Journal of Food Engineering 108 (2012) 427–435

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Journal of Food Engineering

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Analytical model for variable moisture diffusivity estimation and drying simulation
of shrinkable food products
I.I. Ruiz-López a,⇑, H. Ruiz-Espinosa a, P. Arellanes-Lozada a, M.E. Bárcenas-Pozos b, M.A. García-Alvarado c
a
Colegio de Ingeniería en Alimentos, Facultad de Ingeniería Química, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, Ciudad Universitaria, Puebla, Mexico
b
Departamento de Ingeniería Química y Alimentos, Universidad de las Américas Puebla, Ex-Hda, Santa Catarina Mártir, C.P. 72820, Cholula, Puebla, Mexico
c
Unidad de Investigación y Desarrollo en Alimentos, Departamento de Ingeniería Química y Bioquímica, Instituto Tecnológico de Veracruz,
Av. M.A. de Quevedo S/N. Col. 5 de Mayo, C.P. 91860, Veracruz, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: An analytical model based on Fick’s second law of diffusion has been developed to both evaluate mass
Received 29 June 2011 transfer properties and describe drying kinetics of shrinkable food products. The proposed model was
Received in revised form 29 August 2011 validated with experimental drying data of chayote slices (0.6 cm thickness) obtained at air temperatures
Accepted 31 August 2011
of 40, 50, 60, and 70 °C. In all cases, an excellent agreement was found between experimental drying
Available online 8 September 2011
curves and predicted results (R2 > 0.9969). As expected, the use of higher drying temperatures increased
effective water diffusivities, while no effect was observed on shrinkage evolution of the product
Keywords:
(p < 0.05). In addition, diffusivity values were found to decrease along with the moisture content of cha-
Diffusion
Drying
yote slices (p < 0.05). Under the described experimental conditions, mean water diffusivities were in the
Modeling range of 4.44  1010–8.60  1010 m2/s. Results demonstrated that the proposed model can be applied
Simulation for the accurate description of experimental drying curves allowing a reliable estimation of mass transfer
Shrinkage properties in shrinkable food products such as chayote.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction In addition, heat transfer into solid is generally represented by a

Hot-air drying is the most widely used technique for the pro-
duction of dehydrated foodstuffs. This operation involves several
heat and mass transfer mechanisms; however, water diffusion
within the product is usually considered the controlling factor,
very often described by a diffusion mechanism based on Fick’s sec-
ond law (Białobrzewski, 2006; Ruiz-López and García-Alvarado,
2007). The unsteady-state mass transfer equation for moisture dif-
fusion within a homogeneous and isotropic material (represented
by V) is expressed as (Białobrzewski, 2006; Ruiz-López et al.,
2011):
@ðqXÞ
¼ r  ½DrðqXÞ in V
@t
where a convection mechanism has been generally used to express
mass transfer from product surface (A) to bulk air, which is repre-
sented by the following boundary condition (Białobrzewski, 2006;
Ruiz-López et al., 2011):
hm
ðHi  HÞ ¼ n  DrðqX i Þ in A
v
⇑ Corresponding author. Tel.: +52 222 2295500x7250.
E-mail addresses: irvingisrael@hotmail.com, irving.ruiz@correo.buap.mx
(I.I. Ruiz-López).
conduction mechanism (Białobrzewski, 2006):
@ðdC p TÞ
¼ r  ½krT in V ð3Þ
@t
In a similar way to Eq. (2), a convection mechanism has been used
to express mass and heat transfer from product surface to bulk air
(Białobrzewski, 2006):
hh ðT i  HÞ ¼ n  krðT i Þ þ n  QDrðqX i Þ in A ð4Þ
Many foods, especially fruits and vegetables, may present a high
shrinkage degree when dried. This phenomenon has been recognized
as the main factor affecting water diffusivity estimation due to
ð1Þ shortening of water diffusion path (Ruiz-López and García-Alvarado,
2007; Janjai et al., 2008; Zielinska and Markowski, 2010; Milczarek
et al., 2011; Thuwapanichayanan et al., 2011). Therefore, an accurate
simulation of food drying curves and the reliable estimation of mass
transfer properties need to consider dimensional changes of the
product. Both numerical and analytical approaches can be taken to
solve the proposed drying models represented by Eqs. (1)–(4)
ð2Þ depending on problem complexity (Ruiz-López and García-Alvarado,
2007).
The numerical solution of heat and mass transfer equations
allows the use of constant or variable food properties and shrink-
age can be readily included in calculations. This approach is used
very often for simulation purposes, where water diffusivity is

