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Journal of Food Engineering 78 (2007) 1029–1033

www.elsevier.com/locate/jfoodeng

Moisture diffusivity in quinoa (Chenopodium quinoa Willd.) seeds:


Effect of air temperature and initial moisture content of seeds
Marı́a C. Gely, Estela M. Santalla *

Chemical Engineering Department, Seeds Technology Program, Facultad de Ingenierı́a UNCPBA. Av. del Valle 5737, B7400JWI Olavarrı́a,
Provincia de Buenos Aires, Argentina

Received 24 September 2005; accepted 21 December 2005


Available online 13 February 2006

Abstract

The moisture diffusivity in quinoa (Chenopodium quinoa Willd.) seeds were evaluated as a function of the air drying temperature and
the initial moisture content of seeds obtaining values between 2.53 · 1012 m2/s (30 C, 12.87% d.b.) and 7.67 · 1011 m2/s (90 C,
23.44% d.b.). From a statistical analysis based on a factorial experiment, moisture diffusivity showed higher dependence with drying
air temperature than with the initial moisture content at P < 0.01.
A model based on an Arrhenius-type equation, temperature-dependence was proposed to estimate the activation energy in quinoa
seeds. An average value of 37.97 kJ/mol (standard deviation 3.9 kJ/mol) was obtained for the range of temperature evaluated.
Linear correlations between moisture diffusivity and the inverse of the absolute temperature was obtained for all the initial moisture
contents evaluated, with regression coefficients above 0.94 (significant at P < 0.05).
ANOVA test reported a significant interaction at P < 0.05 for both temperature and initial moisture content on moisture diffusivity.
Based on these results, a linear relationship initial moisture content-dependence was proposed for the pre-exponential Arrhenius factor.
A good agreement was found for the equation proposed (D = (B Æ M0 + C) Æ exp(Ea/RT)) obtaining a correlation coefficient of 0.97
(significant at P < 0.05).
 2006 Elsevier Ltd. All rights reserved.

Keywords: Quinoa; Thin-layer drying; Moisture diffusivity

1. Introduction properties of quinoa seeds are useful for the design of unit
operations and equipments related to the post harvest pro-
Quinoa seeds are originate from South America and cess such as cleaning, classification, transport, aeration,
constitutes a potential agronomic culture because it can drying and storage and they have been studied previously
adapt to produce high yields under adverse conditions (Vilche, Gely, & Santalla, 2003). Moisture transport (diffu-
(Wilson, 1985). Quinoa flour is low in gluten due the low sivity) has been found to vary widely in food materials, due
content of prolamines and glutamines (Herencia, Alı́a, mainly to different physical structure. The drying curves
González, & Urbano, 1999) and is higher in protein, lysine, obtained from drying experiments under controlled condi-
fat and fibre in comparison with common cereals (Coulter tions provide useful information on the mechanism of
& Lorenz, 1990). moisture transport and they are utilized for the determi-
The processing of quinoa seeds in Argentina are in its nation of the effective moisture diffusivity (Saravacos &
previous stages since the use of the grain is limited to pri- Maroulis, 2001).
mary consumption mainly in a handled way. Physical The objective of the current study was to determine and
model the moisture diffusivity in quinoa seeds. A statistical
*
Corresponding author. Tel./fax: +54 02284 451055. arrange was used to determine the air drying temperature
E-mail address: esantall@fio.unicen.edu.ar (E.M. Santalla). and the initial moisture content (M0) dependence. The

