ARTICLE IN PRESS

Biosystems Engineering (2003) 86 (4), 441–446 Available online at www.sciencedirect.com

doi:10.1016/j.biosystemseng.2003.07.003
PH}Postharvest Technology

Thermal and Moisture Diffusion Properties of Amaranth Seeds

M.G. Vizcarra Mendoza; C. Mart!ınez Vera; F.V. Caballero Dom!ınguez
! rea de Ingenier!ıa Qu!ımica, San Rafael Atlixco No. 186, Col. Vicentina, 09340 Iztapalapa,
Depto. de Ingenier!ıa de Procesos e Hidr!aulica, A
Mexico, DF; e-mail of corresponding author: mgvm@xanum.uam.mx

(Received 24 October 2002; accepted in revised form 30 July 2003; published online 28 September 2003)

The physical characteristics, thermodynamic and transport properties of amaranth seeds relevant to the
modelling and simulation of the drying processes of these seeds were studied. The water activity as a function
of the temperature and moisture content was modelled by means of the Henderson’s expression from water
activity experimental data. The desorption–vaporisation heat was also calculated. From the solution to Fick’s
second law for a spherical geometry and assuming equilibrium conditions at the solid–gas interface, an
effective diffusion coefficient was evaluated from experimental drying curves obtained in a moisture chamber.
The effect of taking into account more than one term in the Fourier series solution was analysed and it is
concluded that the diffusion coefficient corresponding to two terms in the series leads to better agreement with
the experimental results for short times.
# 2003 Silsoe Research Institute. All rights reserved
Published by Elsevier Ltd

1. Introduction 2. Procedures and methods

Amaranth is a small size, nearly spherical, attrition- 2.1. Physical characterisation

resistant seed with high nutritional value. The variety
used in this study was Amaranthus hypochondriacus. The The parameters that characterise the size, shape and
amaranth seed is harvested with moisture content of mass of the particle such as the effective diameter, sphericity
approximately 20% dry basis (d.b.). In order to avoid and specific weight are fundamental to modelling of drying
the growing of microorganisms and the development of operations. The average diameter dav in m is given by
fungus, inhibit enzymatic reactions, minimise the lost of !1
Xn
xi
flavours and textures, the seed moisture content must be dav ¼ ð1Þ
reduced to about 10% d.b. i¼1
di
The design, optimisation and control of the drying
where: xi is the weight fraction of the ith sieve; and di is
operation require a model adequate for the specific
the diameter in m of the ith sieve.
purpose of this operation. These models include certain
The effective diameter de is calculated according to
physical parameters that need to be known. The main
objective of this work is to determine the parameters de ¼ fs dav ð2Þ
relevant to the modelling and simulation of the drying where fs is the sphericity. The true and bulk densities rp
processes of amaranth seeds. There are no reported and re in kg/m3 are given by
values of these parameters in the literature. Tosi and R!e
(1999) report kinetic expressions for the drying curves rp ¼ m=ðV  vÞ ð3Þ
obtained in a fluidised bed dryer, but the authors do not and
report values or expressions for more fundamental
re ¼ m=V ð4Þ
properties that could allow the simulation of the
fluidised bed drying of amaranth seeds under different respectively, where m is the seed mass in kg; V is the
operation conditions or the drying of these seeds in a reference volume in m3; and v is the seed volume without
different drying process. void space in m3.
1537-5110/$30.00 441 # 2003 Silsoe Research Institute. All rights reserved
Published by Elsevier Ltd
 ARTICLE IN PRESS
442 M.G. VIZCARRA MENDOZA ET AL.
Notation
a; a0 ; b; b0 ; c; c0 empirical constants
aw water activity, dimensionless
A; B empirical constants
CD heat capacity of dry seed, J kg1 K1
CH heat capacity of moist seed, J kg1 K1
dav average diameter, m
de effective diameter, m
di diameter of the ith sieve, m
D diffusion coefficient of water, m2 s1
DH isosteric heat of vaporisation, J kmol1
m seed mass, kg
M seed moisture content, kg kg1 d.b.
M% average seed moisture content, kg kg1 d.b.
Mds dimensionless moisture content, dimensionless
Me equilibrium seed moisture content, kg kg1
d.b.
M0 initial moisture content, kg kg1 d.b.
2.2. Thermodynamic properties
The heat capacity parameters CD and CH in
J kg1 K1 for the dry (5% moisture content d.b.) and
moist (20% moisture content d.b.) seeds were deter-
mined using a differential scanning calorimeter (TA
Instruments, model 2010, USA). The temperature range
covered was from 5 to 758C. A heating ramp of
58C min1 and a nitrogen flow of 50 ml min1 were
employed. The use of ramp rates between 5 and
208C min1 provides the best compromise between the
maximum heat flow displacement and minimum thermal
gradients (TA Instruments, 1997). The results, expressed
as functions of temperature T in K are:
Dry seeds : CD ¼ a þ bT þ cT 2 ð5Þ
Moist seeds : CH ¼ a0 þ b0 T þ c0 T 2 ð6Þ
where a; a0 ; b; b0 ; c; c0 are empirical constants.
The water activity aw of amaranth seeds was
determined using a moisture chamber (Ebro, model
AWX-3001, Germany) and a constant temperature
bath. There are several expressions reported in the
literature that have been employed for predicting the
equilibrium moisture content of biological material.
From those, the modified Henderson’s equation (Zahed
& Epstein, 1992) was chosen:
lnð1  aw Þ ¼ ðATMe ÞB ð7Þ
where: A and B are constants, Me is the equilibrium
moisture content in kg kg1; and R is the gas constant in
J kmol1 K1.
n order of approximation, dimensionless
N number of time values, dimensionless
r radial distance, m
R gas constant, J kmol1 K1
Rav average seed radius, m
t time, s
T temperature, K
v seed volume without void spaces, m3
V reference volume, m3
xi weight fraction in the ith sieve, dimensionless
rp true density, kg m3
re bulk density, kg m3
fs sphericity, dimensionless
Superscript
exp experimental
The desorption–vaporisation heat can be estimated in
terms of the heat of vaporisation of pure water at the
corresponding temperature plus the net heat of desorption
at the same temperature and at given solid moisture
content according to the next equation (Zahed et al.,
1995):
 
