the inequalities
stated by Eq. (1). This dilemma may be tackled in the
following way. F(GAB) is related to F(BET) by
FBET aw =1 aw xaw
1 kaw =1 aw FGAB

11

and by introducing here the expression (10) of F(GAB)

and multiplying out the resulting expression, a second
relationship for F(BET), named F (BET), is obtained,
now in terms of the three constants of the GAB isotherm. It results
F BET  1 kaw =1 aw 1=kcG xmG
cG 1=cG xmG aw



1=cBG xmG cBG 1 21 k

=cBG xmG aw


1 k cBG 1 k

=cBG xmG aw =1 aw ;

12

where Eq. (9) has been used to introduce cBG . This

second expression for F(BET) shows that, if k < 1,
F(BET) will not be linear in aw , but will present an hyperbolic behaviour
F BET A Baw C aw =1 aw
A C B Caw C=1 aw ;

13

where
Fig. 1. (a) Fish our; (b) corn barn; (c) wheat starch BET and GAB
plots for food materials. Note that GAB plots are displaced 0.02 units
downwards to avoid overlapping. Values of the k-constant for sh
our, corn bran and wheat starch are 0.81, 0.76 and 0.68, respectively.

A  1=cBG xmG ;

B  cBG 1 21 k =cBG xmG ;

C  1 k cBG 1 k =cBG xmG :

14

xmB (calc)

cB (calc)

10

Tomato (A)
30C/NEF

Corn bran (A)

25C/NEF

Fish our
(25C)/NEF

Potato starch (native) (A)

20C/NEF

Wheat starch (native) (A)

20C/NEF

Wheat (D)
25C/NEF

Chicken (cooked) (D)

19.5C/NEF

6.81 0.06
0.88

7.64 0.41
5.50

7.93 0.17
2.57

8.07 0.24
3.84

4.91 0.65
4.17

6.12 0.36
3.10

14.5 1.1
5.49

4.56 0.19

5.92 0.14

14.3 0.5

22.6 1.1

21.7 5.7

7.0 0.2
1.31

7.73 0.59
3.04

32.8 4.7
7.95 0.54
(0.04040.4013)b

26.9 4.8
8.22 0.45
(0.03990.4027)b

5.00 1.1
(0.1150.443)b

9.5 1.3
(0.0630.379)b

61.8 67.5
(0.1130.432)b

21.5 3.5

22.7 8.9

38.0 20.9
3.64

25.0 7.5
2.52

5.8 0.5
1.32

10.3 0.6
1.36

68.8 39.5
2.48

11

16

7.75 0.31
1.76

10.24 0.1
5.40

9.89 0.21
1.94

9.79 0.27
3.11

5.80 1.23
5.58

7.21 0.75
3.38

16.6 0.6
2.38

xmG

0.81 0.33

0.76 0.20

0.83 0.06

18.7 0.8

18.6 1.0

0.86 0.07

0.62 0.02

26.7 3.8
0.68 0.04
(0.04040.8663)b

20.4 3.4
0.75 0.05
(0.03990.8887)b

5.1 3.7
(0.1150.848)b

9.8 4.5
(0.0630.716)b

31.4 9.3
(0.1130.836)b

cG

nG

cB (exp)

nB
xmB (exp)

GAB (range: 0:05 6 aw 6 0:8)

BET (range: 0:05 6 aw 6 0:4)

Table 1
BET and GAB constants for water sorption in foods and foodstusa

16.1 1.9

11.4 0.9

18.1 2.2

15.4 3.6

4.1 4.7

7.5 5.4

26.1 9.6

cG k

22
E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

Turkey (cooked) (D)

22C/NEF

Corn our (degermed)

25C/NEF

Rice (A)
25C/NEF

Corn (D)
30C/NEF

Wheat gluten (A)