0260-8774/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2005.12.015
1030 M.C. Gely, E.M. Santalla / Journal of Food Engineering 78 (2007) 1029–1033

moisture diffusivity was estimated from the experimental expansion, a diffusional equation of two terms was devel-
data from thin-layer drying tests. Relationships between oped from the Fick diffusion equation of the form:
moisture diffusivity, temperature and initial moisture con- M  Me 2 pffiffiffiffiffi f
tent dependence were analyzed. MR ¼ ¼ 1  pffiffiffi aV Dt þ a2V Dt ð2Þ
M0  Me p 2
where f = 0.661, Me = equilibrium moisture content (%,
2. Materials and methods
d.b.), t = drying time (seg) and the surface area/particle
volume (m1) is aV = 3/R, for spherical geometry. Eq. (2)
The quinoa (Chenopodium quinoa Willd.) seeds used in
is called ‘‘short time’’ equation and is valid for moisture ra-
the present study were obtained from a crop grown during
tio MR between 0.2 and 1.
autumn season of the year 2001 in the Humahuaca Queb-
The Me for each temperature and relative humidity was
rada (2334 0 S, 6522 0 W) province of Salta, Argentina. The
adjusted from modified GAB equation that includes the
seeds were manually cleaned to remove foreign matter,
dependence of the GAB parameters with temperature
broken and immature seeds. The seeds were conditioned
(Rohvein, Santalla, & Gely, 2004).
to five initial moisture content ranging from 8.57% to
The adjusting of the thin-layer drying dates to obtain the
23.44% d.b. The original m.c. of seeds was 15.42% d.b.
diffusion coefficient at different air drying temperatures and
The samples at the m.c. below this value were prepared
M0 was done using the nonlinear model of Systat Statistical
by drying a sample in a convection air oven at 20 C.
Software (Wilkinson, 1990).
The samples at the m.c. above the initial value were
A laboratory thin-layer dryer was used to evaluate the
obtained by spraying pre-calculated amounts of distilled
drying rates of quinoa seeds. A fan drove the air through
water followed by continuous tumbling of the samples in
a heating unit towards the drying chamber in which the
sealed containers. Before being used, the samples were then
seeds were spread on a 0.0232 m2 removable tray. The
stored at 5 C in a refrigerator for a minimum of a week to
hot air flowed uniformly across the sample at constant
allow uniformity of moisture sample distribution. Before
velocities from 0.28 to 0.31 m/s controlled by a damper
each test, the required quantities of the conditioned
and measured on a calibrated orifice plate. Thin-layer dry-
seeds were allowed to warm up to room temperature
ing of seeds is independent of air velocity above 0.2 m/s
(Deshpande, Bal, & Ojha, 1993).
(Henderson & Pabis, 1962; Hutchinson & Otthen, 1983).
Moisture contents were determined by the air-oven pro-
Before each run the air was heated at the desired dry bulb
cedure described in ASAE Standard S352.1. All m.c. were
temperature through electrical resistances. Relative humid-
determined using two replications. The thin-layer drying
ity (HR) was measured by using an aspirated psicrometer
experiences were determined at five initial moisture con-
(Paspst, Type 8550 VW). In order to stabilize the condi-
tents: 8.57%, 12.87%, 15.42%, 17.32% and 23.44% d.b.
tions before each test the equipment was previously run
(dry basis). and four air drying temperatures (T): 30, 50,
for 1 h. Drying runs were carried out at the four tempera-
70 and 90 C.
tures and five M0 described above. The moisture loss was
The transport of water in solids is usually assumed to be
registered along time and the test was concluded when
controlled by molecular diffusion thanks to the equivalent
the moisture of the sample reached a moisture ratio
moisture gradient. For simplified analysis one-dimensional
between 0.2 and 0.3. Standard deviations of final m.c. of
diffusion is considered and the Fick diffusion equation is
duplicate drying runs resulted lower than 0.5% for all cases.
applied:
Analysis of variance was used to estimate the effect of
  the air temperature and the M0 on the diffusion coefficient.
oM o oM
¼ D ð1Þ A factorial 22 experiment was proposed to determinate the
ot or or
effect of the two factors which were studied at two levels: 30
where M = moisture content; D = moisture diffusivity and 90 C for temperature and 8.57% and 23.44% d.b. for
(m2/s) and r = equivalent radio of seed, mm. The diffusion M0. The experiment was carried out in four treatments by
coefficient D of water in seeds is an overall transport prop- duplicates reaching eight runs developed under a random
erty that involves other transport mechanisms such as design. Correlation analysis of the data was performed
hydrodynamic and capillary flow. In seeds, drying takes using Systat Statistical Software. Significance of effects
place mainly in the falling rate period and the internal mass and interactions were analyzed at a level of 95% and 99%
transport becomes very important. A constant slope of the confidence.
drying curve in semi-log plots of log MR (moisture ratio,
dimensionless) vs t indicates a constant moisture diffusivity 3. Results and discussion
which can be estimated by analytical techniques. In this
study, the diffusion coefficient was obtained from ‘‘short 3.1. Diffusion coefficient: air temperature and M0
time’’ equation (Giner, 1999) obtained from the diffusional dependence. Factorial arrange.
analysis of one particle drying and based on the experimen-
tal thin-layer drying. According to Becker (1959) based on Drying kinetics of wet quinoa seeds is shown in Fig. 1
semi-infinite medium concept and the Mc Laurin serie where moisture ratio is represented along drying time for
M.C. Gely, E.M. Santalla / Journal of Food Engineering 78 (2007) 1029–1033 1031

