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Sorption Isotherms and Isosteric Heat of Peanut Pods,

Kernels and Hulls


P.C. Corra1, A.L.D. Goneli1, C. Jaren2*, D.M. Ribeiro1 and O. Resende1
1Department

of Agricultural Engineering, University Federal of Viosa, Campus UF,


P.O. Box 270, 36570-000 Viosa-MG, Brazil
2Department of Proyect and Rural Engineering, Public University of Navarre, Campus Arrosadia,
31006 Pamplona, Spain
This study was carried out to evaluate the sorption isotherms of peanut pods, kernels and hulls for several
temperature and humidity conditions and to fit different mathematical models to the experimental data,
selecting the one best fitting the phenomenon. The dynamic method was applied to obtain the hygroscopic
equilibrium moisture content. The environmental conditions were provided by means of an atmospheric
conditioning unit, in which removable perforated trays were placed to allow air to pass through peanut
mass, each one containing 50 g of the product. The mathematical models frequently used for the representation of hygroscopicity of agricultural products were fit to the experimental data. Based on those results,
it was concluded that peanut pods, kernels and hulls presented differentiated hygroscopicity. The equilibrium
moisture content for peanut pods, kernels and hulls increased with an increase in the relative humidity at any
particular temperature and decreased with increase in temperature at constant relative humidity. At a
constant water activity, peanut hulls samples had higher equilibrium moisture content than the pods and
kernels samples. Based on statistical parameters, the modified Henderson and Chung-Pfost models were
found to adequately describe the sorption characteristics of peanut pods, kernels and hulls. Isosteric heat
of desorption were evaluated by applying the ClausiusClapeyron equation to experimental isotherms
and decreased with increasing moisture content. The peanut hulls had higher isosteric heat of sorption
than that peanut pods and kernels.
Key Words: equilibrium moisture content, Arachis hypogaea, mathematical models, desorption, isosteric heat

INTRODUCTION
Peanut (Arachis hypogaea L.) is a dicotyledonous leguminous plant originated from Central America and
adapted to equatorial-tropical climate, presenting high
contents of proteins, vitamins, lipids, carbohydrates and
mineral salts. Peanuts are composed of a hull, kernels
and some air enclosed between two components, thereby
making their structure quite complex. Limited data on
the sorption properties of peanuts has been reported in
the literature.
Peanut harvesting is many times conducted under
adverse climatic conditions, especially during heavy
*To whom correspondence should be sent
(e-mail: cjaren@unavarra.es).
Received: 19 October 2005; revised: 17 October 2006.
Food Sci Tech Int
2007; 13(3): 231238
SAGE Publications 2007
Los Angeles, London, New Delhi and Singapore
ISSN: 1082-0132
DOI: 10.1177/10820132013207079601

raining seasons, which may induce fungus development


and toxin production due to traditional harvesting, drying and storage practices.
The control of moisture content of foods during processing and storage is very important as water has many
roles in food reactions and food quality. In this respect
the moisture sorption isotherm is an extremely important tool in food science because it can be used to predict changes in food stability and to select appropriate
packaging materials and ingredients (Ayranci and
Duman, 2005).
All agricultural products have the capacity to loss or
absorb ambient water, thus maintaining a constant equilibrium relation between their moisture content and the
ambient air conditions. Equilibrium moisture content
(EMC) is attained when partial water vapor pressure is
equal to that of the air that surrounds it. The relation
between the moisture content of a given product and
the equilibrium relative humidity (ERH) for a specific
temperature may be expressed by mathematical equations, termed moisture sorption isotherms. In every food
product there is an inherent relationship between water

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232

P.C. CORRA ET AL.