3C/NEF

Skimmilk (A)
34C/NEF

3.92 0.20
4.68

5.33 0.68
1.02

7.39 0.26
3.67

7.74 0.23
2.38

7.93 0.38
7.47

6.24 0.44
3.99

5.36 0.31
3.49

52.6 31.7
(0.10.4)b

21.9 14.8
(0.10.4)b

22.6 4.0

32.9 7.4
(0.10.4)b

79 61.4

7.0 1.0

7.7 0.9

3.87 0.11
1.32

5.36 0.24
1.52

7.49 0.55
2.96

7.94 0.60
2.83

7.91 0.64
5.80

6.20 0.30
0.95

5.35 0.21
0.37

67.3 28.9

21.7 4.9

23.3 8.9

31.1 16.6

138 314

7.2 0.7

7.8 0.7

10

10

4.27 0.11
2.98

6.38 0.54
4.40

9.78 0.21
1.27

11.0 0.53
2.04

10.27 0.16
1.07

6.92 1.59
3.74

6.29 0.26
3.87

38.0 10.2
(0.10.9)b

16.4 7.6
(0.10.8)b

18.8 2.3

19.2 5.3
(0.10.8)b

42.4 5.4

7.50 0.45
(0.050.9)b

7.41 1.22
(0.050.9)b

0.876 0.05

0.78 0.15

0.633 0.037
7

0.58 0.08

0.59 0.03

0.79 0.10

0.82 0.07

33.0 13.1

12.9 8.5

11.9 2.1

11.2 4.6

25.1 4.3

5.9 1.0

6.1 1.7

A: adsorption, D: desorption; xm : in g H2 O/100 g dry matter; nB , nG : number of experimental points; (exp): obtained using the direct regression by F(BET); (calc): calculated in terms of the GAB
constants using F (BET); NEF: normalized error function (Eq. (21)). Source of sorption data: Tomato: Kiranoudis, Maroulis, Tsami, and Marinos-Kouris (1993); Corn bran: Duras and Hiver
(1993); Fish our: Labuza, Kaanane, and Chen (1985); Potato starch (native): van den Berg (1981); Wheat starch (native): idem; Wheat: Hubbard, Earle, and Senti (1957); Chicken (cooked): Taylor
(1961); Turkey (cooked): King, Lam, and Sandall (1968); Corn our (degermed): Kumar (1974); Rice: Nemitz (1963); Corn: Hubbard et al. (1957); Wheat gluten: Bushuk and Winkler (1957);
Skimmilk: Berlin, Anderson, and Pallanach (1970).
b
Other evaluation range than that stated in the headings.

Turkey (cooked) (A)

22C/NEF

E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

23

24

E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

Conversely, if k 1, Eqs. (3), (13) and (14) become

identical as C (k 1) 0.
Eq. (13) readily explains qualitatively and quantitatively (Eq. (14)) the usually observed upswing in the
BET plots at aw > 0.40.5, if k < 1. In the graphs of
Fig. 1, F (BET) has been represented in terms of the
corresponding GAB constants taken from Table 1. It is
shown that this function reproduces quite well the (nonlinear) experimental F(BET) within the whole GAB
applicability range 0.05 < aw <0.8.
Furthermore, it is evident that, if F(BET) responds to
Eq. (13) but analysed using Eq. (3), the so-obtained (and
associated to the BET isotherm) values of xmB and cB
will certainly be functions of the three GAB constants
xmG , cG and k through Eqs. (12)(14) and of the aw interval over which the regression is performed. And this
functional dependence determines the dierence between
the BET and the GAB sets for the monolayer capacity
(xm ) and the principal energy constant (cB ) and, therefore, the inequalities stated by Eq. (1).


2.4. BET regression by F (BET)

The second expression (13) of F(BET) may also be
adjusted by the same linear polynomial (4), but now
using an analytical formulation as F (BET) is known as
a function of aw and not by a set of numerical data. The
calculation implies the adjustment of a function of a
known functional dependence of a higher degree than
one to a straight line. This regression of F (BET) can be
made either in a discrete form or in a continuous form,
as it is shown elsewhere (Timmermann, 2000).
In the discrete procedure, F (BET) given by Eq. (13)
is explicited into condition (5), which becomes
in
X

f A C B Cxi C=1 xi a0 a1 xi g

i1

minimum

15

and this expression can now be solved analytically for a0

and a1 in the usual way of least squares. As it is to be
expected, it results (Timmermann, 2000) that a0 and a1
become functions of the constants A, B and C of Eq.
(13) on one side, and of regression sums over the values
of the independent variable xi on the other.
The nal expressions are the following:
a0 A C Cd0 =d;

16a

a1 B C Cd1 =d;

16b

where a0 and a1 are the minimum squares estimates in

terms of F (BET). The functions d, d0 and d1 contain
only the regression sums of aw over the employed regression interval with the following signs: d0 /d < 0, d1 /
d > 0 and d0 /d + d1 /d > 0 for aw < 1 (Timmermann, 2000).