0260-8774/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2011.08.025
428 I.I. Ruiz-López et al. / Journal of Food Engineering 108 (2012) 427–435
Nomenclature
A denotes product surface
A,B subsets of positive real numbers
Bim Biot number for mass transfer (dimensionless)
b1,b2 parameters for Page’s model (dimensionless)
c0,c1,c2 parameters for moisture diffusivity equation (m2/s)
c3 parameter for moisture diffusivity equation (dimension-
less)
Cp specific heat of product (J/kg K)
D effective diffusivity of water in food (m2/s)
D1,D2 Page’s model-based functions for moisture diffusivity
equation (dimensionless)
e basis vector of the orthogonal coordinate system
f,g,h arbitrary functions
k0 parameter for moisture diffusivity equation (m2/s)
k3 parameter for moisture diffusivity equation (m2/s K)
Keq water partition ratio between gas and solid phases
H absolute humidity of drying air (kg water/kg dry air)
hh external heat transfer coefficient (W/m2 K)
hm external mass transfer coefficient (m/s)
k effective thermal conductivity of food (W/m K)
k1,k2 parameters for moisture diffusivity equation (dimen-
sionless)
L characteristic length for moisture diffusion (m)
m power constant in shrinkage equation (dimensionless)
MRD mean relative deviation
N number of experimental data
n1,n2 parameters for moisture diffusivity equation (dimen-
sionless)
Q sorption heat of water (J/kg water)
R+ set of positive real numbers
R2 ; R2log determination coefficient: based on the original re-
sponse and its common logarithm transformation,
respectively
x arbitrary real number
X moisture content of product (dry basis) (kg water/kg dry
solids)
known in advance from previous studies or estimated from simpli-
fied solutions. This procedure has been followed during drying
simulation of several materials including apple, carrot, chitosan,
fish muscle and mango (Białobrzewski, 2006; Pinto and Tobinaga,
2006; Batista et al., 2007; Białobrzewski et al., 2008; Janjai et al.,
2008). Water diffusivity can also be iteratively estimated during
the numerical solution of these models as exemplified by the stud-
ies of Hadrich and Kechau (2009), Ramos et al. (2010) and Thuwa-
panichayanan et al. (2011) in products such as bananas and grapes.
However, the use of simple analytical models is preferred for water
diffusivity prediction due to several practical advantages such as
easier implementation and lower computational effort. Existing
analytical solutions to mass transfer equation are obtained under
negligible product shrinkage, and can be fitted to experimental
data to obtain constant diffusion coefficients (Janjai et al., 2008;
_
Al-Muhtaseb et al., 2010; Doymaz and Ismail, 2011); however, to
account for shrinkage of food material and moisture-dependent
diffusivity it has been common practice to adapt these models to
a number of circumstances, even though they were originally
developed for constant diffusivity and negligible shrinkage
assumptions (Dissa et al., 2008; Burmester and Eggers, 2010; Her-
nandez et al., 2010; Zielinska and Markowski, 2010; Milczarek
et al., 2011). Another particular interesting method for water diffu-
sivity estimation is the slopes method, which is a simple technique
based on the slope comparison of experimental and theoretical
semi-logarithmic drying curves (Perry and Green, 1997) and
t drying time (s)
T food temperature (K)
u spatial coordinate in food system
v humid volume of drying air (m3 humid air/kg dry air)
V denotes the product volume
^; y
y; y  arbitrary response: experimental, fitted and arithmetic
mean, respectively
Greek letters
d bulk density (kg/m3)
u resulting fraction of the initial characteristic length for
diffusion at the end of the drying process
kn exponential decay coefficient of the generalized analyt-
ical solution for one-dimensional mass transfer equa-
tion (for n = 1, 2, . . ., 1)
ln series coefficient of the generalized analytical solution
for one-dimensional mass transfer equation (for
n = 1, 2, . . ., 1)
q volumetric concentration of dry solids (kg dry solids/m3
product)
h modified Fourier number for mass transfer in shrinkable
products with time-dependent diffusivity (dimension-
less)
H air temperature (K)
s Fourier number for mass transfer (dimensionless)
n,f spatial coordinates in food system for analytical and
numerical solutions, respectively (dimensionless)
w,W free moisture fraction of product: local and average,
respectively (dimensionless)
Subscripts
0 at the beginning of the drying process
e at equilibrium
i at the air-product interface
deserves further insight. The application of this method to drying
data results in a series of diffusion coefficients for every experi-
mental point available in the drying curve, even if it was developed
under the assumption of constant diffusivity. This method has a
widely extended use for the estimation of moisture diffusivities
(Karathanos et al., 1990; Babalis and Belessiotis, 2004; Sakin
et al., 2007; Xanthopoulos et al., 2010) and has also been general-
ized for the shrinkable products-case (Pinto and Tobinaga, 2006;
Batista et al., 2007).
All of the above studies dealing with moisture diffusion evalua-
tion through analytical approaches to the mass transfer equation
solution where developed under the assumption of constant food
temperature (Dissa et al., 2008; Janjai et al., 2008; Al-Muhtaseb
et al., 2010; Burmester and Eggers, 2010; Hernandez et al., 2010;
_
Zielinska and Markowski, 2010; Doymaz and Ismail, 2011; Milcz-
arek et al., 2011). While this assumption is not necessarily a good
approximation, it is the only way to deduce an analytical solution
for unsteady-state diffusion equation, thought recent investiga-
tions have been conducted to obtain approximate analytical solu-
tions considering simultaneous heat transfer, but only for
simulation purposes with constant diffusivity and negligible
shrinkage (Barati and Esfahani, 2011a,b). Our group has previously
reported an analytical drying model (Ruiz-López and García-
Alvarado, 2007) allowing the estimation of variable diffusion coef-
ficients in shrinkable foods. However, the referred model was
deduced from a macroscopic mass balance under negligible heat
 I.I. Ruiz-López et al. / Journal of Food Engineering 108 (2012) 427–435 429