content and the relative humidity of the atmosphere in


information about the dehydration process energy
equilibrium with it, which is equivalent to water activity.
requirement, the properties of water, food microstrucThe chemical composition of a product has a direct
ture and physical phenomena on the food surfaces, and
influence on the humidity sorption process. According
sorption kinetic parameters. One method widely used
to Brooker et al. (1992), grains with high oil content
for calculation of isosteric heat of sorption of many
adsorb smaller amount of moisture from the environfoods is based on the ClausiusClapeyron equation,
ment than grains with high starch content. Moreover,
which assumes temperature-independent heat of sorpthe variety, degree of maturity, and physical and sanition and allows an easy calculation of the isosteric heat
tary conditions as well as the method through which
from the sorption isotherms (Aguerre et al., 1988).
equilibrium was obtained (adsorption or desorption)
In view of the importance of understanding the
are also determining factors in the establishment of the
hygroscopicity of agricultural products, this work aimed
equilibrium humidity of hygroscopic products (Chen,
to determine the sorption isotherms of peanut pods,
2000b; Fan et al., 2000).
kernels and hulls for various temperature and air relative
Moisture sorption isotherms may be obtained experhumidity conditions and to fit different mathematical
imentally by means of the dynamic and static methods.
models to the experimental data, selecting the best-fitting
In the dynamic method, the pod is submitted to air flow
model, and calculate the isosteric heat of sorption at
under controlled and fixed temperature and relative
different moisture levels.
humidity conditions until equilibrium is reached. In the
static method, the hygroscopic equilibrium between the
product and the environment, under controlled condiMATERIAL AND METHODS
tions, is reached without air movement (Wang and
Brennan, 1991; Jayas and Mazza, 1991; Chen, 2000b).
The present work was carried out in the Laboratory
Several researchers have studied the hygroscopic
for the Physical Properties and Quality Evaluation of
behaviour of several agricultural products, describing
Agricultural Products of National Grain Storage
differentiated models to express the EMC as a function
Training Center CENTREINAR, Federal University
of the temperature and air relative humidity. However,
of Viosa, Viosa, MG, Brazil.
for the establishment of isotherms that represent this
The initial moisture content of peanut pods, kernels
equilibrium relation, empirical mathematical models
and hulls were 31.0, 25.0 and 47.0% dry basis, respecare used, since no theoretical model has been capable
tively. Samples were stored in polythene bags kept in a
of precisely predicting the EMC for a wide range of
refrigerator to attain moisture uniformity. When needed
temperature and air relative humidity.
for experiments, samples were allowed to equilibrate at
Over 200 equations are currently available in the
ambient condition for 6 h. The peanut pods, kernels and
literature proposing to represent the hygroscopic equihulls moisture content was determined by applying the
librium phenomenon of agricultural products. Such
drying in an oven at 105 1C, for a 24 h period, in tripmodels differ in their theoretical or empirical basis and
licate according to the seeds analysis standard of Brazil
number of parameters involved (Mulet et al., 2002).
(Ministrio da Agricultura e Reforma Agrria, Brazil,
The modified Henderson equation and Chung Pfost
1992).
equation were the best models for many starchy grains
The sorption method used was the dynamic techand fibrous materials. The modified Halsey equation was
nique or gravimetric method, in which the material is
the best for high oil and protein products. The modified
brought into equilibrium with air of fixed temperature
Oswin model was good for popcorn, peanut pods and
and relative humidity and the equilibrium moisture conother varieties of corn and wheat (Chen, 2000b; Chen
tent (EMC) of the material is measured. Thin-layer dryand Morey, 1989). The GAB model was very popular to
ing was carried out at different controlled temperature
be adopted by some researchers (Ayranci and Duman,
(20, 35, 50 and 65C) and air relative humidity of the dry2005; Mulet et al., 2002; Pagano and Mascheroni, 2005;
ing air (between 0.2 and 0.8) until the product reached
Van den Berg, 1984). However, this model was found to
equilibrium humidity at the specified air condition.
be inadequate to describe the relationship between
The environmental conditions for the performance of
moisture content and water activity for some agricultural
the tests consisted of a temperature controlled chamber,
products (Chen, 2002, 2003; Chen and Jayas, 1998).
manufactured by Aminco, model Aminco-Aire 150/300
Moisture sorption isotherms constitute an essential
CFM. Removable perforated trays containing 50 g of
part of the theory of drying and provide useful informaproduct were placed inside the equipment to allow air to
tion in the design of drying equipment and in the study
pass through the samples. Air flow was monitored with
of storage of dehydrated products. A thermodynamic
an anemometer with rotating blades and kept around
parameter such as isosteric heat is frequently evaluated
10 m3/min/m2. Temperature and air relative humidity
from equilibrium data at different temperatures
were monitored with a psychrometer installed next to
(Iglesias and Chirife, 1976).
the trays containing the samples.
The application of thermodynamic principles to
The trays containing the product were periodically
sorption isotherm data has been used Downloaded
to obtain
more
weighed
during drying. Hygroscopic equilibrium was
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Sorption Isotherms Peanut Pods, Kernels and Hulls


