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JOWIU/ of Food &gineer;ng 37 (1098) 259-269

0 1998 Elsevicr Science Limited. All rights reserved

Printed in Great Britain
ELSEVIER PII: SO260-8774(98)00092-Z

A Temperature Dependence Function of Equilibrium

Sorption Isotherms Established by a Reaction Engineering

Xiao Dong Chen

Food Science and Process Engineering Group, Department of Chemical and Materials
Engineering, The University of Auckland, Private Bag 92019, Auckland, New Zealand

(Received 1 March 1997; accepted 22 June 1998)


This paper reports a new approach to the equilibrium isotherms for water
sorption in food materials. Isotherms of 19 different materials taken from the
existing literature have been examined. This approach is a chemical reaction
engineering approach which allows a temperature dependence function for the
water sorption isotherms of each maten’al to be deduced, i.e.

f (X,T)
Equilibrium relative humidity (%) = lOO.exp - -
i RT i’
which has the familiar Arrhenius form. In the above equation, X is the water
content on wet basis (Yo), T is the absolute temperature (K). The approach
unifies the dynamic process of drying and the terminal state of drying (i.e. the
equilibrium state) in that the format of the rate equation for drying/wetting can
be reduced to the equilibrium relationship. 0 1998 Elsevier Science Limited. All
rights reserved.


Equilibrium water sorption isotherms are important quantitative measures in the

practice of food preservation, storage, packaging and drying. These isotherms are
usually temperature dependent, e.g. the isotherms of vegetables and fruits (regard-
less of whether they are processed or not). It is always desirable to have simple
260 Xiao Dong Chen

mathematical models which can be used to correlate accurately the equilibrium

sorption data over a wide range of water content and temperature. It is also
desirable to have a generalised model which can be used to describe all the food
materials. It is, of course, even better if the model can be associated with some
fundamental mechanisms involved in sorption/desorption phenomena.
Because of the great difficulty in achieving the above, many simple models have
been proposed which are not necessarily associated with any physical mechanism.
Sometimes, it is even argued that the theoretical support is less important (Labuza,
1968). In any case, one will find generally thare are two classes of models: one is the
‘two-parameter models’ and the other is the ‘three-parameter models’. As summa-
rized by Rahman (1995), the first group includes the Smith model, Oswin model,
Henderson model, BET model, Halsey model, Chung and Pforst model, Iglesias and
Chirife model and the modified versions of these models; the second group typically
consists of the cubic model of Alam and Shore, the model by Bakker-Avkema et al.,
the Schuchmann-Ray-Peleg model, and the GAB model. There are also other
more complicated models, e.g. the four-parameter model by Dural and Hines
(1993a). The GAB model has been widely accepted as the most flexible model
which correlates well with many sets of existing data on different materials.
Not all the above models incorporate explicitly the effect of temperature. Some of
the models are modified versions of the two-parameter models which include the
temperature effect on a fairly emipirical basis, e.g. the modified Henderson model,
and the Oswin model by Diamante and Munro (1990). The GAB model does have
the temperature dependence functions or temperature dependent coefficients pro-
posed which may have certain physical meaning (Weisser, 1985; Kiranoudis et al.,
1993). There are typically six parameters needed for the GAB model in order to
incorporate the temperature effect.
The present study takes a different approach from the above modelling exercises,
i.e. a chemical reaction engineering approach, to explore the temperature effect
upon the equilibrium isotherms. This approach assumes that the drying is an evap-
oration reaction. With some luck, a more general, but still relatively simple, model
may be obtained which is at least comparable with the GAB model. It has been
shown that the temperature dependence function obtained depends strongly on the
nature of the material of interest. This function may also be used as a fingerprint for
the material of interest under equilibrium conditions because the ‘apparent activa-
tion energy’ is accepted to be an indication of the level of difficulty involved in water


It is known that, if the material of concern is initially covered up with liquid water,
the rate of ‘drying’ would be similar or equal to the rate of water evaporation under
the same boundary conditions, like gas velocity, temperature, vapour concentration
and surface area. In this case, the evaporation rate should be well correlated by the
following (Keey, 1992):
- = hrApv,s,, - pv. x )
Sample Materials, Temperature and Relative Humidity Ranges, Correlation Constants, Correlation Coefficients and Types of
Curve Fitting Functions