2 6887 531 ½daw =dT M
DH ¼ RT  þ ð8Þ
T2 T aw
where DH is the isoteric heat of vaporisation in
J kmol1.
2.3. Diffusion coefficient estimation
A schematic diagram of the experimental equipment
for the diffusion coefficient determination is shown in
Fig. 1 (Caballero, 1999). The humidity chamber (Kar-
atas, 1997) consisted of an acrylic tube 005 m in internal
diameter and 001 m in length in which samples of the
seeds (001 kg of amaranth) were introduced in a small
bag for the diffusion coefficient determination. The
moisture content was determined by weight differences.
The experimental drying tests were done in the
following way. The amaranth seeds were re-wetted
before each experimental run until they reached the
initial moisture content (20% d.b.). This was done by
immersing the seeds in a container with water at room
temperature for 6 h and, after that, the seeds were left
24 h at room temperature before the experimental runs
for allowing the uniform distribution of moisture inside
the seeds. The humidity chamber (Fig. 1) was loaded
with 0010 kg of moist amaranth for each experiment.
 ARTICLE IN PRESS
PROPERTIES OF AMARANTH SEEDS 443

3. Results and discussion

The amaranth diameter and the bulk and true

densities were determined by triplicate. The average
(A) (B)
(E) values obtained for these parameters are reported in
Table 1.
The heat capacity as a function of temperature was
P determined at two levels of moisture content (5 and 20%
(D)
d.b.). The sample sizes for the differential scanning
calorimeter tests were 1684 mg. The values for the
coefficients in Eqns (5) and (6) were estimated by means
of a regression procedure and the resultant expression
for the dry solid heat capacity as a function of
Trap (C) temperature (regression coefficient of 098) is given by
Fig. 1. Experimental installation for humidity determination; CD ¼ 91258  55162T þ 00978T 2 ð10Þ
(A) rotameter; (B) electrical heater; (C) temperature control;
(D) humidity chamber; (E) thermocouple type J; (P) pump and the corresponding equation for moist seeds is
(regression coefficient of 099)
CH ¼ 16469  64432T þ 00231T 2 ð11Þ
The experiments were carried out at four different
drying temperatures: 313, 323, 333 and 343 K. The experimental values of water activity versus seeds
The diffusion coefficient was determined from the moisture content at different constant temperatures are
solution to Fick’s second law. Considering the diffusiv- shown in Fig. 2. The continuous lines correspond to
ity independent of the moisture content and equilibrium the water activity fitted by means of the Henderson’s
conditions at the gas–solid interface, the solution, in equation. The constants A and B in Eqn (7) are
spherical geometry, to the Fick’s equation is (Crank, 00377 and 10679, respectively. The heat of
1975): desorption–vaporisation was obtained from Eqns (7)
"   #
M%  Me 6 X 1
1 np 2 Table 1
Mds ¼ ¼ exp  Dt ð9Þ
M0  Me p2 n¼1 n2 Rav Physical parameters of amaranth seeds
Average
where: Mds is the dimensionless moisture content; M % is diameter Sphericity True density Bulk density
the seed average moisture content; M0 is the initial (dav), m (fs) (rp), kg m3 (re), kg m3
moisture content; Rav is the seed average radius in m; D 0001 10 1370 860
is the diffusion coefficient in m2 s1; t denotes the drying
time in s; and n is the order of approximation.
From the analysis of Eqn (9) it is evident that the
truncation of the infinite series solution will induce an 1.0
error that will be more considerable for very short times.
As the numerical values of the successive terms of the
series diminish rapidly, the series can be truncated after 0.8
a few terms without causing an appreciable error. The
Water activity

