Research Article

Drying Kinetics of Silica Gel: Statistical

Discrimination Using Nonlinearity Measures
The objective of the present work was to analyze the drying kinetics of silica gel
based on an experimental study performed in a thin-layer dryer and a statistical
discrimination of the main drying kinetic equations. Most semi-empirical drying
kinetics equations presented in the literature are nonlinear; thus, care should be
taken when estimating parameters, since in some situations the estimators may
not be appropriate. There are procedures available to validate the statistical
properties of the least squares estimators of nonlinear models. In this study, five
semi-empirical drying kinetics equations were discriminated using measures of
curvature and bias. The results showed that the Overhults equation is the best
one to describe the drying kinetics of silica gel.
Keywords: Bias measurement, Curvature measurement, Nonlinear regression, Thin layer
Received: July 01, 2011; revised: October 02, 2011; accepted: January 18, 2012
DOI: 10.1002/ceat.201100342
1 Introduction
The use of dry air by adsorbents can be an interesting option
for drying since the air conditions play an important role in
the drying kinetics. The appropriate use of these conditions
can significantly reduce the drying time, improving the final
quality of the product [1] while reducing the energy consump-
tion by the system. Silica gel is the most common type of
adsorbent used as air desiccant [2] due to its high capacity of
removing water vapor present in moist air, since it presents a
microporous structure with great surface area [3].
A porous desiccant like silica gel removes water from the
surrounding air by two mechanisms: multi-layer adsorption
and capillary condensation. Multi-layer adsorption is the
attraction of thin layers of water molecules to the surface of
the desiccant. Since the desiccant is very porous, the surface
area is high and significant amounts of water can be attracted
and adsorbed. Capillary condensation is when the smaller
pores become filled with water. Capillary condensation occurs
when the saturated water vapor pressure in a small pore is re-
duced by the effect of surface tension. Adsorbent columns of
silica gel can be coupled to the drying process. This technique
presents several advantages, such as low initial investment, low
operational cost and the possibility of silica gel regeneration by
drying at low temperatures. Thus, silica gel products can be
dried and reused as new.
Obtaining the drying kinetics is of utmost importance to de-
termine the parameters that control the phenomena of heat
and mass transfer [3, 4]. The classic mode of approaching the
problem is through drying experiments in a thin layer [5]. The
literature reports semi-empirical drying kinetics equations,
generally based on the diffusive model, which is a simplifica-
tion of Luikovs theory [6] for drying in porous media. These
equations, in general, are nonlinear, and the parameters are es-
timated from experimental results by the least squares (LS)
method.
Since the majority of the drying kinetic equations in the
literature are nonlinear [5, 713], care should be taken when
estimating their parameters from experimental data. In some
situations, the estimators (especially, confidence intervals) may
not be appropriate [14]. Thus, some procedures are available
in the literature to validate the statistical properties of the LS
estimators of nonlinear models. Box [15] presented a useful
formula for estimating the bias in the LS estimators; Bates and
Watts [16] developed new measures of nonlinearity based on
the geometric concept of curvature.
The present study focuses on the use of nonlinearity mea-
sures to select, from five semi-empirical equations, the best
one to represent the drying kinetics of silica gel.
2 Equations of Drying Kinetics
A number of empirical and semi-empirical equations have
been proposed in the literature [7, 8 1719] to describe the
drying kinetics of several materials. Among them, Tab. 1
presents the drying kinetics equations applied to porous mate-
rials.
Chem. Eng. Technol. 2012, 35, No. 5, 797802 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Glaucia de Fatima M. V. Souza
1
Ricardo F. Miranda
1
Edu B. Arruda
2
Oscar S. H. Mendoza
1
Marcos A. S. Barrozo
3
1
Federal University of
Uberlndia, Mechanical
Engineering School, Campus
Santa Mnica, Uberlndia,
MG, Brazil.
2
Federal University of
Uberlndia, Chemical School
of Faculty of Integrated
Sciences of Pontal, Ituiutaba,
MG, Brazil.
3
Federal University of
Uberlndia, Chemical
Engineering School,
Campus Santa Mnica,
Uberlndia, MG, Brazil.

