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Determination of Moisture
Diffusivity by Thermo-
Gravimetric Analysis under
Non-Isothermal Condition
a b
Zhanyong Li & Noriyuki Kobayashi
a
College of Mechanical Engineering, Tianjin
University of Science and Technology , Tianjin,
China
b
Division of Energy Science , EcoTopia Science
Institute, Nagoya University , Nagoya, Japan
Published online: 06 Feb 2007.

To cite this article: Zhanyong Li & Noriyuki Kobayashi (2005) Determination of

Moisture Diffusivity by Thermo-Gravimetric Analysis under Non-Isothermal Condition,
Drying Technology: An International Journal, 23:6, 1331-1342, DOI: 10.1081/
DRT-200059523

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 Drying Technology, 23: 1331–1342, 2005
Copyright Q 2005 Taylor & Francis, Inc.
ISSN: 0737-3937 print/1532-2300 online
DOI: 10.1081/DRT-200059523

Determination of Moisture Diffusivity by

Thermo-Gravimetric Analysis under
Non-Isothermal Condition
Downloaded by [Moskow State Univ Bibliote] at 14:42 27 January 2014

Zhanyong Li
1 and Noriyuki Kobayashi2

1
College of Mechanical Engineering,
Tianjin University of Science and Technology, Tianjin, China
2
Division of Energy Science, EcoTopia Science Institute,
Nagoya University, Nagoya, Japan

Abstract: In drying of solids, the diffusion model based on Fick’s second law is
usually applied to interpret the moisture migration within the solid. Then the
temperature dependence of the moisture diffusivity, generally described by an
Arrhenius-type equation, is obtained through the drying kinetics. In this article,
a nonisothermal (linearly increasing temperature) procedure was used to deter-
mine the moisture diffusivity as a function of temperature with the complex
optimization method, and the result was accessed by comparison with a classical
isothermal procedure. All the experiments were conducted in a thermogravimetric
analyzer (TGA) for accurately recording the mass loss from the sample and easily
programming the heating profile.

Keywords: Complex optimization; Drying; Isothermal; Mung beans;

Nonisothermal

INTRODUCTION

Diffusivity is an important parameter for describing the diffusion

mechanism in solids in the course of drying or adsorption, if mass trans-
fer can be considered as a diffusion process controlled by Fick’s second
law. In the literature, a two-step method has generally been used to
determine the temperature dependence of diffusivity under isothermal
zconditions. First, diffusivity (D) is determined from the moisture con-
tent versus time curves for each of several constant temperatures. A set


Correspondence: Zhanyong Li, College of Mechanical Engineering, Tianjin
University of Science and Technology, No. 1038 South Dagu Road, Hexi
District, Tianjin 300222, China; E-mail: lizhanyong68@yahoo.com.cn
 1332 Li and Kobayashi

of diffusivities is then correlated as a function of temperature using the

well-known Arrhenius-type equation in terms of two relevant para-
meters, namely the activation energy (Ea) and the preexponential factor
(D0). This method has the advantages of mathematical simplicity and
intuitive appeal; however, the analysis needs several experiments and
samples, which would be expensive and time consuming. On the other
hand, the experiment is not performed isothermally in practical processes
(e.g., food processes), because instantaneous heating or cooling of the
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sample to the required temperature is not easy to achieve practically