usual criterion is that if the Fourier number for mass 0.6

transfer Dp2 t=r2 > 12 (where r is the radius of the
particle in m) the error caused when only the first term 0.4
of the series is taken into account is less than 5%
(Brooker et al., 1992). Usually just one term is taken
into account for the estimation of the diffusion 0.2
coefficient and, therefore, the estimation can be made
by a linear regression procedure. Also, the effect of 0.0
taking into account more than one term in the Fourier 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
series solution is analysed and the corresponding values Moisture content, kg/kg
when two and three terms are taken into account are Fig. 2. Water activity of amaranth seeds at different tempera-
estimated. tures: &, 293 K; m, 303 K, ^, 313 K; c, 323 K
 ARTICLE IN PRESS
444 M.G. VIZCARRA MENDOZA ET AL.

and (8): 1.0

 
6887 00322 Me10679 T 00679 531
DH ¼ RT 2 þ 
T 2 10679 T 0.8

Dimensionless moisture content

exp½ð00377 Me TÞ 1
ð12Þ
0.6
The values of the desorption–vaporisation heat at
each of the experimental temperature values for a 10%
moisture content d.b. are reported in Table 2. 0.4
The set of experimental data obtained in the moisture
chamber for four different temperatures were fitted with
0.2
an exponential model as a function of time and
temperature. The fitted model is
h t i 0.0
Mds ¼ exp  ð13Þ 0 2000 4000 6000 8000 10000 12000
16303  44006 T Time, s
The experimental moisture content data in dimen- Fig. 4. Experimental moisture content data (&) and moisture
sionless form versus time at four different temperatures content predicted with different models:       , moisture content
are shown in Fig. 3. Also are shown the fitted values calculated with one term (n ¼ 1) in the solution to the diffusion
equation [Eqn (5)] and the diffusion coefficient estimated taking
with Eqn (13) at the corresponding temperatures into account one term in Eqn (5); - - - - -, two terms in the
(continuous line). The fitted model was used as a source Fourier series solution (n ¼ 2) but using the diffusion coefficient
of experimental data in the estimation procedures determined with one term in the series solution; }}}, moisture
described below. content calculated with two terms in the Fourier series solution
(n ¼ 2) and using the diffusion coefficient determined taking in
account two terms in the series solution
Table 2
Desorption-vaporisation heat at 10% moisture content
Taking into account just the first term of the infinite
Isosteric heat of vaporisation (DH),
Fourier series solution [Eqn (9)] for the dimensionless
Temperature (T), K kJ kmol1
moisture content, the diffusion coefficient at each of the
293 443445 four temperatures was estimated by a linear regression
303 439030
procedure. Assuming an Arrhenius type functional
313 434616
323 430201 dependency of the diffusion coefficient of the tempera-
ture, the activation energy and the pre-exponential
factor were estimated by a linear regression procedure.
1.0
The diffusion coefficient functional dependency of the
temperature obtained in this way was used in Fourier
series solution [Eqn (9)] truncated to one term for
0.8 predicting the dimensionless moisture content. The
results were compared with the experimental values
and are shown in Fig. 4. As can be appreciated in this
Moisture content