transfer. In order to elucidate the implications of the constant food case of mass transfer for constant D in a non-shrinkable product.
temperature assumption, it is necessary a direct analytical solution A similar procedure was presented by Crank (1975) for obtaining
to mass transfer by diffusion described by Eqs. (1) and (2) consid- analytical solutions to mass transfer equation with time-dependent
ering shrinkage and variable water diffusivity. Therefore, the aim diffusion coefficients. Crank (1975) provided the analytical solu-
of this work was to develop and validate an analytical model, tions to Eqs. (7) and (13) under the assumption of uniform initial
deduced from Fick’s second law of diffusion, to both evaluate mass distribution of the diffusing substance within the solid. The corre-
transfer properties and describe drying kinetics in shrinkable food sponding solutions for mean moisture content W in products with
products. In the model development, the implication of constant flat slab, infinite circular cylindrical or spherical geometries exhibit
temperature assumption is discussed. Besides, the theoretical con- the following general form:
nection of proposed model with the slopes method is presented. X
1
2
W¼ ln ekn h ð14Þ
n¼1
2. Materials and methods
The use of analytical solution (14) and variable transformation (10)
2.1. Theoretical development to both evaluate mass transfer properties and describe drying kinet-
ics in shrinkable food products will be developed in the following
Mathematical description of drying process given by Eqs. (1)–(4) sections. The theoretical connection between Eqs. (10) and (14)
was simplified in order to obtain a simple analytical solution to with the slopes method for moisture diffusivity estimation is
mass transfer equation in shrinkable food products. By assuming presented in Appendix A.
(i) negligible heat transfer, (ii) constant properties of drying air,
(iii) constant volumetric concentration of dry solids, and (iv) one- 2.2. Moisture diffusivity estimation
dimensional mass transfer in products with flat slab, infinite circu-
lar cylindrical or spherical geometries, the corresponding drying Drying kinetics data, in the form of W vs. t and L vs. t, can be
model may be expressed as follows: used for moisture diffusivity estimation using the following
  procedure:
@X 1 @ @X
¼ a  Dua in V ð5Þ
@t u @u @u
(a) Calculate h for every W value in the drying curve by solving
hm @X i
ðH  HÞ ¼ n  D eu in A ð6Þ Eq. (14).
v i @u
(b) Calculate the derivative dh/dt.
where a takes value 0, 1, or 2, for slabs, cylinders or spheres, respec- (c) Moisture diffusivities can be estimated from Eq. (10) at
tively. Let us consider that both diffusion coefficient D and charac- every experimental t as
teristic length for diffusion L are explicit drying time functions, i.e.,
D = D(t) and L = L(t). Therefore, Eqs. (5) and (6) can be rewritten as dh
DðtÞ ¼ L2 ðtÞ ð15Þ
2 dt
@w 1 @ w
¼ in V ð7Þ Because of Eqs. (10) and (14), then W = f(t), where f:R+ ? A
@h na @n2
@wi (A  Rþ ¼ fx : 0 6 x 6 1g) is a bijection and thus t = f1(W). More-
¼ Bim wi in A ð8Þ over, it was considered that L = g(t) where g:R+ ? B and
@n
B  Rþ ¼ fx : L0 / 6 x 6 L0 g. Therefore, it is possible to define
where the following dimensionless groups and variables were L = g(f1(W)) = h(W) where h:A ? B. The latter result indicate that
introduced: shrinkage data in Eq. (15) could also be provided in the form of
L = L(W) since W is a function of drying time t. A similar reasoning
X  Xe
w¼ ð9Þ can be applied to demonstrate that time-dependent diffusion coeffi-
X0  Xe
cients D(t) could be related with mean moisture content W in order to
DðtÞ
@h ¼ 2 @t ð10Þ express the results in the form D = D(W).
L ðtÞ Above discussion was developed under the assumption of con-
1 stant product temperature, which is widely adopted in several stud-
@n ¼ @u ð11Þ
LðtÞ ies dealing with analytical approaches to mass transfer equation
ð1=v Þ hm solution during drying (Ruiz-López and García-Alvarado, 2007; Dis-
Bim ¼ K eq ð12Þ sa et al., 2008; Hernandez et al., 2010; Zielinska and Markowski,
q ½DðtÞ=LðtÞ
2010; Milczarek et al., 2011). If product temperature were variable,
An equilibrium distribution coefficient (Keq) has been used in the then free moisture fraction could be expressed as W = f(t, T0, H). At
definition of Biot number for mass transfer (Bim) to relate water any given T0 and constant air drying temperature H, f:R+ ? A contin-
content between solid and gas phases (Hi = KeqXi) (Cordova-Quiroz ues being a bijection (where A  Rþ ¼ fx : 0 6 x 6 1g). Therefore, if
et al., 1996). If the internal resistance to mass transfer by diffusion instantaneous mean product temperature T were evaluated under
is accepted as the only mechanism controlling drying rate, i.e., if constant H, then D = D(W, T) could be estimated from D(t). This
Bim > 40 throughout the drying process (Ruiz-López et al., 2011), same criterion applies to time-varying characteristic length for dif-
then moisture content at product surface Xi can be considered to fusion L(t). Nevertheless, this approach is limited because most
reach its equilibrium value Xe instantaneously. Under this assump- temperature recording devices used in drying processes mainly
tion, boundary condition presented in Eq. (8) is then simplified to rely in thermocouples, which inherently provide a local measure-
ment. Furthermore, even if temperature profiles can be integrated
wi ¼ 0 in A ð13Þ
to obtain mean temperature, product shrinkage may prevent an
The proposed variable transformations given by Eqs. (10) and (11) accurate positioning of thermocouples in sample during drying,
allow the simplification of the original problem for moisture diffu- rendering mean temperature evaluation unreliable and constant
sion in a shrinkable body with variable diffusivity to the simpler temperature assumption justified.
430 I.I. Ruiz-López et al. / Journal of Food Engineering 108 (2012) 427–435