due to the thermal lag. Therefore, a nonisothermal method was proposed
as a promising alternative for determining the temperature dependence of
diffusivity.
The nonisothermal method was first introduced by Rogers[1] to study
the first-order decomposition of riboflavine and of sucrose in aqueous
solution. Later, this method has been applied for the study of other reac-
tion kinetics.[2–6] Moreira et al.[7] applied this method to investigate the
diffusion of acetic acid into turnips using an analytical solution with an
average diffusivity. Good results were obtained in comparison with two
isothermal methods (i.e., a two-step and a one-step method). Their
further research,[8] based on the pseudo-experimental data generated by
computer with a standard deviation of 5 and 6%, shows that the average
deviations between pseudo-experimental and reference diffusivity to the
temperature range of interest for the runs with a 6% error are on average
2.6 times the values obtained with a 5% error.
Hence, to improve the accuracy in estimating the parameters for dif-
fusion or chemical reaction problems, it is most important to minimize the
experimental errors. A thermogravimetric analyzer (TGA, a standard
instrument) can accurately record the mass loss from the sample during
heating at programmed temperature profiles. However, current numerical
methods are effective for solving the mathematical models for diffusion or
other phenomena, especially when the analytical solution is not available
and the diffusivity is time dependent. In this article, our objective is to
determine the diffusivity by a numerical method (i.e., finite difference
method) with the experiments conducted in a TGA and then to compare
the characteristics for the isothermal and nonisothermal procedure. In
order to estimate the parameters (D0 and Ea) in a rational range for the
nonisothermal procedure, we used the complex optimization method.[9]

MATHEMATICAL CONSIDERATIONS

The solid-side heat transfer resistance is ignored in the case of small Biot
number.[10] For drying of moist grain, the temperature gradients do not
have to be considered in practical design problems.[11] It is generally
agreed that mass transfer in a grain kernel takes place by liquid diffusion
 Determination of Moisture Diffusivity 1333

as described by Fick’s second law. With the assumption of constant

diffusivity within the particle as well as no shrinkage of particle, we
obtain the following governing equation for a sphere:


@w D @ 2 @w
¼ r ð1Þ
@t r2 @r @r
where the dependence of the moisture diffusivity (D) on the temperature
is given by the Arrhenius equation
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Ea
D ¼ D0 exp  ð2Þ
Rg T
where D0 is the preexponential factor or frequency factor, Ea is the
activation energy, Rg is the universal gas constant, and T is the absolute
temperature at time t. For a nonisothermal process, for example, the lin-
ear heating procedure with a heating rate a in this study, the temperature
is expressed as
T ¼ T0 þ a  t ð3Þ
It is noted that the parameters in Eq. (2), D0 and Ea, are highly collinear
and not easily regressed directly. To overcome this problem and improve
the convergence rate, Eq. (2) is transformed as:[12]


Ea 1
D ¼ exp d  b ð4aÞ
Rg T
For the linear heating profile
Ea
d ¼ lnðD0 Þ  b ð4bÞ
Rg
Z tR

1 dt 1 T0 þ a  tR
b¼ ¼ ln ð4cÞ
tR 0 TðtÞ a  tR T0
where d is a dummy variable, b may be regarded as the reciprocal of mean
temperature, and tR is the drying period.
Thus, d and Ea can be determined by minimizing the deviation (root-
mean-square deviation in this study, r) between the experimental and
theoretical data. The complex method[9] is used for this purpose, because
we can set the values of D0 and Ea in a rational range according to the
reported data in the literature. D0 is then calculated with the known
parameters d and Ea.
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u n
2
u1 X M i
r¼t  1 ð5Þ
n i¼1 Mi

 1334 Li and Kobayashi

where n is the total number of experimental data for one run, Mi
is the
experimental data, and Mi is the calculated data.
In this study, the boundary condition is assumed the first kind (the
condition of Dirichlet type), and hence we can respectively write the
boundary and initial conditions as follows:
w ¼ we ðr ¼ R; t > 0Þ ð6Þ
and
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w ¼ w0 ðt ¼ 0Þ ð7Þ
where we and w0 are the equilibrium and initial moisture contents (d.b.),
respectively.
For nonisothermal procedure, because the diffusivity is dependent
upon temperature or time, in other words, the numerical solution was
obtained with the finite difference method with a constant diffusivity,
D(t þ 0.5Dt) to approximate the diffusivity in the short time interval
(Dt). In addition, Dt and Dr were selected to satisfy the stability condition
of the numerical solution. For the isothermal procedure, the moisture
diffusivity is constant in the drying process. The analytical solution to
Eq. (1) was applied[13] to obtain the moisture diffusivity at any tempera-
ture using simplex optimization method.[14] In addition, the diffusivity
obtained by Eq. (1) is an effective value for the solid shapes not including
a sphere, and hence the intrinsic diffusivity is estimated according to the
research of Li et al.[15,16]