Correspondence: Dr. M. A. S. Barrozo (masbarrozo@ufu.br), Federal

University of Uberlndia, Chemical Engineering School, Block 1K,
Av. Joo Naves de vila, 2121, Campus Santa Mnica, 38400-902,
Uberlndia, MG, Brazil.
Curvature measurement 797
In the equations of Tab. 1, MR
1)
is the moisture ratio. The
parameter K presented in the equations is known as drying
constant and varies with temperature, according to the Arrhe-
nius function for Eqs. (1)(4), while for Eq. (5) the function
that represents this variation is different.
3 Nonlinearity Measures
Extensive methodology has been developed to investigate
whether a proposed model provides a good description of the
experimental data. Comparisons of the R
2
values and residuals
analysis may be insufficient to discriminate between nonlinear
regression models [20].
The LS estimators of linear regressions are non-biased, nor-
mally distributed, and present the least possible variance
among any other classes of estimators. However, for nonlinear
regressions, these properties are valid only when the sample
size is large enough. Consequently, it can be stated that the re-
sults become more applicable as the sample size increases.
When the LS estimators present small bias, near-normal distri-
bution and almost constant variances, it can be stated that the
estimators present a near-linear behavior and, consequently,
the inferences will be more reliable [21]. The extent of the bias,
the deviation from normal distribution and the excess variance
differ greatly from model to model. The extent of nonlinear
behavior can be evaluated through nonlinearity measures.
Thus, nonlinearity measurements are known as expressions
used to evaluate adequability of the linear approximation and
their effects on the inferences [22]. Box [15] presented a useful
formula for estimating the bias in the LS estimators; Bates and
Watts [16] developed new measures of nonlinearity based on
the geometric concept of curvature.
3.1 Curvature Measures of Bates and Watts
Bates and Watts [16] developed measures of nonlinear-
ity based on the geometric concept of curvature. These
authors demonstrated that the nonlinearity of a model
can be decomposed into two components: intrinsic
nonlinearity (IN), which is characteristic of the model,
and the nonlinearity due to the effect of parameters
(PE), which depends on the sequence in which the pa-
rameters appear in the model.
IN measures the curvature of all possible solutions
for the problem of LS in the sampled space. The solu-
tion of LS is the point in estimation space that is
nearest to the vector of response variables. A linear
regression model presents a nil IN measure, since the
estimation space is a straight line, a plane or a hyper-
plane. In contrast, the estimation space of a nonlinear
model is curved, and IN measures the extent of this
curvature. A negligible IN will mean a negligible bias
in the predicted values of response.
Nonlinearity due to parameter effects is a consequence of
the lack of uniformity of the coordinate system in the estima-
tion space. In the linear case, the parameter lines are parallel.
The measure PE is a scale quantity that represents the maxi-
mum value of the parameterization effect, obtained from a tri-
dimensional vector, known as acceleration vector. The accel-
eration matrix in a linear model is made of zeros, thus result-
ing in PE equal to zero. In contrast, in a nonlinear model with
a given IN value, the value of PE increases as its behavior devi-
ates from the linear behavior, since PE measures the extent of
the nonlinear behavior caused by parametrization. When the
nonlinearity is mostly due to the effects of parameters, a repar-
ametrization becomes important. If the parameter effects non-
linearity is negligible, the statistical tests of the consistency of
the fitted parameters will be valid.
Details about the development, procedure and equations for
determining IN and PE are found in the work of Bates and
Watts [16]. The statistical significance of these measures can
be evaluated by comparing the IN and PE values with 1=2

F
p
,
where F = F(a, np, p) is the inverse of Fishers probability
distribution obtained at the significance level a. The value
1=2

F
p
may be regarded as the radius of the curvature of the
100(1a)% confidence region. Hence, the solution locus may
be considered to be sufficiently linear within an approximately
95 % confidence region if IN < 1=2