The corresponding relations are, where Gaussian

brackets have been used,
 
d0  1=1 aw a2w aw =1 aw aw ;
17a
d1  aw =1 aw n 1=1 aw aw ;
 
d  n a2w aw 2 :

17b
17c

n is the number of data included in the regression.

As the Eqs. (6) and (7) remain valid, the BET constants are now given by
xmB 1=a0 a1
1=f A B C d0 d1 =d 2g

18a

and

cB a0 a1 =a0
f A B C d0 d1 =d 2g=f A C d0 =d 1g:
18b
Finally, by Eq. (14) A, B, C f(xmG , cG , k) and after
some algebra, explicit expressions for xmB and cB in
terms of the three GAB constants are obtained (Timmermann, 2000):


19a
xmB xmG = 1 21 k=cBG Rm
and



cB cBG 1 21 k=cBG Rc ;

19b

where the functions Rm and Rc are given by




Rm  1 1 k cBG 1 k = cBG


21 k d0 d1 =d 2

20a

and



Rc  Rm = 1 1 k cBG 1 kd0 =d 1 :

20b
These functions are always greater than unity (Timmermann, 2000). In consequence, Eqs. (19a) and (19b)
reproduce the inequalities (1) if k < 1.
Eqs. (19a) and (19b) explicit and quantify the dierences between the BET set (xmB ) cB ) and the GAB set
(xmG ) cBG ) of constants. These dierences are directly
related to k < 1 through the factor (1 ) k) present in
these equations and hence, explain the inequalities set in
Eq. (1). They become more important with decreasing
values of k as well as with an increase of the regression
interval. On the other hand, if k 1, all these expressions coincide with the classical results shown before.
Eqs. (16a), (16b), (19a) and (19b) have been used to
calculate the linear correlation of F(BET)GAB in terms of
the corresponding GAB constants and for the same
water activity interval used for the empirical BET
equation (numerical values are stated in Table 1); the
results are shown in Fig. 1(ac). The reproduction of the
empirical BET constants and of the inequalities stated in

E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

Eq. (1) are quite acceptable. For the case of sh our

(Fig. 1(a)), a slight dierence between the linear
F(BET)exp and the linear F(BET)GAB is observed, a difference which is determined by the empirical dispersion
of the experimental sorption data. In the case of corn
bran (Fig. 1(b)), this dispersion is less and the coincidence of F(BET)exp and F(BET)GAB is better. Finally, in
the case of wheat starch (Fig. 1(c)), this dispersion is
minimal and F(BET)exp and F(BET)GAB become practically undistinguishable.
Thus, the approach given here solves the dilemma of
the inequalities stated by Eq. (1). It also explains the
restricted range of linearity of the BET regression, the
dependence of the values of the BET constants on

25

the activity range used for the regression, and the upswing of the BET plots at higher water activities.

3. Analysis of water sorption data for various foods and

food materials
Two groups of sorption systems were analysed, (1)
various foods and foodstus, and (2) proteins. The
second group corresponds exclusively to the comprehensive data set of water sorption by proteins due to
Bull (1944), where this author tested the applicability
of the BET isotherm to these sorption systems. The
results are presented in Tables 1 and 2, and in Fig. 2.

Table 2
Monolayer moisture contents for various proteinsa;b
Protein

BET (range: 0:05 6 aw 6 0:3)

GAB (range: 0:05 6 aw 6 0:8)

NB

xmB (exp)

cB (exp)

xmB (calc)

cB (calc)

nG

Collagen

21.0 1.3

18.6 1.4

Seroalb.

13.3 0.7

Elastinc

17.3 2.1

Wool

11.5 0.7

a=b-pseudo
Globulin
c-pseudo
Globulin
Lactoglob.
Crist.
Lactoglob.
f.dried
Eggalbum.
Coag.d
Egg album
f.dried
Egg album
Not f.dried
c-zein

10.2 0.19
NEF 0.92
9.11 0.18
NEF 1.01
6.71 0.12
NEF 0.75
6.39 0.2
NEF 2.2
7.00 0.18
NEF 0.99
7.11 0.13
NEF 0.75
7.09 0.13
NEF 0.76
6.77 0.12
NEF 0.59
6.390.12
NEF 0.60
5.46 0.11
NEF 0.76
6.02 0.11
NEF 0.72
6.45 0.13
NEF 0.76
3.93 0.06
NEF 0.64
4.11 0.08
NEF 0.64
4.33 0.09
NEF 0.86
11.6 0.12
NEF 0.10