2.3. Drying kinetics simulation values D(t) were plotted against free moisture fraction W in order
to both examine their behavior and propose a functional relation-
Eq. (10) can be used to simulate drying curves once the func- ship D(W) between these variables. Mean water diffusivities for
tional relationships between D(t) and W and L(t) and W have been every drying temperature were evaluated from the numerical
established by solving the ordinary differential equation: integration of instantaneous values using the trapezoidal rule
according to:
dt L2 ðtÞ L2 ðWÞ R W2
¼  ð16Þ DðWÞdW
dh DðtÞ DðWÞ W1
D¼ R W2 ð18Þ
subjected to the initial condition t(h = 0) = 0, where W is calculated W1 dW
from h in each iteration by solving Eq. (14), and W is further used to
Functions L(W) and D(W) were further used to simulate drying
evaluate both D(W) and L(W).
curves by integrating Eq. (16) with a variable order method based
on the numerical differentiation formulas by using the Matlab
2.4. Convective drying kinetics R2010a routine ode15s (MathWorks Inc., Natick, MA, USA). The
fitness quality of the proposed models was assessed with the deter-
Fresh, well-graded chayote fruits were washed, peeled, trans- mination coefficient (R2) and the mean relative deviation (MRD):
versally cut into circular slices (0.6 cm thick, 7 cm diameter), and PN P
resulting samples were subjected to convective drying at air tem- y Þ2  Nn¼1 ðyn  y
n¼1 ðyn
^ n Þ2
R2 ¼ PN 2
ð19Þ
peratures of 40, 50, 60, and 70 °C with an air velocity of 2 m/s. A 
n¼1 ðyn  yÞ
single slice (particle drying) was placed flat on a non-perforated 1X 1
yn  y^n
tray (25  20 cm) in a tunnel dryer (Armfield UOP8, Ringwood, MRD ¼ j j ð20Þ
N n¼1 yn
UK) with air flow parallel to the product. Experimental conditions
were selected to better fulfill several hypothesis made during mod- For drying kinetics, an additional determination coefficient (R2log )
el development. For example, air velocity and slice thickness were was also calculated with the common logarithm transformation of
chosen to allow for a diffusion-controlled process (negligible exter- moisture content to better measure the fitness characteristic of the
nal resistance to mass transfer) according to the analysis presented model at low moisture contents. Nonlinear regression (based on
by Pavón-Melendez et al. (2002), whereas slice geometry facilitates ordinary least squares) and statistical analyses were performed with
that one-dimensional mass transfer with shrinkage occurs almost the Matlab Statistics Toolbox 7.3 (MathWorks Inc., Natick, MA, USA).
exclusively in the minor dimension of product. Additionally, the As previously mentioned, our group developed an analytical
assumption of constant air properties is favored by the combina- drying model (Ruiz-López and García-Alvarado, 2007) allowing
tion of single particle drying and the use of a high airflow. Moisture the estimation of variable diffusion coefficients in shrinkable foods
evolution was calculated by continuously weighing the product from a macroscopic mass balance. However, there are major differ-
every 15 min during drying. Initial moisture content was deter- ences between current and previous solving-problem approaches
mined by oven-drying (Binder ED 53, Germany) the samples at deserving special attention:
105 °C until constant mass weight (when mass change was less
than 0.001 g over an 8 h period). Meanwhile, product shrinkage (a) Former solution was developed for shrinkage data expressed
was determined by measuring changes in product thickness with as a fixed straight line function of moisture content W. That
a micrometer during additional tests conducted under the same is, shrinkage representation was restricted to Eq. (17) with
conditions as above. A different sample set was prepared with a constant m = 1. Even so, shrinkage data can be related with
K-type thermocouple placed in the center to follow temperature t or W by means of any functional form or given as tabulated
evolution during drying. Temperature was registered every 10 min. data in the present solution.
(b) A fixed (both monotonically decreasing or increasing) diffu-
2.5. Method implementation sivity exponential function of moisture content W was used
to develop earlier solution, resulting in a predefined water
The following relationship is proposed in this study to relate diffusivity behavior when that model is used for estimation
dimensional changes of product with moisture content, purposes. In current model, moisture diffusivity behavior is
identified without constraints and can be also related with
LðWÞ ¼ L0 / þ L0 ð1  /ÞWm ð17Þ
t or W by either continuous or discrete functions for simula-
Above formula, with m = 1, has been used to express linear shrinkage tion purposes.
of food products during drying (Ruiz-López and García-Alvarado,
2007). This equation has been generalized to express possible devi- 2.6. Numerical validation
ations from the linear shrinking behavior. For example, if 0 6 m < 1
then the plot of L vs. W follows a concave function behavior (concave Functional relationships D(W) and L(W) were also used for the
downwards), while if m > 1 then the corresponding plot is a convex direct numerical solution of mass transfer equation to demonstrate
function (concave upwards). The case m = 0 represents a product its applicability in a detailed simulation. Eqs. (5) and (6) were
where shrinkage is negligible. Shrinkage data were fitted to Eq. expressed in dimensionless form considering: (i) constant proper-
(17) to determine m and u. Significance of the regression parameters ties of drying air, (ii) constant volumetric concentration of dry
was tested by constructing their 95% confidence intervals (95% CI). solids, (iii) one-dimensional mass transfer in products with flat
Thereafter, drying kinetic data were used to estimate moisture slab, infinite circular cylindrical or spherical geometries, (iv)
diffusivities by using the proposed methodology, where Eq. (14) variable diffusivity and (v) negligible heat transfer
was numerically solved with the bisection algorithm and the term    
@w 1 @ @w @ @w ag @w
dh/dt was estimated with central finite differences. Flat slab ¼ a fa g ¼ g þ ð21Þ
parameters for Eq. (14) are given as ln = 8/[(2n  1)2p2] and
@ s f @f @f @f @f f @f
k2n ¼ ð2n  1Þ2 p2 =4 for the case of negligible external resistance to @wi
¼ Bim wi ð22Þ
mass transfer (Bim > 40) (Crank, 1975). The identified diffusivities @f
 I.I. Ruiz-López et al. / Journal of Food Engineering 108 (2012) 427–435 431