reached when the mass variation of the containers
remained constant during three consecutive readings.
In this work, the relationship between the equilibrium
moisture content data and the relative humidity and
temperature for peanuts pods, kernels and hulls was
evaluated according to the models of ChungPfost
(Pfost et al., 1976), Copace (Corra et al., 1995), modified Halsey (Iglesias and Chirife, 1976b), modified
Henderson (Thompson, 1972), modified Oswin (Chen
and Morey, 1989) and GAB (Anderson, 1946). These
models are presented in Table 1 where Me is the equilibrium moisture content (% dry basis), t is the temperature (C), rh is the relative humidity (decimal), A, B
and C are parameters of models.
The experimental data were interpreted by means of
non-linear regression analysis by the Quasi-Newton
method, using a computer program STATISTICA 6.0.
The models were selected based on the significance of
the regression coefficients by the t-test, at 1% probability, the mean relative error (MRE), the standard error
of estimate (SEE), the determination coefficient (R2)
and residual distributions plots were used to evaluate
the fitting quality.
The mean relative error value lower than 10 was one of
the criteria for selecting the models, according to
Mohapatra and Rao (2005).The mean relative error MRE
and the standard error of estimate SEE are given by:
MRE =

100 n M exp M pre


M
n i=1
exp

( M
n

SEE =

i =1

M pre
exp

(6)

(7)

Df

Table 1. Mathematical models used to identify the


EMC of products of vegetable origin.
Model

Model Expression

Chung-Pfost

Me

Copace

Me

Modified Halsey

Me

Modified Henderson

Me

Modified Oswin

Me

GAB

Me

where, Mexp is the experimental value of EMC; Mpre is


the value predicted by the model; N is the number of data
points; Df is the degrees of freedom of regression model.
The residuals were plotted against predicted values of
EMC. A model is considered acceptable if the residual
values fell in horizontal band centered around zero, displaying no systematic tendencies (i.e., random in nature)
towards a clear pattern. If the residual plot indicates
clear pattern, the model is not considered acceptable.
The net isosteric heat of sorption was determined
from moisture sorption data using the following equation, which is derived from the ClausiusClapeyron
equation (Iglesias and Chirife, 1976a):
q
ln(rh)
= st 2
T
R T

(8)

Integrating Eq. (12), assuming that the net isosteric


heat of sorption (qst) is temperature independent, gives
the following equation (Wang and Brennan, 1991):
q 1
ln(rh) = st + K
R T

(9)

where qst is the net isosteric heat of sorption (kJ/kg), R


is the universal gas constant (kJ/kg/K), T is absolute
temperature (K).
The sorption isosteric heat Qst can be calculated by
adding the latent heat of vaporization for pure water L
to the net sorption isosteric heat qst (Sanchez et al.,
1997):

Qst = qst + L = a. exp( b. M e ) + L

233

(10)

where Qst is the sorption isosteric heat (kJ/kg), L is the


latent heat of vaporisation for pure water, kJ/kg for
the temperatures taken into account; a and b are
constants.