F
p
(a =0.05). Similarly, if
PE < 1=2

F
p
, the projected parameter lines may be regarded as
being sufficiently parallel and uniformly spaced, i.e., the LS
estimates of the parameter do not depend on the user being
able to supply a good initial prediction and the tests of
parameter invariance will be adequate.
To perform all the calculations required to determine the IN
and PE values, a computer program in Fortran language was
developed for the present work.
3.2 The Bias Measure of Box
Box [15] proposed a statistics to evaluate the bias of LS estima-
tors of parameters of a univariate nonlinear regression model,
given by:
www.cet-journal.com 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2012, 35, No. 5, 797802
Table 1. Drying equations.
Equation Reference
MR = exp(Kt)
(1) Lewis (1921)
where K = A exp(B/T)
MR = C exp(Kt)
(2) Brooker et al. (1974)
where K = A exp(B/T)
MR = C expKt
1
9
exp9Kt
_ _
(3) Henderson and Henderson (1968)
where K = A exp(B/T)
MR = exp(Kt
n
)
(4) Page (1949)
where K = A exp(B/T)
MR = exp[(Kt)
n
]
(5) Overhults et al. (1973)
where K = exp(A+B/T)

1) List of symbols at the end of the paper.

798 M. A. S. Barrozo et al.
Bias
^
h
r
2
2

n
i1
F
i
F
i
T
_ _
1

n
u1
F
u
tr

n
i1
F
i
F
i
T
_ _
1
H
u
_ _
6
In practice,
^
h and ^ r
2
are usually used in place of the unknown
quantities.
The bias expressed as a percentage of the LS estimate is a useful
quantity, as an absolute value in excess of 1 % appears to be a
good rule of thumb for the identification of which parameter,
or parameters, are responsible for the nonlinearity behavior
[23]. Once these parameters are known, a reparametrization
can be sought to reduce the nonlinearity. The percentage bias
is given by:
% Bias
^
h
100 Bias
^
h
_ _
^
h
(7)
4 Experimental Methodology
4.1 Material
The experiments were performed with blue silica gel, with
d
p
= 2.6 10
3
m. The silica gel used in the experiments was sub-
jected to a slow artificial remoistening process, through contact
with nearly saturated ambient air [24]. In the experiments, the
initial moisture content was 0.28 kg water/kg dry solid.
4.2 Experimental Apparatus
The experimental setup used is illustrated in Fig. 1. The equip-
ment consists of a blower (2), an electric heater (3) connected
to a voltage variators single (4), gate valves (1), a flow me-
ter (5), copper-constantan thermocouples and a measuring
cell (6). The measuring cell consists of a cylindrical tube of
8.1 10
2
m in diameter and 1.5 10
2
m in length, having me-
tallic screens at the two extremities (details in Fig. 1).
The experimental conditions were chosen to analyze the
effect of air velocity and temperature on the drying kinetics
based on a factorial composite design [25] with four replica-
tions in the center level. The range of the variables was: air
velocity (0.93.5 ms
1
), air temperature (35.884.2 C). The
probable errors of the variable measurements are: air flow rate
4 %, temperature 0.25 C, solids moisture 1.0 %.
The equilibrium moisture (M
eq
) used for the calculation of
the moisture ratio (MR) in Eq. (8) was obtained by the dynamic
method [2628], reaching values from 0.002 (84.2 C) to
0.08 kg water/kg dry solid (40 C).
MR
M M
eq
M
0
M
eq
(8)
5 Results
5.1 Experimental Results
The drying curves presented in Figs. 2 and 3 were established
to visualize the effects of air velocity and temperature, individ-
ually. Fig. 2 presents the drying curves as a function of air
Chem. Eng. Technol. 2012, 35, No. 5, 797802 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
8.110
2
m
1.510
2
m
Figure 1. Scheme of the experimental apparatus.
0 40 80 120 160 200 240
Time (min)
0.0
0.2
0.4
0.6
0.8
1.0
M
o
i
s
t
u
r
e