where the following dimensionless groups and variables are intro-

duced in addition to those previously described:

D0
s¼ t ð23Þ
L20
1
f¼ u ð24Þ
L0
D
g¼ ð25Þ
D0

while terms D(t) and L(t) are replaced with their initial values D0
and L0, respectively, in the Bim definition given in Eq. (12). Eqs.
(21) and (22) were numerically solved for the flat slab geometry
(a = 0) by using the method of lines (MOL) with central finite differ-
ences for space derivatives. The dimensional changes of product
were estimated with mean moisture fraction and global product
dimensions. A similar approach to that used for product shrinkage Fig. 1. Shrinkage characteristics of chayote slices during air-drying.
was considered for moisture diffusivity estimation. Both implemen-
tations were selected to closely match the experimental conditions
in which these properties were obtained. The MOL produced the 3. Results and discussion
following ordinary differential equation (ODE) system with s as
independent variable (for j = 1, 2, . . ., nf): 3.1. Shrinkage description

dwj wjþ1  2wj þ wj1 Initial moisture content of chayote was evaluated as 93.38 ±
¼g ð26Þ 1.03 g water/100 g product (mean ± s.d.). Shrinkage data obtained
ds ðDfÞ2
during convective drying of chayote slices are plotted in Fig. 1. An
wjþ1 ¼ wj1  2DfBim wj for j ¼ nf ð27Þ excellent agreement was found between experimental and pre-
wj1 ¼ wjþ1 for j ¼ 1 ð28Þ dicted data (R2 = 0.9871). Drying of chayote slices resulted in sam-
ples with about 11% of their original dimensions (/ = 0.1135, 95%
where nodes j = 1 and j = nf represent the food center and surface, CI = 0.0997/0.1273). Moreover, shrinkage data showed a significant
respectively. Symmetry or isolate boundary condition was applied departure from the linear behavior (m = 0.6670, 95% CI = 0.6393/
at node j = 1 (o W/o f = 0) to express the value of the auxiliary node 0.6948). No significant temperature effect on product shrinkage
j = 0 outside computational domain. The resulting ODE system was was observed (p < 0.05). Non-straight shrinking behavior can be
integrated for a diffusion-controlled process (implemented with related to both product deformation and cellular structure collapse.
Bim = 1000) with nf = 100 using the Matlab R2010a routine ode23s For free moisture fractions W > 0.4, the product shrinkage exhibited
based on a modified Rosenbrock formula of order 2 (MathWorks a straight behavior, where reduction in thickness is directly related
Inc., Natick, MA, USA). Mean moisture content of the product was to evaporated water volume. As drying proceeds, product deforma-
evaluated from the numerical integration of local values using the tion (flounce-shape edges and slight surface rugosity, especially at
trapezoidal rule according to formula: 60 and 70 °C) became apparent at moisture contents W  0.4 which
caused the shrinkage plot to curve. A further bending in the same
Rf plot was observed at W  0.1, where severe cellular structure
wdf
W ¼ R0 f ð29Þ damage is very likely to occur. This fact was reflected in a sharp
0
df decrease of moisture diffusivity during this drying period, as dis-
cussed in the next section. It is worth mentioning that severe defor-
Product shrinkage and water diffusivity were estimated from mean mation may be present in many foods at such low moisture contents
moisture fraction by performing the following procedure in each
time-step iteration:
(a) Set fk = 1 in the first iteration (k = 1).
(b) Calculate Df = fk/(nf  1).
(c) Calculate mean moisture content Wk with local moisture
(wj) and shrinkage (Df) values by solving Eq. (29).
(d) Calculate the corrected total characteristic length for
diffusion fk+1 as

Lk
fk ¼ ¼ / þ ð1  /ÞWm
k ð30Þ
L0
(e) Repeat steps (b)–(d) until differences in corrected total char-
acteristic length for diffusion from consecutive iterations is