Material T (“C) RH(%) n rJ MRE (%) Function

Rough rice 20-40 11-85 5.5 0.994 2.9 4.96 x 10sX-’ + 5.95 x lO”X- ’ - 2.57 x 1OL4
Brown rice 20-40 11-85 4 0.997 2.7 -9.35 x 1O’oX-2+ 1.38 x lO’*X-‘-5.49 x 10”
Hull 20-40 11-85 5 0.997 2.2 2.72 x 1O14X- ’ - 1.26 x lo3
Potato 30-60 11-90 11 0.973 10.5 1 04 x 103ox- 1.74
Carrot 30-60 11-90 0.978 6.6 -4:03x 1O24X-2+5.O3 x 1O24X-‘-8.O1 x 1O22 &
Tomato 30-60 11-90 ; 0.981 8.2 4.01 x 1O24X-z + 7.05 x 1O24X- ’ - 1.29 x 102” E.
Green pepper 30-60 11-90 12 0.987 12.4 6 96 x 1O32X-2.62 =
Onion 30-60 11-90 11 0.982 13.8 2:14 x 1O3oX-2.62 9
Yogurt” 20-50 11-84 5.5 0.991 4.3 5.58 x lO”X- ‘.‘a 3
Spray dried yogurt” 20 -50 11-84 15 0.986 7.9 9.89 x 103% ‘.”
Spray dried cont. yogurt” 20-50 11-84 7.5 0.996 4.2 1 28 x lo*’ X- lxx 8
4.0 Z.
Cont. yogurt” 20-50 11-84 6 0.995 -1:27x1016X~2+3.72x1016X~‘-6.90x1014 g
Freeze dried yogurt” 20-50 11-84 15 0.998 1 80 x 1O39X- 1.3s rZ;’
Microwave oven dried yogurt” 20-50 11-84 5.5 0.980 Z.2
6:8 1:19 x lo’sx-“.96 %
Khoa” 15 -45 11-97 6.5 0.994 1.73 x lo1xx- I.** $
Safflower seed” 25-55 11-96 5 0.996 9.8 4.00 x lo’4x-2.8o 2
Rasin (Sultana)” 30-60 11-90 3 0.996 8.6 8.05 x 10sX- 1.66
Cellulose” 10-30 10-90 2 0.990 9.3 1.09 x 1o7x-2.68
Wheat flour” 25-55 Not listed 4 0.996 6.0 3.84 x 1O13X-2.6o

“Value calculated from fitted GAB parameters.

MRE, Mean relative error = + Lgy I$, ,,., - $,~,.Jlrjli ,,,,

where (i) is the number of each data point, (N) is the total number of points and ‘lit’ denotes the data taken from the literature.
262 Xiao Dong Chen

4500 ,
4000 l
3500 l
3000 4
I- %
% 2000 t

0 5 10 15 20 25

Fig. 1. The additional activation energy AE_ vs water content X (%) established using the
original Arrhenius equation (for brown rice).

where: h, = mass transfer coefficient (m.s-‘); A = surface area (m’); pv,sat = sat-
urated vapour concentration at the material boundary (kg.mP3); p_ = vapour
concentration in the environment (kg.m-3).
When the drying is beginning to be ‘hindered’ by the presence of solid compo-
nents or structures, the drying rate of the moist solid can be written similarly as in
eqn (1):
= h,A(p,, - pv,,> (2)
where,P",~ is the vapour concentration at the solid-gas interface. This is, of course,
an unknown parameter during the dynamic process of drying. pv,s can be assumed to
be a fraction of the saturated vapour concentration which is expressed as:
Pw = WP”,S,,VS) (3)
where Y is the fractionality relative to the saturation vapour concentration at the
interface (thus Al), T, is the interface temperature. As such, eqn (2) may be re-
written as:
- = h,M-‘pv,s,,Vs) - pv,,> (4)
The surface area, A, can of course change with the water content because shrinkage
may happen during drying, and swelling may occur during wetting. One can see that
Y becomes 1 if liquid water covers all the solid surfaces but becomes smaller than
Equilibrium sorption isotherms 2.63





8 6E+lo


*a **
0 5 IO 20 25
x l5

Fig. 2. The water content dependence function ,f(X) of the additional activation energy
UK I vs water content X (9%) established using eqn (12) with n = 4 (for brown rice).