R
a
t
i
o

(
M
R
)
a) T = 40C
V=1.1 m/s
V=3.3 m/s
0 40 80 120 160 200 240
Time (min)
0.0
0.2
0.4
0.6
0.8
1.0
M
o
i
s
t
u
r
e

R
a
t
i
o

(
M
R
)
b)
T = 60C
V = 0.9 m/s
V = 2.2 m/s
+ V = 3.5 m/s
0 40 80 120 160 200 240
Time (min)
0.0
0.2
0.4
0.6
0.8
1.0
M
o
i
s
t
u
r
e

R
a
t
i
o

(
M
R
)
c) T = 80C
V = 1.1 m/s
V = 3.3 m/s
Figure 2. Drying curves for different experimental air velocities
at (a) 40 C, (b) 60 C, and (c) 80 C.
Curvature measurement 799
velocity under constant temperature and Fig. 3 presents the
drying curves as a function of air temperature under constant
air velocity.
On analyzing these figures, it can be noted that the influence
of temperature (T) on the moisture ratio (MR) is more signifi-
cant than the influence of air velocity (V). The results of Fig. 2
show that there is only a small convective effect on the drying
kinetics, indicating that, under the studied conditions, the in-
ternal mechanism takes control on mass transfer.
5.2 Statistical Results
Tab. 2 presents the results obtained by the LS parameter esti-
mation for the five drying kinetics equations listed in Tab. 1.
These results include the estimated parameter values, as well as
the respective values of the quadratic regression coefficient
(R
2
), the intrinsic curvature measure (IN), the parameter
effects measure (PE) and the bias percentage.
It can be seen in Tab. 2 that the IN of all five equations ana-
lyzed was not significant. In contrast, for the curvature mea-
sure due to effects of parameters (PE) only the equations of
Page and Overhults had values below 1=2

F
p
. The non-signifi-
cant values for IN indicate small nonlinearity for the solution
locus [24]. The significant values of the PE curvature for the
first three equations show that at least one parameter of these
equations has a strong nonlinear behavior. For the Overhults
equation, better results are observed, since the curvature
measures (PE) are the smallest of all. Thus, for this equation,
besides the higher R
2
value (0.992), the nonlinearity due to
www.cet-journal.com 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2012, 35, No. 5, 797802
0 40 80 120 160 200 240
Time (min)
0.0
0.2
0.4
0.6
0.8
1.0
M
o
i
s
t
u
r
e

R
a
t
i
o

(
M
R
)
a) V=1.1m/s
T = 40C
T = 80C
0 40 80 120 160 200 240 280
Time (min)
0.0
0.2
0.4
0.6
0.8
1.0
M
o
i
s
t
u
r
e

R
a
t
i
o

(
M
R
)
b) V = 2.2 m/s
T = 35.8C
T = 60.0C
T = 84.2C
Figure 3. Drying curves for different experimental air tempera-
tures at (a) 1.1 ms
1
, (b) 2.2 ms
1
.
Table 2. Results of LS and curvature and Box bias measures for the drying equations in thin-layer silica gel.
Equation R
2
Curvature Parameter Estimated value Boxs bias [%]
Lewis
a
R
2
=0.931 IN=0.0019 a 83.611 4.08
F =5705 PE=0.8844 b 2230.425 0.00
Brooker
b
R
2
=0.967 IN=0.0023 a 73.179 2.65
F =8076 PE=0.8729 b 2297.756 0.00
c 0.856 0.00
Henderson-Henderson
b
R
2
=0.977 IN=0.0170 a 66.415 1.96
F =11 657 PE=0.7510 b 2299.026 0.00
c 0.801 0.00
Page
b
R
2
=0.992 IN=0.0470 a 15.913 0.27
F =33 836 PE=0.2979 b 1404.802 0.01
n 0.601 0.03
Overhults
b
R
2
=0.992 IN=0.0013 a 4.61 0.00
F =33 841 PE=0.0027 b 2338.92 0.00
n 0.60 0.00
a) 1=2