1.2 results are in agreement with those reported for wheat by


23.44% d.b.m.c. Gastón, Abalone, Giner, and Bruce (2004).
1.0 Analysis of variance was carried out to determine the
90 °C
0.8
significance of the drying temperature and M0 on the diffu-
70 °C
sion coefficient. To carry out the ANOVA, the diffusion
50 °C
MR

0.6 coefficient was considered as the parameter of the factorial


30 °C
experiment. The extremes values for M0 and temperatures
0.4 were used to carry out the test. The results demonstrated
0.2
that air temperature and M0 have both significant effect
on the diffusion coefficient at a level of 99%. The F values
0.0 obtained for temperature effect was FT = 116.74 and for
0 50 100 M0 effect F M 0 ¼ 299:9 comparing with the critical value
a Drying time, min
for T-test of F0.01;3;4 = 28.71. An interaction effect T–M0
1.20 was detected at P < 0.01 with a value of F T –M 0 ¼ 86:67.
90 °C Tukey test was applied on unidirectional averages of tem-
1.00 perature and M0 and the results obtained demonstrated
8.57% db that all means resulted not significantly different at
0.80 initial m.c. P < 0.05.
Fig. 2 shows the interaction T–M0 effect on moisture dif-
MR

0.60 fusion coefficient. For example, an increase of air tempera-


23.44% d.b.
initial m.c. ture between 30 and 90 C causes a relative increase of
0.40
512% on the value of diffusion coefficient for an M0 of
8.57% d.b. while an increase of 869% was observed for
0.20
23.44% d.b. M0. The magnitude of the moisture effect is
0.00 different according the level of temperature of the grain.
0 10 20 An increase of 15% in the M0 causes changes in the diffu-
b Drying time, min sion coefficient of 96% at 30 C and 210% at 90 C.
Fig. 1. (a) Variation of MR along drying time for air temperatures
between 30 and 90 C at M0 = 23.44%. (b) Variation of MR along drying 3.2. Diffusional coefficient, air temperature,
time at 90 C for initial moisture content of 8.57% and 23.44%. M0 relationships