17.2 1.1

Gelatin

9.64 0.15
NEF 0.94
8.47 0.48
NEF 3.22
6.52 0.26
NEF 1.75
6.54 0.98
NEF 11.1
6.73 0.31
NEF 1.87
6.72 0.26
NEF 1.90
6.74 0.32
NEF 2.32
6.62 0.40
NEF 1.90
5.910.08
NEF 0.49
5.19 0.12
NEF 0.99
5.64 0.27
NEF 1.99
6.28 0.16
NEF 1.05
3.83 0.07
NEF 0.83
4.10 0.15
NEF 1.43
4.15 0.24
NEF 2.40
5.94 0.29
NEF 3.27

13.7 0.7

13.5 0.7

9.3 0.3

9.00.3

4
4
4
4
4
4
4

b-zein

Silk

Salmine

23.9 6.1
14.3 1.7
15.0 8.0
12.6 1.6
16.3 2.1
15.7 2.4
9.7 1.3
10.80.4
13.2 0.9
13.3 1.8
12.1 0.8
13.7 0.7
12.5 1.2
14.3 0.2
40.0 13.6

11.5 0.6

10

11.3 0.5

11.4 0.6

12.6 0.5

12.5 0.7

12.8 0.7

2.2 0.02

xmG

cG

cG k

11.5 0.5
NEF 3.01
10.3 0.8
NEF 4.31
7.55 0.42
NEF 2.57
7.61 1.3
NEF 9.2
8.47 0.52
NEF 2.42
7.99 0.45
NEF 3.28
7.98 0.41
NEF 2.84
7.72 0.45
NEF 1.93
7.350.52
NEF 3.39
6.30 0.26
NEF 2.70
6.88 0.47
NEF 3.06
7.43 0.30
NEF 1.68
4.37 0.21
NEF 4.42
4.75 0.21
NEF 1.88
5.00 0.30
NEF 2.62
13.6 19.4
NEF 1.54

17.3 4.4

0.80 0.09

13.8 5.1

18.7 7.8

0.78 0.14

14.6 8.7

13.6 3.7

0.81 0.10

11.0 4.4

15.5 13.8

0.77 0.32

11.9 15.5

12.2 3.6

0.71 0.11

8.7 3.9

13.9 3.9

0.81 0.11

11.3 4.5

13.8 3.5

0.81 0.10

11.2 4.2

9.5 2.4

0.81 0.10

7.7 2.9

9.32.8

0.800.13

7.43.5

11.8 2.3

0.78 0.07

9.3 2.6

11.6 3.7

0.80 0.12

9.2 4.3

11.7 2.2

0.78 0.07

9.2 2.5

12.8 3.0

0.83 0.09

10.5 3.6

12.9 2.8

0.77 0.08

9.9 3.2

13.2 3.9

0.77 0.11

10.2 4.4

2.15 6.6

0.89 1.4

1.9

nB , nG , number of experimental points; xm : in g H2 O/100 g dry matter; (exp): obtained using the direct regression by F(BET); (calc): calculated in
terms of the GAB constants using F (BET); NEF: normalized error function (Eq. (21)).
b
Experimental data: Bull (1944).
c
BET range: 0.050.4.
d
GAB range: 0.050.9.
e
The isotherm presents two branches which are incompatible with each other; at aw 0:050:3 BET applies, but at aw 0:30:8, the application of
GAB is quite questionable (see error gures) and the BET and GAB monolayer and energy values cannot be related.

26

E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

Fig. 2. Experimental and calculated water sorption isotherms for

(a) foods/foodstus and (b) proteins (Bull). Note that the isotherms
have been displaced upwards a certain amount of units for a better view.

The left-side sections of Tables 1 and 2 present the sets

of BET constants obtained by (a) the direct regression
by F(BET) (Eqs. (6) and (7)) and (b) in terms of the
GAB constants using F (BET) [Eqs. (14), (16a)(18b)];
and the right-side section contains the set of GAB
constants obtained using a parabolic regression (Eq.
22) (see also Fig. 3). The general regression ranges are
given in the headings, with exceptions indicated in
each case. The error of each numerical value has been
calculated using the regression covariance of each
parameter. Finally, the normalised error function
(NEF), dened as
"
NEF 100

in
X

i1

x exp xcalc

2
i

!, #1=2,
n

xm

21

is also given. This function is related to, but simpler than

the relative percentage root, mean square value often
used in the literature.