F
2;319;0:95
_
0:2875.
b) 1=2

F
2;318;0:95
_
0:3081.
800 M. A. S. Barrozo et al.
parametrization is small, which leads to valid inference results
based on asymptotical approximations for the LS estimators.
Since Eqs. (1)(3) present significant nonlinear parameter
effects (PE), the bias measures could show which parameters
are responsible for this behavior (%bias >1 %). Large bias
percentages are given for the Lewis equation (parameter A).
Another important result is that the nonlinear behavior in the
equations of Lewis, Brooker and Henderson-Henderson, was
always associated with parameter A of the Arrhenius function.
The results of Tab. 2 also show that the equation of Overhults
presents the lowest %bias.
Thus, the results obtained in the present work show that the
Overhults equation is the best equation to represent the drying
kinetics data of silica gel. The intervals of confidence (95 %) of
its parameters for t (min), T (K) and M (g water/g dry solid)
are the following:
A= 4.61 0.46
B = 2338.92 150.84
n = 0.60 0.01
Fig. 4 shows the good agreement between the results pre-
dicted by the Overhults equation and the experimental data.
The difference between the results measured and those com-
puted was in the range of 0.066.37 %.
6 Conclusions
It can be concluded, from the results obtained in the present
study, that:
for the studied conditions, the internal mechanisms take
control on mass transfer;
from the discrimination approach based on nonlinearity
measures, it was possible to identify the best equation to
represent the drying kinetics data of silica gel;
the values of R
2
and the F proportion of the Page and Over-
hults equations indicate them as adequate to represent the
kinetics of silica gel drying; however, the analysis of nonline-
arity indicated that the Overhults equation was better. The
nonlinearity due to parametrization for the Overhults equa-
tion is very small, which leads to valid inference results
based on asymptotical approximations for the LS estima-
tors.
Acknowledgment
The authors acknowledge the financial support received from
the National Council for Scientific and Technological Develop-
ment (CNPq).
The authors have declared no conflict of interest.
Symbols used
A [s
1
] parameter of the equations
B [K] parameter of the equations
C [] parameter of the equations
d
p
[m] diameter medium
F [] Fishers statistic
F
i
(= F
u
) [] vector (px1) of first
derivatives of f(X
i
, h)
H
u
[] matrix (pxp) of second
derivatives of f(X
i
, h)
M [kg water/kg dry solid] moisture content
MR [] moisture ratio
n [] parameter of the equations
PE [] effect of parameter
R [] correlation coefficient
T [K] fluid temperature
t [min] drying time
V [ms
1
] air velocity
X
i
[] independent variable
(i = 1,2...,n)
Greek letters
a [] level of significance
^
h [] LS estimator
^ r
2
[] amostral variance
Subscripts
eq equilibrium
0 initial
Chem. Eng. Technol. 2012, 35, No. 5, 797802 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
0 40 80 120 160 200 240
Time (min)
0.0
0.2
0.4
0.6
0.8
1.0
M
o
i
s
t
u
r
e

R
a
t
i
o

(
M
R
)
a) Overhults equation
Exp. T=40C , V= 1.1m/s
Exp. T=80C , V= 1.1m/s
0 40 80 120 160 200 240
Time (min)
0.0
0.2
0.4
0.6
0.8
1.0
M
o
i
s
t
u
r
e