RESULTS AND DISCUSSION

The mathematical models tested to determine the


equilibrium
moisture content of peanuts pods presented
= A B ln (t + C ) ln( rh)
significant regression coefficients at 1% probability and
= exp A ( Bt ) + (Crh)
values of determination coefficient (R2) above 93%
(Table 2). The modified Halsey model gave a relative
1/ C
exp( A Bt )
mean error above 10%, showing to be inadequate to
=

ln( rh)
describe the equilibrium moisture content (zdemir
and Derves, 1999). The residual plot of modified Halsey
1/ C
ln(1 rh)
model displayed a clear pattern. Thus, the model was
=

A (t + B)
also non acceptable. However, the Copace, ChungPfost, modified Henderson and modified Oswin models
1/ C
rh
= ( A + Bt )
presented a better fitting to the experimental data of

(1 rh)
equilibrium moisture content of peanut pods, showing
random residual plot, smaller mean relative error
ABC ( rh)
=
(lower than 10%). Thus, the application of these four
[1 B( rh)][1 B( rh) + BC ( rh)]
models is recommended to estimate the equilibrium
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P.C. CORRA ET AL.

234
Table 2.

Estimated parameters and comparison criteria for the equilibrium moisture content models
of peanut pods desorption data.
Model Parameters*

Models

Chung-Pfost
Copace
Modified Halsey
Modified Henderson
Modified Oswin

23.8213
1.1878
3.6073
0.0005
8.3203

4.1930
0.0079
0.0158
51.6250
0.0510

49.3712
1.9151
1.8467
1.5244
2.3683

R2 (%)
96.52
96.27
95.06
96.72
96.30

SEE (% d.b.)
0.5542
0.5733
0.6601
0.5381
0.5717

MRE (%)
7.1140
9.2428
10.7800
7.8789
8.8750

Residual Plot
Randon
Randon
Patterned
Randon
Randon

*Significant at 1% probability by the t-test.

humidity of peanut pods. Chen (2000a) obtained also a


better fit to the experimental data of equilibrium moisture content of peanut pods with the Oswin model.
For the peanut kernels, the coefficients estimated for
the models showed significance at 1% probability by
the t-test and relative mean error below 10% (Table 3).
In addition, all the models showed a coefficient of
squared above 95%, except the modified Halsey model.
However, only the modified Henderson and ChungPfost models presented a random residual plot. The
Chung-Pfost model exhibited a higher determination
coefficient and lower estimated and mean relative error
and standard error of estimate, being thus recommended
for predicting the hygroscopic equilibrium of peanut
kernels. This result disagreed with Chen (2000a) who
recommended the modified Halsey model, and with
Chen and Morey (1989) who used modified Halsey and
modified Oswin models to estimate the hygroscopic
equilibrium of peanut kernels.
For the peanut hull, all the models presented values of
determination coefficient above 96% (Table 4). Besides,
the models studied presented significant coefficients at
1% probability by the t-test, and mean relative error
below 10%.As well as the peanut pods, only the modified
Halsey model was inadequate to describe the equilibrium
moisture content in peanut hulls because the residual plot
indicated clear pattern. Chen and Morey (1989) observed
that the modified Henderson equation satisfactorily

Table 3.

represented the hygroscopic equilibrium experimental


data, and Chen (2000a) recommended the Chung-Pfost
model to predict equilibrium humidity of the peanut hull,
being both in agreement with this work.
All residual plots of the GAB model for samples
dried at four temperatures had systematic patterns
(Table 5). The results indicated that the GAB equation
was not an adequate model either for peanut pods, kernels or hulls. A similar systematic pattern of residual
plots also were found for the GAB models of desorption and adsorption data for potato slices (Wang and
Brennan, 1991) and cassava (Sanni et al., 1997). These
results agreed with Chen and Jayas (1998) investigations on adequacy of the GAB equation to describe
EMC/ERH relation for agricultural products.
The desorption isotherms for peanut pods, kernels
and hulls obtained at 20, 35, 50 and 65C (Figures 14,
respectively) were adjusted by fitting the modified
Henderson model, Eq. (4), to the experimental data.
The equilibrium moisture content at each water activity
represents the mean value of three replications. As
expected, the equilibrium moisture contents increased
with an increase in the relative humidity at any particular temperature and decreased with increase in temperature at constant relative humidity.
At higher temperature water molecules reach higher
energy levels and this allows them break away from
their sorption sites, thus decreasing the equilibrium

Estimated parameters and comparison criteria for the equilibrium moisture content models
of peanut kernels desorption data.
Model Parameters*

Models
Chung-Pfost
Copace
Modified Halsey
Modified Henderson
Modified Oswin

A
19.8681
1.0877
3.6797
0.0003
6.8118

B
3.2246
0.0051
0.0120
85.5428
0.0302

C
75.5245
1.6755
2.0960
1.7519
2.7020

R2 (%)
97.08
95.54
93.68
96.54
95.65

SEE (% d.b.)