It can be seen (see also the top graphs of Fig. 4) that

GAB monolayer values are about 1040% higher than
the BET value, while the energy constant cBG is much
lower (3550% and even more) than the BET value. In
the same way, the errors of the energy constant values
are much stronger (1525% up to 6070% and more)
than that of the monolayer (48%). It is also to be noted
that the error of the third GAB constant, k, is in the
order 1015% and therefore, the value of this constant
should be given with only two signicant gures. For
the constant k, the values already stated elsewhere
(Chirife et al., 1992) for proteins and protein foods
(k  0.8, range 0.780.85) and for starchy foods (k  0.7,
range 0.650.75) are conrmed. A lower value of k indicates a much less structured state of the sorbate in the
layer following the monolayer, the so-called GAB layers, as in the sorbate's pure liquid state (Timmermann,
2000).
In food science studies, preferred or almost exclusive
attention is paid to the monolayer value (Karel, 1973;
Iglesias & Chirife, 1976b). However, the values of the
energy constants should not be overlooked nor ignored
because they are simultaneous outputs of the regression
processes and they inuence the sigmoidal shape of the
isotherms, i.e., the form of the normalised x/xm vs aw
plot, since cB and cG determine the more or less pronounced form of the `knee' at the lower water activity
range. On the other hand, the third GAB constant k
determines the prole of the isotherm at the higher
water activity range, regulating the upswing after the
plateau at medium water activity range. Higher values
of k determine a more pronounced upswing. This can be
readily observed in Fig. 2; proteins and protein-foods
(k  0.8) present a much more noticeable upswing than
starchy foods (k  0.7).
Finally, the function NEF is a measure of the experimental dispersion of the sorption data; good (mean)
values of NEF are in the order 25%. If this dispersion is
homogeneous over the whole GAB range, NEF has
coincident values for the BET as well as for the GAB
regressions indicating the much better ability of the
GAB equation to represent the data as it embraces a
much broader range of water activity. But if this dispersion is heterogeous (in the BET region dierent than
in the GAB region), then NEF oscillates about the same
values being in some cases the BET values lower than
the GAB values and in others the opposite is observed,
but always within the range 25%. A case markedly
beyond this range is the protein elastin, the sorption
data of which present NEF values of 9% (GAB) to 11%
(BET). Morover, the NEF values of the calculated BET
parameters by Eqs. (19a) and (19b) using the GAB
constants are due to the intrinsic hyperbolic curvature of
F (BET) (Eqs. (12) and (13)) over the BET range of
activities. The experimental NEF values of the BET
regression include this eect and therefore, by the

E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

27

Fig. 3. (a) Inverse and (b) parabolic plots for various foods, foodstus and proteins. Symbols: experimental data. The arrows in the graphs indicate
the upper limit of each equation.

experimental dispersion of the data, the NEF values

uctuate (upwards or downwards) about the `theoretical' values indicated by the former.
Fig. 2 shows calculated food isotherms obtained by
the BET and GAB regressions as well as by the BET
constants calculated in terms of the GAB parameters,
using the constants given in Tables 1 and 2. The limited
range of applicability of the BET equation and the
ability of the GAB equation to represent the experimental data up to aw  0.85 is observed in all cases; as
well as the good agreement between calculated BET
isotherm by the GAB constants with the BET curve
obtained directly by the regression of the experimental
data.
To determine the GAB constants, a simple method
was used which is straightforward; it uses the so-called
transformed form of the GAB equation (Schaer & Ruegg, 1988), i.e., the following parabolic expression,
which is easily derived from Eq. (8):
aw =x a baw ca2w ;

22

where
a  1=xmG cG k;

23a

b  cG 2=xmG cG ;

23b

c  cG 1k=xmG cG :

23c

The three constants a, b and c are readily determined by

a least-square regression of this second degree polynomial and from these, the three GAB constants are calculated by
k f 1=2 b=2a;

24a

xmG f 1=2 1=b 2ka k=k 2 a c;

24b

cG 1 c=k 2 a 2 b=ka f 1=2 =ka;

24c

where
f  b2 4ac:

24d

The constants stated in Tables 1 and 2 were obtained

by this method. The upper limit of the regression or

28

E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

Fig. 4. Comparison of (a) experimental BET and GAB constants and (b) experimental and calculated BET constants: (from data shown in Tables 1
and 2). Error bars are indicated in each case.