1 as solid structure starts to play a restricting role to its removal. It can also be seen
that the system should approach equilibrium state when:
~‘Pv,sat-‘Pv, / 3V-v = ~,,,l~v,sat(T-, h T+T, (5)
This means that Y becomes the equilibrium relative humidity, cp E (0, I], which has
a definite relationship with the equilibrium water content and temperature. If we
assume that evaporation is an ‘activation’ process having to overcome an ‘energy
barrier’ whilst condensation or adsorption is not, we should then expect a simple
relationship for ‘Y(X, 73 may exist in the following form (Chen and Xie, 1997) i.e.

Y=exp - (6)
i RT

where, A,!?, is a ‘correction factor’ or an ‘additional activation energy’ to that for

pure water evaporation, due to the increasing difficulty of removing water at low
water content levels. AE, is expected to decrease to zero when liquid water fully
covers the solid (making V+l) and increase to a large value when the water
content becomes minimal. When equilibrium, AE, should become AE,, , , i.e. an
equilibrium value. Knowing that the saturation vapour concentration (P~,~J can be
expressed accurately by the following:

= K,exp
i- E,
RT 1
264 Xiao Dong Chen

where, E, has similar value as the latent heat of water vaporisation which may be
termed as the activation energy for pure water evaporation, K, is the apparent
‘reaction frequency’. Combining eqns (6) and (7) and substituting them into eqn (4),
one has

- = h,AK,exp (- “;Ty 1 -h,Ap,,

The first term on the right is therefore a zero-order ‘drying reaction’, whilst the
second term on the right is a first-order wetting ‘reaction’. As such, when equili-
brium, eqn (8) becomes:

exp - - = P,VJPsatV) = cp (9)

A%x_ is the equilibrium value of AE, is expected to be a function of water content

and temperature as those found in chemical reaction engineering literature for
multiple simultaneous reactions. A general expression of this function may be writ-
ten as:






-pred. 30deg.C
____-_ pred. 40deg.C

20 exp. 30deg.C

10 A exp. 40deg.C

0 5 10 15 20 25 30

Fig. 3. Comparison between the predicted and the literature data of the isotherms of brown
Equilibrium sorption isotherms 265

AK,, = F(X,T) (10)

Therefore, the equilibrium relative humidity may be written as a function of water
content and temperature:

or in percent as that written in the abstract of the paper. X in this study is based on
wet mass (%).
In the forthcoming sections, it has been found that this additional activation
energy (in addition to the latent heat for drying) has common features of those
having mixed chemical reactions going on simultaneously but each reaction’mechan-
ism may become more significant at different temperatures (therefore, it becomes a
function of temperature). The material of concern may interact with water differ-
ently in different water contents (therefore, the activation energy may have water
content dependence also).
As an initial approximation to eqn (ll), the following temperature dependence
function is proposed:

9E+38 ,
8E+38 A
7E+38 t + 20 deg.C
n 35 deg.C
A 50 deg.C

2E+38 --
lE+38 -- x
10000 +wa ‘4 4, I A
0 10 20 30 40

Fig. 4. The water content dependence functiqn f(X) of the additional activation energy
&CC vs water content X (%) establish;tguus:;g eqn (12) with n = 15 (for freeze dried
266 Xiao Dong Chen










0 IO 30 40

Fig. 5. Comparison between the predicted and the literature data of the isotherms of freeze
dried yogurt.

AE,,= - (12)
where: m is a power which may well be a key feature of the material of concern.
Using this approximation, eqn (11) can be re-written as:

q=exp - RT”
( 1
where, n = VI+ 1 and F(X,T) z f(X)IT”.
This relationship does not describe the ‘cross-over’ behaviour of high sugar con-
tent foods. To this end, it is expected that other types of temperature-water content
dependence functions (F(X,T)) should be explored but this is beyond the scope of
this study.