MRE (%)

Residual Plot

0.3730
0.4607
0.5484
0.4059
0.4549

6.1137
8.6219
9.9758
7.2175
8.2203

Randon
Patterned
Patterned
Randon
Patterned

*Significant at 1% probability by the t-test.


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Sorption Isotherms Peanut Pods, Kernels and Hulls


Table 4.

235

Estimated parameters and comparison criteria for the equilibrium moisture content models
of peanut hulls desorption data.
Model Parameters*

Models

Chung-Pfost
Copace
Modified Halsey
Modified Henderson
Modified Oswin

37.2538
1.7432
4.6864
0.0002
14.0039

6.6636
0.0089
0.0179
38.4115
0.0925

C
37.7956
1.8720
1.8827
1.5619
2.4131

R2 (%)

SEE (% d.b.)

MRE (%)

96.72
97.39
96.55
97.66
97.35

0.8787
0.7831
0.9011
0.7421
0.7895

7.2498
7.0524
8.5662
5.8444
6.7912

Residual Plot
Randon
Randon
Patterned
Randon
Randon

*Significant at 1% probability by the t-test.

moisture content (Palipane and Driscoll, 1992). As temperature changes, the excitation of molecules, as well as
the distance, and thus attraction between molecules
varies. This causes the amount of sorbed water to
change with temperature at a given relative humidity
(Mohsenin, 1986).
The temperature shifts observed have an important
practical affect on the chemical and microbiological
reactions which cause quality deterioration. An increase
in temperature causes an increase in the water activity,
at the same moisture content, which in turn causes an
increase in the reaction rates leading to quality deterioration (Van den Berg and Bruin, 1981).
The sorption isotherms of peanut pods, kernels and
hulls samples showed type II behaviour according to
the BET classification. At a constant water activity,
peanut hulls samples had higher equilibrium moisture
content than the pods and kernels samples, indicating a

Table 5.

higher hygroscopicity of the product. This might be due


to the separation of hulls from peanut kernels, since
hulled process reduces the fibre content, which absorbs
more water. These results agreed with those found by
Kaya and Kahyaoglu (2006) who evaluated the influence of dehulling and roasting process on the thermodynamics of moisture adsorption in sesame seed. In all
range of temperature used, the sorption isotherms of
peanut pods and kernels had similar values.
The interaction between water vapour and the adsorbent food material should be determined to define
effect of temperature, isosteric heat of sorption (Qst). At
constant moisture content, relative humidity of the
equilibrium at each studied temperature were determined using the modified Henderson model (since it
fitted the experimental data satisfactorily). The isosteric
heat of sorption values was calculated by applying
Eqs. (9) and (10), and represented with respect to

Estimated parameters of GAB model for peanut pods, kernels and hulls desorption data.
Model Parameters*

t(C)

Pods
20
35
50
65

5.5786*
4.5593*
22.2841 ns
21.5076 ns

0.6337*
0.6868*
0.0097 ns
0.0035 ns

7.0288
11.6252
69.7799
166.3946

ns

Kernels
20
35
50
65

5.7234*
4.9688*
14.4176 ns
32.0225 ns

0.7402*
0.7497*
0.2435 ns
0.0067 ns

7.4220
8.5307
4.1322
58.6284

ns

Hulls
20
35
50
65

8.3337*
8.3536*
8.4497*
31.6009 ns

0.7945*
0.7249*
0.6869*
0.0154 ns

11.3414 ns
8.5374 ns
5.4861*
46.6346 ns

ns
ns
ns

ns
ns
ns

R2 (%)

SEE (% d.b.)