applicability range of the GAB isotherm (the lower limit

is, as in the BET case, aw 0.05) is determined with the
so-called inverse plot (Timmermann, 1989). At high aw ,
for strongly sorbing substances (cG  1), both isotherms
become very simple for the inverse of x(aw ):
BET : 1=x 1=xmB 1 aw ;

25a

GAB : 1=x 1=xmG 1 kaw :

25b

These relations indicate that 1/x is linear at high

enough aw for both isotherms and that the limits for
1/x 0 (x ! 1) are at the points (aw 1, 1/x 0; BET)

and (aw 1/k (>1), 1/x 0; GAB), respectively. Thus, if

the linear part at higher aw of the inverse plot 1/x vs aw
do not extrapole to aw 1 for 1/x 0 (BET condition),
it is readily concluded that k < 1 (see Eq. (25b)) and
that the GAB equation applies. The extrapolation to
1/x 0 gives 1/k directly as the intercept with the
aw -axis (Timmermann, 1989). Hence, these plots
readily illustrate which isotherm applies. Furthermore,
if after the linear part the graph becomes curved
downwards (usually at aw  0.850.9), then this is a
direct evidence of the presence of the third sorption
stage (Timmermann, 1989; Timmermann & Chirife,

E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

1991), these points should not be used for the GAB

regression. These procedures (inverse and parabolic
plots) are shown in Fig. 3 for various food materials.
The calculated BET and GAB isotherms are also
drawn and the upper limits of both equations are
shown by arrows.
An alternative method to obtain the GAB constants
consists in a non-linear least-squares regression of the
GAB equation. It has been claimed (Schaerr & Ruegg,
1988) that this method and that of the parabolic transform give dierent results, but it can be shown (Timmermann et al., 1991) that if the points of the third
sorption stage are not included, both regressions give
identical results. Accordingly, it has already been stated
that, if points belonging to the third sorption stage are
included in the GAB regression, NEF increases very
sharply this being another criterion to x the upper limit
of the GAB regression.
The results contained in Tables 1 and 2 are illustrated
in Fig. 4; the BET monolayer value (xmB ) and energy
constant (cB ) are plotted against the GAB monolayer
value (xmG ) and the value by GAB (cBG cG k), respectively (Figs. 4(a)). These plots illustrate the inequalities stated by Eq. (1); i.e., that the BET evaluation
always underestimates the monolayer, while it overestimates the energy constant. Figs. 4(b) shows the plot of
the two BET constants against the respective values
calculated in terms of the GAB constants. Within the
corresponding error intervals, the `experimental' BET
values are well reproduced by the calculated ones, and
the scatter is much lower for the monolayer capacity
than for the energy constant.
It is therefore straightforward to conclude that the
GAB constants are to be taken as the representative
parameters of the multilayer sorption. A much more
precise description of multilayer sorption of water by
food materials can be achieved if the analysis is made
with a set of experimental data, which span over the
`quasi'-complete water activity range.
4. The stoichiometry of water sorption by proteins:
Paulings (1945) hypothesis
In 1945, short after Bull's (1944) paper about the
water sorption by proteins, Pauling (1945) published a
now classical paper about the hydration of proteins. He
advanced that the water sorption monolayer of proteins
can be thought in terms of the attachment of one water
molecule to each polar group of the side chains of the
aminocids in the protein. In his analysis, Pauling utilised
BET monolayer values reported by Bull (1944). The
agreement of these BET monolayer values with the
number of polar groups of the proteins was roughly
satisfactory in as much both values were of the same
order of magnitude. However, it is worth noticing that