In order to analyze the relationship between the mois-


air temperatures between 30 and 90 C. The curves show
ture diffusion coefficient with the drying air temperature
values of MR until 0.2 in order to apply Eq. (2). The upper
and the M0 of the seeds, the following experimental thin-
figure shows the behaviour obtained for the higher M0
layer runs were considered: 30, 50, 70 and 90 C and
(23.44%). The same behaviour was observed for the rest
8.57%, 12.87%, 15.42%, 17.32% and 23.44% d.b. M0.
of the m.c. evaluated. The lower figure shows the behaviour
Based on the T–M interaction found through the
obtained for two different M0 at 90 C. Similar response
ANOVA test, both variables were taken into account to
was obtained for the other temperatures.
found a relationship that involves this behaviour. At first,
A nonlinear model was used to adjust the experimental
an Arrhenius-type equation, temperature-dependence was
data to Eq. (2) in order to obtain the moisture diffusion
coefficients. Table 1 shows the obtained values for the
lower and higher values for M0 and temperature studied
and the significance of the statistical parameters at a confi- 8.00E-11
dence level of 95%.
Moisture diffusion coefficient, m2/s

7.00E-11 8.57%
Values of the diffusion coefficient indicate that drying d.b. initial
rates in quinoa seeds increase when air temperature 6.00E-11 m.c.
increases and also when seeds have a higher M0. These 5.00E-11 23.44%
d.b. initial
4.00E-11 m.c.
3.00E-11
Table 1
Average diffusion coefficients (m2/s) 2.00E-11
11 2 2 1.00E-11
T, C m.c. % b.s. D · 10 m /s Standard deviation R
12
30 8.57 0.379 1.18 · 10 0.971 0.00E+00
30 23.44 0.742 6.52 · 1013 0.993 0 20 40 60 80 100
90 8.57 2.32 3.37 · 1013 0.993 Air drying temperatures , ºC
90 23.44 7.19 6.76 · 1012 0.991
Fig. 2. Interaction T–M0 on moisture diffusivity coefficient.
1032 M.C. Gely, E.M. Santalla / Journal of Food Engineering 78 (2007) 1029–1033

Table 2 lnðDÞ ¼ ðB  M 0 þ CÞ  expðEa =RT Þ ð5Þ


Activation energy for quinoa seed drying process at different M0
Similar equation was proposed by Giner and Masche-
M0, % d.b. A Ea, kJ/mol R2
roni (2002) for wheat. The results of the adjustment are
8.57 9.67 · 107 32.498 0.942 shown in Table 3.
2.87 2.83 · 105 40.986 0.998
15.42 1.59 · 105 38.658 0.992
Differences between moisture diffusivities obtained
17.32 3.52 · 105 40.521 0.987 through Eqs. (2) and (5) resulted lower than 1.6%.
23.44 1.51 · 105 37.230 0.963

4. Conclusions

Variations between 0.379 and 7.19 · 1011 m2/s were


-23.0
0.0027 0.0028 0.0029 0.0030 0.0031 0.0032 0.0033 0.0034
found for the moisture diffusivity of quinoa seeds in the
-23.5 range of 30–90 C of air temperature and 8.57–23.44%
M0 = 8.57%
d.b. M0. A factorial arrange was used to evaluate the effect
-24.0
M0 = 12.87 % and significance of the two variables considered. The
-24.5 M0 = 15.42 % results of the ANOVA test showed a significant interaction
temperature–M0 at P < 0.01 on the moisture diffusivity in
ln D

-25.0 M0 = 17.32 %

M0 = 23.44 %
spite of the effect of the air temperature resulted higher.
-25.5 Based on the interaction found, an Arrhenius-type temper-
-26.0 ature functionality was proposed, to analyze the effect of
these two factors, constricting the effect of the M0 to the
-26.5 pre-exponential factor of Arrhenius equation. A linear
-27.0 relationship of the form B Æ M0 + C was proposed for the
1/ T pre-exponential Arrhenius factor–M0 dependence. A good
Fig. 3. Relationship between moisture diffusion coefficient and tempera- agreement of the experimental data was found for the
ture for five different M0 of quinoa seeds. Straight lines represent Eq. (4) equation proposed, obtaining a correlation coefficient of
and rotules indicate the values of D obtained from Eq. (2). 0.97 at a 99% level of significance. A constant value of
37.9 kJ/mol for the activation energy was found for the
considered to correlate the values of moisture diffusivity range of temperature used.
with temperature:
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