lower than a given tolerance.
(f) Calculate g with mean moisture fraction from the last
iteration.

Finally, the differences between experimental and simulated

results were quantified by means of the statistical indices R2, R2log
and MRD. Fig. 2. Experimental and simulated air-drying curves of chayote slices.
432 I.I. Ruiz-López et al. / Journal of Food Engineering 108 (2012) 427–435

Fig. 5. Estimated water diffusivities during drying of chayote slices.

Fig. 3. Experimental temperature evolution of chayote slices at product center
during drying.

making precise diffusive drying modeling and accurate shrinkage

measurement very complex, especially in products with important
water losses along all dimensions. Hence, product geometry should
be chosen not only for fulfilling model assumptions, such as one-
dimensional mass transfer with shrinkage occurring in minor
dimension of product, but to minimize as well product deformation.

3.2. Moisture diffusivities

Experimental drying curves of chayote slices are shown in

Fig. 2. These data were used to evaluate moisture diffusivity as
described in Section 2.2. Estimated water diffusivities are plotted
in Fig. 3. As expected, the use of higher drying temperatures
promoted a higher water mobility in the food system (p < 0.05).
Moisture diffusivity data exhibited a complex behavior at all
drying temperatures, where their values increased as the free
moisture fraction diminished (Fig. 4), showing a maximum value
at W  0.6, and further reduction thereafter. The experimental
temperature evolution of chayote slices at product center is shown
in Fig. 5. Similar trends have been reported for center and surface
temperature during fish muscle or single-coffee bean drying (Pinto
and Tobinaga, 2006; Burmester and Eggers, 2010). Despite the fact
that central temperature history could not necessarily match the
mean temperature evolution, these data indicate that product
Fig. 4. Central temperature behavior of chayote slices during air-drying as a
function of moisture content.
Fig. 6. Effect of moisture content on water diffusivity.
temperature does not remain constant during drying. Nonetheless,
constant product temperature (negligible heat transfer) assump-
tion is still widely adopted in drying studies due to some theoret-
ical and experimental limitations exposed in preceding sections.
Temperature data are further plotted as a function of the corre-
sponding moisture content in Fig. 6. A simultaneous analysis of
Figs. 4 and 6 reveals that an increase in moisture diffusivity up
to W  0.6 coincides with a rise in product temperature. As a
result, the gradual increase in water diffusivity at the beginning
of the drying process (i.e., for high moisture contents) is very likely
caused by product preheating. The initial heating phase is followed
by a stationary period where drying air energy is mainly used for
water evaporation with a second heating phase up to drying tem-
perature occurring afterward (Burmester and Eggers, 2010). At this
point, deceleration in water mobility may be caused by the begin-
ning of cell structure collapse. Comparable results for moisture dif-
fusivity behavior have been reported by several authors during
convective drying of different materials including chitosan, fish
muscle, grapes and fresh and pre-osmosed carrot cubes (Azzouz
et al., 2002; Pinto and Tobinaga, 2006; Batista et al., 2007; Singh
and Gupta, 2007).
Mean water diffusivities were estimated as 4.44  1010,
6.00  1010, 7.04  1010 and 8.60  1010 m2/s for drying
processes at 40, 50, 60 and 70 °C, respectively. Mean moisture-
dependent diffusivities, corrected for product shrinkage, are
comparable to the literature data for other vegetable products such
 I.I. Ruiz-López et al. / Journal of Food Engineering 108 (2012) 427–435 433

Table 1
Regression parameters for water diffusivity model.