29

the monolayer values were in most cases lower than the

number of polar groups.
In view of the results stated in the previous sections, it is
straightforward to compare Pauling's data with the
monolayer capacity obtained here by the GAB evaluation, as this equation is directly related and is an improvement of the original BET formulation. Pauling
(1945) expressed his numerical data in terms of the
number of polar groups or moles of water per 105 g of
protein. We retain here these units, the monolayer values
given as grams of water per 100 g of proteins in Table 2 are
to be multiplied simply by 55.5 ( 1000/18) mol H2 O/g.
Table 3 shows the results of this new analysis of
Pauling's hypothesis. The BET monolayer values stated
in Table 2 are slightly dierent from those reported by
Bull (1944) in his original paper, data which are given
within parenthesis in the same table. This is likely due to
some dierences in the water activity interval used for
the BET regression (interval which is not stated exactly
in Bull's paper) and to the fact that Bull's values are the
mean between the values at 25C and at 40C. As in
Pauling's (1945) original paper, the second value of the
second column (Table 3) corresponds to the value obtained by taking also into account the aminoacids proline and hydroxiproline. Data within [ ] are the number
of polar groups reported by other authors found in a
rapid and not-exhaustive search of the literature, as a
more profound revision of Pauling's values in terms of
modern literature of protein aminoacid composition, is
beyond the scope of this paper.
The inspection of Table 3 shows that the rough
agreement noted by Pauling is certainly improved when
the GAB monolayer values are used for comparison.
This conclusion becomes even more evident when the
BET and GAB monolayers are graphically plotted
against the number of polar groups (Fig. 5). The
agreement is quite better for collagen, gelatin, serumalbumin, lactoglobulin, c- and b-zein. For silk, the BET
value seems to be better and, on the other side, for
salmin, the GAB value correlates surprisingly well, although its isotherm presents two branches (see Fig. 2
and note 4 of Table 2), a fact observed already by
Pauling (1945) and by Bull (1944) themselves. Furthermore, in the case of egg albumin and wool, the agreement is improved when the number of polar groups
reported in more modern publications are considered
instead. In the case of collagen and gelatin, Pauling
(1945) noted that the BET value failed to reach the value
of the number of polar groups including the proline and
hydroxiproline, and advanced some possible explanation for this discrepancy. However, when the GAB
monolayer value is used, a close agreement is observed.
Casein, a protein not considered by Pauling in his paper
and not stated in Table 2, has been included in the
present analysis. The sorption data due to Schaerr and
Ruegg (1988) were evaluated elsewhere (Timmermann

30

E.O. Timmermann et al. / Journal of Food Engineering 48 (2001) 1931

Table 3
Comparison between number of polar groups and BET or GAB monolayer valuesa
Protein

Collagen
Gelatin
Seroalbumin
Wool
Lactoglob.crist.
Idem, f.dried.
Eggalbum, coag
Idem, f.dried
Idem, not f.dried
c-zein
b-zein
Silk
Salmin
Casein

Number of polar groups

(mol/105 g)

Monolayer capacity
(mol/105 g)

Paulingb

BET

GAB

k (GAB)

328609
Idem
424
303, 341, 420c
472, 508
Idem
277, 313, 380d
Idem
Idem
305, 390
Idem
219228
611707
416e , 456, 521f

535
470
362
373
367
328
288
313
348
212
227
230
330
306g

638
572
419
470
428
408
350
382
413
242
263
278
755
343g

0.80
0.78
0.81
0.71
0.81
0.80
0.78
0.80
0.78
0.83
0.77
0.77
0.89
0.89

In Fig. 5, the underlined values of the polar group number are represented in the abscissa axis.
Reported by Pauling (1945).
c
Value reported by Windle (1956).
d
Value reported by Fogiel and Heller (1966).
e
Value reported by Ruegg and Hani (1975).
f
Values reported by McLaren and Rowen (1951).
g
Calculated by Timmermann et al. (1991).
b

et al., 1991) using the BET and GAB equations and the
corresponding monolayer capacities are stated directly
in Table 3. It is observed that casein also ts well into
the picture given by Fig. 5.

Finally, it is interesting to consider also the case of

another biopolymer, namely starch. The BET and GAB
monolayer values for potato and wheat starch (Table 1)
were 0.45 and 0.55 mol H2 O/100 g, respectively. Since
the polar group number (one water molecule per anhydroglucose monomer) is 0.62, as reported by McLaren
and Rowen (1951), it follows that again the GAB
monolayer correlates much better than the BET value.
Thus, it is to be concluded that the present ndings
that GAB parameters are more representative than the
corresponding BETs ones, obtains additional support
when Pauling's hypothesis of initial hydration of proteins, is considered.

Acknowledgements
The nancial support from University of Buenos
Aires and CONICET (Argentina) are greatfully acknowledged.

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Fig. 5. Comparison of BET and GAB monolayer values with number
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col: collagen; gel: gelatin; sal: salmin. The underlined values of the
number of polar groups are used (see Table 3); in the cases of silk and
lactoglobulin, both values are represented.

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