97.05
95.44
93.19
92.77

0.3211
0.4156
0.4151
0.3268

3.2341
4.3730
7.3296
7.0494

Patterned
Patterned
Patterned
Patterned

91.94
96.36
93.29
90.88

0.7803
0.4996
0.4647
0.4121

6.8384
5.0275
7.3610
8.3395

Patterned
Patterned
Patterned
Patterned

95.08
95.67
95.52
96.77

1.0325
0.8516
0.5815
0.3541

5.4565
5.8888
6.3883
3.9581

Patterned
Patterned
Patterned
Patterned

*Significant at 1% probability by the t-test; ns: not significant.


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MRE (%)

Residual Plot

P.C. CORRA ET AL.

236

Figure 1. Equilibrium moisture content values of


peanut pods (), kernels () and hulls () obtained
by desorption at 20C, and their isotherms calculated
by the modified Henderson model.

Figure 3. Equilibrium moisture content values of


peanut pods (), kernels () and hulls () obtained
by desorption at 50C, and their isotherms calculated
by the modified Henderson model.

Figure 2. Equilibrium moisture content values of


peanut pods (), kernels () and hulls () obtained
by desorption at 35C, and their isotherms calculated
by the modified Henderson model.

Figure 4. Equilibrium moisture content values of


peanut pods (), kernels () and hulls () obtained
by desorption at 65C, and their isotherms calculated
by the modified Henderson model.

equilibrium moisture content (Figure 5). At low moisture content the heat of sorption is high, indicating the
highest binding energy for removal of water. Increasing
moisture content decreased the heat of sorption due to
reduced water interactions. As the moisture content
increases further, the heat of sorption tends to that of
pure water an indication of the moisture existing in the
free form. The isosteric heat of sorption peanut hulls
was lower than those of pods and kernels samples for all

moisture content values. These results agreed with those


found by Martinez and Chiralt (1996), who reported
that the hulled process decreased the heat of sorption
values of hazelnut, almond and peanut samples, likely
due to enhancement of lipidlipid interaction that
increases the hydrophobicity of cellular components of
seeds. The net isosteric heat of sorption with respect to
equilibrium moisture content was adequately described
by the power law relation of the form:

Peanut pods:

Qst = 1691.86 exp( 0.24 M e ) + 2400.43 ( R 2 = 0.9999)

Peanut kernels:

Qst = 1617.41 exp( 0.31 M e ) + 2400.43

Peanut hulls:

Qst = 2062.27 exp( 0.31 M e ) + 2400.43 ( R 2 = 0.9999)

(R 2 = 0.9999)

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Sorption Isotherms Peanut Pods, Kernels and Hulls

237

REFERENCES

Figure 5. Isosteric heat of sorption at different moisture


contents for peanut pods (), kernels () and hulls ().

The knowledge of the magnitude of the heat of


sorption, at a specific moisture content, provides an
indication of the state of the sorbed water and hence, a
measure of the physical, chemical and microbiological
stability of the food material under given storage conditions. In addition the variation in heat of sorption with
moisture content, and magnitude relative to the latent
heat of vaporization of pure water, provides valuable
data for energy consumption calculations and subsequent
design of drying equipment, and an understanding of
the extent of the watersolid versus waterwater interactions (McMinn and Magee, 2003).

CONCLUSION
The experimental results illustrated that the equilibrium moisture content (EMC) increased with decreasing temperature, at constant equilibrium relative
humidity (ERH). Furthermore, at constant temperature, the EMC increased with increasing ERH. Peanut
pods, kernels and hulls have different hygroscopicity.
The order in the magnitude of equilibrium moisture
contents at each water activity values was found as
peanut hulls peanut pods peanut kernels. Based on
statistical parameters, the models modified Henderson
and Chung-Pfost were the ones best representing the
hygroscopicity phenomenon of peanut pods, kernels
and hulls, compared with the Copace, modified Halsey
and modified Oswin models. The GAB equation was
not an adequate model for either peanut pods, kernels
or hulls. The isosteric heat of desorption of all samples,
calculated using the ClausiusClapeyron equation,
showed power relations with moisture content; whole
peanut hulls has higher isosteric heat of sorption than
that peanut pods and kernels.

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