Temperature Parameters* R2/MRD**

(°C) 9 2 11
k0  10 (m /s) k1 k3  10 n1 n2
(dimensionless) (dimensionless) (dimensionless) (dimensionless)
40 1.2122 (1.0993/1.3251) 2.6809 (1.6497/ – 8.3422 (5.5704/ 0.5374 (0.4619/ 0.9327/0.1325 (0.9239/
3.7121) 11.1139) 0.6130) 0.1441)
50 1.5656 (1.3159/1.8153) 2.6534 (0.5029/ – 10.4726 (3.4944/ 0.5634 (0.4195/ 0.8329/0.1663 (0.8266/
4.8039) 17.4508) 0.7072) 0.1713)
60 1.9092 (1.6891/2.1293) 2.6443 (1.2208/ – 9.4435 (5.2197/ 0.5710 (0.4734/ 0.9466/0.1637 (0.9448/
4.0679) 13.6673) 0.6687) 0.1674)
70 2.3946 (2.0769/2.7122) 2.6506 (1.1886/ – 8.7742 (4.6882/ 0.5876 (0.4751/ 0.9446/0.1407 (0.9434/
4.1125) 12.8602) 0.7000) 0.1361)
40–70 0.2508 (0.4720/ 2.6378 (1.9827/ 3.6706 (3.2188/ 9.1689 (7.2508/ 0.5684 (0.5208/ 0.9330/0.1545
0.0295) 3.2929) 4.1225) 11.0870) 0.6160)
*
Refer to Eqs. (33)–(36) in body text with k2 = 1. Values in parentheses indicate the 95% CI.
**
Values in parentheses indicate the R2/MRD values produced by Eq. (32) for the given temperature.

as carrots (2.58  1010 to 1.72  109 m2/s, 60–90 °C) and mango
(2.61  1010 to 1.30  109 m2/s, 40–70 °C) in which shrinkage
has also been considered (Dissa et al., 2008; Zielinska and Markow-
ski, 2010).
The studies of Pinto and Tobinaga (2006) and Batista et al.
(2007) have modeled diffusivity data described by a concave func-
tion. These models can be expressed in terms of free moisture frac-
tion W as:
DðWÞ ¼ c0 þ c1 W  c2 ec3 W
c3 W
DðWÞ ¼ c0 þ c1 We
Both models were fitted to moisture diffusivity data of chayote but
failed to accurately reproduce the experimental behavior. In particu-
lar, Eq. (32) achieved a very poor data description (0:5011 6 R2 6
0:7300, 0:3934 6 MRD 6 0:8406). However, Batista et al. (2007)
used Eq. (32) to successfully describe concave diffusivity data with
positive skew (defined similarly as in a statistical distribution) from
chitosan drying (R2 = 0.996). On the other hand, while Eq. (31)
achieved very good fitness indices (0:8942 6 R2 6 0:9631,
0:1125 6 MRD 6 0:1486), the model cannot reproduce the sharp
decrease of moisture diffusivity observed at lower moisture con-
tents (W < 0.1). Pinto and Tobinaga (2006) applied Eq. (31) to model
moisture diffusivity data with negative skew during thin-layer
drying of fish muscle with similar findings. These authors reported
a high determination coefficient (R2 = 0.96) but the model did not
capture the experimental data shape (a fast reduction in water
diffusivity) at X/X0 < 0.025. Consequently, the following model
was formulated for the mathematical description of moisture
diffusivity at each drying temperature:
DðWÞ ¼ k0 D1 D2
n
D1 ¼ ek1 W 1
D2 ¼ 1  e k2 Wn2
This model was constructed as the product of both monotonically
decreasing (0 6 D1 6 1) and increasing (0 6 D2 6 1) exponential-
type functions of free moisture fraction W based on the Page’s mod-
b
el (W ¼ eb1 t 2 ), which is used to describe thin-layer drying kinetics
and exhibits the same mathematical structure as Eq. (34) (Jangam
et al., 2008; Al-Muhtaseb et al., 2010). The product of D1 times D2
produces a concave function (0 6 D1 D2 6 1) where the peak width,
shape and displacement can be adjusted with parameters k1, k2, n1
and n2. Finally, the proper scaling of D(W) is obtained with param-
eter k0. Eq. (33) was able to accurately describe moisture diffusivity
data. However, parameter estimates k0 and k2 were not statistically
significant for all data sets (p < 0.05). Thus, either k0 or k2 were
removed from the original model (i.e., the parameters were set to
unity) and the nonlinear regression procedure was repeated. The
model with k0 = 1 resulted in a poor description of moisture diffu-
sivity data and non-significant parameter estimates for n1, n2 and
k2 (p < 0.05). On the other hand, the model with k2 = 1 retained
the fitting characteristics of the original five-parameter equation
but statistical analysis revealed that all constants were significant
(p < 0.05).
Summarized statistics for this last model are shown in Table 1.
A careful examination of these results allow identifying that tem-
ð31Þ perature effect is mainly reflected in the k0 values. Thus, the fol-
ð32Þ lowing modified model was proposed to account for temperature
effect over diffusivity:
n
 n