0.6
figure and as could be expected, there is a significant
error in the prediction for short times. The error is
0.4 significant even at time values as large as 1500 s.
Figure 5 shows the values of Dp2 t=r2 (Fourier number
for mass transfer) corresponding to the values for D of
0.2 between 1 and 100 mm2 s1 and time values between 0
and 1  103 s. The curve on the figure represents pairs of
values of D and t that produce values for Dp2 t=r2 of 12.
0.0
0 2000 4000 6000 8000 10000 12000 The region on the left side of this curve represents values
Time, s of D and t that led to values of Dp2 t=r2 512. It can be
Fig. 3. Experimental moisture content data and fitted moisture appreciated that this region corresponds to considerable
content with Eqn (6) at four temperatures: &, 313 K; *, 323 K; time values (as large as 1000 s). Therefore, in order to
m, 333 K; $, 343 K obtain a better agreement between the experimental and
 ARTICLE IN PRESS
PROPERTIES OF AMARANTH SEEDS 445

expression the resulting correlation is

 
5 358931
D ¼ 44131  10 exp  ð15Þ
T
Taking two terms of the solution to the drying
4 problem given by Eqn (9) and the diffusivity corre-
3 sponding to each temperature level analysed in this
1000
Dπ2t/r 2

2 work as described above, the following Arrhenius

1 750 expression for D as a function of T is obtained:
0  
333461

t, s
5
0 500 D ¼ 12586  10 exp  ð16Þ

e
T

Tim
25
Dif 250
fusi
o
50 The values of the diffusion coefficient obtained for
n co
effi
cien 75 a third-order approximation do not differ significantly
t D, 0 from those obtained with a second-order approxima-
mm 2 100
s tion. This means that the value of the diffusion
Fig. 5. Fourier number for mass transfer (Dp2t/r2) for values of coefficient obtained for a second-order approximation
the diffusion coefficient (D) between 1 and 100 mm2 s1 and time could be used in a higher-order approximation leading
values (t) between 0 and 1  103 s. The particle radius (r) is to a better agreement between the experimental data and
0005 m; the solid curve represents pairs of values of D and t the predicted values of the moisture content at short
that produce values of Dp2t/r2 ¼ 12; this curve delimits the
region, defined by values of D and t, for which the error times. The improvement in the prediction of the
committed taking just one term in the series in Eqn (9) leads to a moisture content values with respect to the experi-
minimum error (less than 5%) from that region for which the mental values can be appreciated in Fig. 4. The values
error committed is appreciable obtained with Eqns (15) and (16) are of the same
order of magnitude as those reported for similar seeds
(Zogzas et al., 1996).

the predicted values of the moisture content the

diffusion coefficient was determined by taking into
account more than one term in the series solution in
the way described below.
An error measurement as a function of the number
of terms in the approximation to Mds [see Eqn (9)]
taken into account n and the diffusion coefficient is
introduced as
X
N
exp 2
eðn; DÞ ¼ ðMds  Mds Þi
i¼1
exp
where: Mds stands for the experimental values [as given
by Eqn (13)] and N is the number of time values at
which the difference between the predicted and the
experimental values is evaluated. For a given order of
the approximation n, the value of D that leads the error
to zero (except for a certain tolerance) is obtained by
means of a Newton–Raphson method giving as the
initial estimate the value of D obtained with an
approximation of order ðn  1Þ.
Taking only the first term of the solution to the drying
problem given by Eqn (9), the diffusivity corresponding
to each temperature level used in this work was
evaluated. An Arrhenius-type relationship between D
and T was fitted. Substituting the activation energy and
the pre-exponential factor obtained in the Arrhenius
4. Conclusions
In this work the physical characteristics of a variety of
amaranth grains were determined. Among these are the
equivalent diameter, the sphericity, the true and bulk
densities. Also some thermodynamic and transport
properties of these grains were determined: heat
capacity, water activity, vaporisation–desorption heat
and the effective diffusion coefficient of water in the
ð14Þ
grain. The estimation of the mass diffusion coefficient
was based on an infinite Fourier series solution to the
mass diffusion equation. The effect on the goodness of
the approximation of the number of terms taken into
account when the infinite series is truncated was
analysed. Mass diffusivity values were estimated when
one and two terms were taken into account. It is
concluded that for time values as large as 1000 s the
experimental drying data for amaranth grains are better
approximated with two terms in the solution series with
the diffusivity determined taking into account also two
terms. Arrhenius-type equations were used to represent
the diffusion coefficient dependency on temperature. The
corresponding parameters (activation energy and the
pre-exponential factor) were evaluated for the diffusivity
values determined with one and two terms in the Fourier
series solution to the diffusion equation.
 ARTICLE IN PRESS
446 M.G. VIZCARRA MENDOZA ET AL.
Acknowledgements
The authors gratefully acknowledge the financial
support received from Consejo Nacional de Ciencia y
Tecnolog!ıa under Project 400200-5-1356PA.
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