As many as 19 different food materials (from vegetables to dairy products) have

been analysed using the current simple model (eqns (9) and (12)). Some data were
straight experimental results tabulated in the literature (Ajisegiri & Sopade, 1990;
Kameoka et al., 1985; Kiranoudis et al., 1993) but others were calculated from the
Equilibtium sorption isotherms 267











0 60 80

Fig. 6. Comparison between the predicted and the literature data of the isotherms of onion.

established GAB parameters (Kim & Bhowmik, 1994; Sawhney et al., 1991; Rah-
man, 1995).
The correlation procedures can be outlined below.
Firstly, the relationships between AE,, and X relationships were plotted for
different II values (at 0.5 intervals). This allowed scattered data points (obtained at
different temperatures) to collapse into single lines. Secondly, the data of f(X) vs
X-’ were correlated using fairly simple functions like linear function, power func-
tion, or a second-order polynomial equation using the Excel Spreadsheet Software:
f(X)=aX-‘+b, f(X)=aX-b,
or f(X)=aX-*+bX-‘+c
where, a, b and c are curve-fitting constants. There is no discrimination in terms of
the type of the approximate equation used. Other equations can also be used if they
fit the data in the range of the experimental data.
Certainly the use of the power function is more acceptable as when X gets very
large, AK,, becomes very small (ZW approaches to 100%) and when X-+0,
fKx +co. These are the expected trends although it is not certain at this stage
whether there should be a finite value of AI?.,, as X+0. Both the linear function
and the second-order polynomial function are useful in the range where the experi-
mental data points lie. Extrapolations to the high water contents are less convincing.
In order to preserve the simplicity of the current work, no further complex fitting
function nor more complex regression procedure (or softwares) were used.
268 Xiao Dong Chen

For each material examined, the most adequate value of it (at 0.5 intervals) was
determined when one of the three simple functions achieved the best fit, judging by
the correlation coefficient 3. It should be interesting to note that if one prefers
using integers for IZ (say 12= 5 rather than 5.5) only a very small difference of less
than 0.005 in ? would be found. All the results are listed in Table 1. One example
of the above analysis is that for brown rice. This is illustrated in Figs l-3. Figure 1
shows the scatters if one uses n = 1 for the results of different combinations of
temperature and relative humidity. Figure 2 shows how the scatters can collapse into
one single line, and Fig. 3 shows the goodness of the fit using eqn (10) with it = 4
and f(X)= -9.353 x 1O1oX-2+1.38 x lO’*X-‘-5.488 x 1O’O
Another example is the freeze dried yogurt with n = 15 and
f(X) = 1.80 x 1O39X-‘1.35 (see Figs 4 and 5). One extreme case, whereby the mean
relative error (MRE) is at its highest (which is 13.8%) among the samples
examined, i.e. the onion pieces, is also illustrated in Fig. 6. It seems that the high
sugar content materials tend to produce less desirable correlations using the
approach with eqn (13) because it does not include the effect of the solubility
change of sugar.
Apparently, for samples of large dimensions it values tend to be larger (in the
range of 9-15) in this study but the small ones (and also encapsulated ones) tend to
have it values in the range of 2-6.5). However, this is not conclusive.
All the above have demonstrated that using eqn (13), one may be able to isolate
the temperature effect such that the residue function is mostly dependent upon
water content. This work is significant in that it unifies the rate equation for the
dynamic process of drying (i.e. eqn (9) developed in Chen and Xie’s model (1997))
and the equilibrium relationship (i.e. eqn (11)). Note here that the present work
only explores the effectiveness of one simple equation as an example (i.e. eqn (13)).
From this work, one can see that it is evident that a single Arrhenius type
temperature dependence with constant activation energy is not appropriate, unless
the material of concern does not show much temperature dependence, e.g. cereal-
bread type dietary fibres (Dural & Hines, 1993b).
The large magnitude of the coefficients in the correlations, as shown in Table 1,
may be of particular concern. These large values are, however, purely due to the fact
that the water content on a wet basis expressed in % is used here (which can be as
high as 25). This problem would not exist if one uses the water content on a dry
basis. However, even with these large coefficients, the model correlates most of the
materials rather well.


This study has illustrated that the chemical reaction engineering approach provides
a framework that allows the temperature dependence function for the water sorp-
tion isotherms of each material to be deduced. The apparent activation energy can
be obtained for each material, which reflects the degree of difficulty in removing
water thus represents the nature of the material of concern. The approach, to a
large extent, unifies the dynamic process of drying and the terminal state of drying
(i.e. the equilibrium state) in that the rate equation can be reduced to the equili-
brium relationship.
Equilibtium sorption isotherms 269


The author thanks his parents for giving him the inspiration over the years that
drives his success in every step of his career. The author also thanks his wife for her
tolerance in letting him complete the write-up during some weekends. Dr. Md.
Farid helped check some details of the work.


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