DðWÞ ¼ ðk0 þ k3 TÞek1 W 1 1  eW 2 ð36Þ
Summarized statistics for Eq. (36) are also listed in Table 1. A good
agreement was found between experimental and predicted results
(R2 = 0.9330). The functional relationship between D(t) and W, i.e.,
D(W), was further used for drying kinetics simulation of chayote.
3.3. Drying kinetics description
Eqs. (14), (16), (17), and (36) jointly with the methodology
described in Section 2.3 were used for drying kinetics simulation.
These results are plotted in Fig. 2. The proposed model achieved
an excellent description of experimental data at all moisture con-
tents (R2 > 0.9969, R2log > 0:9959, MRD < 0.1518). Fitness character-
istics of this model at all drying temperatures jointly with the
corresponding results for the direct numerical solution of mass
ð33Þ
transfer equation, obtained with Eqs. (26)–(30) and (36) and the
ð34Þ methodology described in Section 2.6, are summarized in Table
ð35Þ 2. Statistical indices of the numerical solution clearly match those
obtained for the drying simulations performed with the proposed
analytical model provided in Section 2.3, with minor differences
caused by numerical errors (the numerical solutions appeared per-
fectly overlapped to the simulated drying curves obtained with the
analytical model). This result was expected because both product
shrinkage and water diffusivity were estimated with mean mois-
ture content values during the numerical solution of diffusion
equation, that is, tested implementation numerically solves the
problem defined in Section 2.1. An straightforward consequence
of these results is that if water diffusivity and shrinkage data come
from mean product characteristics measurements (such as mean
moisture content and product thickness), drying simulation should
be performed with implementations matching these assumptions
to achieve the best experimental data description.
434 I.I. Ruiz-López et al. / Journal of Food Engineering 108 (2012) 427–435

Table 2 where [d ln W/ds]theoretical represents the expected asymptotic slope

Statistical indices obtained during drying kinetics simulation of chayote with of the plot of ln W vs. s obtained under negligible shrinkage and
numerical and proposed analytical solutions to diffusion equation.
constant diffusivity for a given set of product geometry and drying
Index Drying temperature (°C) Analytical model Numerical solution conditions, and is evaluated from Eq. (14) by simply replacing
Rt
R2 40 0.9987 0.9986 h ¼ 0 ½DðtÞ=L2 ðtÞdt with the traditional Fourier number for mass
50 0.9969 0.9969 transfer s = Dt/L2. The slopes method was originally proposed as a
60 0.9994 0.9994 mean to estimate constant diffusion coefficients in the straight sec-
70 0.9990 0.9990
tion of the plot of ln W vs. s (Perry and Green, 1997). Yet, the applica-
R2log 40 0.9959 0.9962
tion of this method to drying data results in a series of diffusion
50 0.9991 0.9991
60 0.9978 0.9980 coefficients for every experimental point available in the drying
70 0.9983 0.9986 curve which can be considered as D(t). This method has been widely
MRD 40 0.1518 0.1458 adopted to calculate the diffusion coefficients in experimental non-
50 0.0742 0.0744 straight logarithmic drying curves (Karathanos et al., 1990) and has
60 0.1182 0.1148
70 0.0932 0.0866
been generalized to shrinkable products by replacing the constant
term L in Eq. (A3) with its variable moisture-function counterpart
L(X) (Pinto and Tobinaga, 2006; Batista et al., 2007), which, as demon-
strated before, is interchangeable with L(t). The plot of ln W vs. h is
unique for any shrinking and moisture diffusivity behavior, but
4. Conclusions
ln W data could also be plotted versus s if this last variable is calcu-
lated from h, by combining Eqs. (16) and (23) and solving the result-
Existing analytical solutions for mass transfer under constant dif-
ing expression. In this case, the slope value d ln W/dh is different from
fusivity and negligible shrinkage have been generalized to describe
d ln W/ds if product exhibits shrinkage and/or variable diffusivity.
drying processes of shrinkable food products with time-dependent
However, the same plot of ln W vs. h overlaps with the traditional plot
moisture diffusivities. Resulting model may be applied for the
of ln W vs. s obtained for a non-shrinkable product with constant dif-
evaluation of time-varying diffusivities, which can be related with
fusivity, and d ln W/dh = d ln W/ds at any moisture content W even if
mean moisture content, and further used for an accurate simulation
h and s are not longer comparable. Thus, when the constant L is re-
of food drying. Moreover, the current approach to moisture
placed with L(X) in Eq. (39), the term [d ln W/ds]theoretical unwittingly
diffusivity estimation is not linked to a predefined water diffusivity
becomes d ln W/dh, making slopes method appropriate to determine
or product shrinking behavior. The proposed methodologies involve
variable diffusion coefficients in shrinkable products.
a relatively low computational effort and represent simple and
feasible ways to perform both the reliable estimation of mass
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