R
a
t
i
o

(
M
R
)
b)
Overhults Equation
Exp. T=35.8C , V=2.2m/s
Exp. T=60.0C , V=2.2m/s
Exp. T=84.2C , V=2.2m/s
Figure 4. Drying curves of the experiments compared with the
responses obtained by the Overhults equation.
Curvature measurement 801
References
[1] T. Madhiyanon, S. Adirekrut, P. Sathitruangsak, S. Sopon-
ronnarit, Chem. Eng. Process. 2007, 46, 282.
[2] J. Sun, R. W. Besant, Int. J. Heat. Mass Transfer 2005, 48,
4953.
[3] A. A Pesaran, A. F. Mills, Int. J. Heat Mass Transfer 1987, 30
(6), 1037.
[4] C. R. Duarte, J. L. Vieira Neto, M. H. Lisboa, V. V. Murata,
M. A. S. Barrozo, Braz. J. Chem. Eng. 2004, 21 (1), 59.
[5] F. B. Freire, M. A. S. Barrozo, D. J. M. Sartori, J. T. Freire,
Drying Technol. 2005, 23 (7), 1451.
[6] M. A. S. Barrozo, H. M. Henrique, D. J. M. Sartori, J. T.
Freire, J. Stored Prod. Res. 2006, 42, 348.
[7] D. G. Overhults, G. M. White, H. E. Hamilton, I. J. Ross,
Trans. ASAE 1973, 112.
[8] D. B. Brooker, F. W. Bakker-Arkema, C. W. Hall, Drying
Cereal Grains, The Avi Publishing Company, Westport 1974.
[9] O. O. Ajibola, J. Food Eng. 1989, 9, 305.
[10] M. A. S. Barrozo, A. M. Souza, S. M. Costa, V. V. Murata, Int.
J. Food Sci. Technol. 2001, 36 (4), 393.
[11] C. Ertekin, O. Yaldiz, J. Food Eng. 2004, 63 (3), 349.
[12] A. Figiel, J. Food Eng. 2009, 94, 98.
[13] R. S. Aware, B. N. Thorat, in Proceedings of the 17th Inter-
national Drying Symposium, Magdeburg 2010, 1587.
[14] T. S. Lira, K. G. Santos, V. V. Murata, M. Gianesella, M. A. S.
Barrozo, Chem. Eng. Technol. 2010, 33 (10), 1699.
[15] M. J. Box, J. R. Stat. Soc. B 1971, 33, 171.
[16] D. M. Bates, D. G. Watts, J. R. Stat. Soc. B 1980, 42, 1.
[17] J. M. Henderson, S. M. Henderson, J. Agric. Eng. Res. 1968,
13, 87.
[18] W. K. Lewis, Ind. Eng. Chem. 1921, 13 (5), 427.
[19] G. E. Page, Master Thesis, Purdue University, West Lafayette
1949.
[20] R. S. Conceio Filho, M. A. S. Barrozo, J. R. Limaverde,
C. H. Atade, Drying Technol. 1998, 16 (9), 2049.
[21] M. A. S. Barrozo, A. A. M. Silva, D. T. Oliveira, J. Stored Prod.
Res. 2008, 44 (1), 65.
[22] J. A. Ribeiro, D. T. Oliveira, M. L. Passos, M. A. S. Barrozo,
J. Food Eng. 2005, 66, 63.
[23] D. A. Ratkowsky, Nonlinear Regression Analysis, Marcel
Decker, New York 1983.
[24] S. Arnosti, Jr., J. T. Freire, D. J. M. Sartori, M. A. S. Barrozo,
Seed Sci. Technol. 1999, 27, 273.
[25] M. J. Box, W. G. Hunter, J. S. Hunter, Statistics for Experi-
menters, an Introduction to Design, Data Analysis, and Model
Building, John Wiley & Sons, New York 1978.
[26] M. E. Katekawa, M. A. Silva, Braz. J. Chem. Eng. 2007, 24
(4), 561.
[27] M. A. S. Barrozo, Ph. D. Thesis, Federal University of
Uberlndia, Uberlndia 1995 (in Portuguese).
[28] M. A. S. Barrozo, D. T. Oliveira, G. P. Sancineti, M. V. Rodri-
gues, Braz. J. Chem. Eng. 2000, 17 (1), 105.
www.cet-journal.com 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2012, 35, No. 5, 797802
802 M. A. S. Barrozo et al.