EXPERIMENTAL

A thermo-gravimetrical analyzer (TGA-50, Shimadzu) was used to

obtain the drying kinetics. The samples put in the furnace can be heated
from room temperature to 1273 K with a heating rate ranging between 0
and 50 K=min. The loss of the sample mass and temperature change with
time can be automatically displayed and recorded in a computer. The
measuring accuracy for sample mass is 1% of the respective measuring
ranges (20 mg and 200 mg), with a reading limit of 0.001 mg. The
measuring resolution for temperature is 0.1 K. Pure nitrogen was used
as purging gas (0–100 mL=min). The gas flow rate was set at 80 mL=min
to approach the first kind of boundary condition. The principle of TGA
is not given here in detail, because it is a popular commercial instrument.
Mung beans (Rav ¼ 2:20  0:25 mm; w0 ¼ 0.6310.037 kg=kg, d.b.)
like ellipsoidal solids were selected as experimental material for drying.
The whole kernel adsorbs moisture in a moist environment with much
difficulty; therefore, the kernels were rewetted in purified water for
several hours and then hung above a water reservoir for more than
48 h in a refrigerator. The kernel dimensions were measured by a vernier
 Determination of Moisture Diffusivity 1335

caliper, and the volume was measured by an ultra pycnometer to obtain

its average diameter. Prior to experimental tests, the whole kernel was
taken out of the container and kept at room temperature. Each run
was conducted in replicate.

RESULTS AND DISCUSSION

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TGA recorded the loss of the sample mass at the specified time interval.
By transformation, the drying curves of moisture content (dimensionless)
versus time were obtained. Two typical examples are shown in Figs. 1 and
2 for isothermal conditions at 333 K and 393 K, respectively. The
sampling frequency for TGA is adjustable (5 s in this study), so its effect
on the calculation precision can be ignored. In these figures, selected
experimental points in a longer time span are shown for clarification.
By using the simplex optimization method, the calculated results, which
show the minimized root-mean-square deviation, are obtained and shown
in the corresponding figures compared to the experimental data. An opti-
mal diffusivity was obtained for each drying temperature, and then the
set of diffusivities was correlated with temperature, as is shown in Fig. 3.
It is found that an Arrhenius-type equation, Eq. (8) can be used to
describe the relationship between diffusivity and temperature, although

Figure 1. Variation of the average moisture content with time under the
isothermal condition (T ¼ 333 K). Cal.1: assuming isothermal condition;
Cal.2: considering the practical heating profile (Fig. 4).
 1336 Li and Kobayashi
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Figure 2. Variation of the average moisture content with time under the
isothermal condition (T ¼ 393 K).

Figure 3. Relationship between moisture diffusivity and temperature obtained

from the isothermal procedure.
 Determination of Moisture Diffusivity 1337

the effect of moisture content is not considered in this study for simplify-
ing the problem.


7 2:328  104
D ¼ 4:000  10 exp  ðR2 ¼ 0:9715Þ ð8Þ
Rg T

In Fig. 2, the larger discrepancy between the experimental and calculated

data is found at the initial period if constant temperature is considered
in the overall drying process (Cal.1), although not serious for low-tem-
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perature drying (e.g., at 333 K, Fig. 1). As a matter of fact, there is a short
temperature rising period before reaching the required temperature,
shown in Fig. 4. With the practical heating profile considered, the predic-
tion for the first half of the drying period can be improved (Cal.2) by
using the same Eq. (8). From this evidence, it is concluded that the
reduction of thermal lag is very important for determining diffusivity
by the isothermal procedure.
In the nonisothermal procedure, the temperature is linearly increased
at the heating rate from 1 to 10 K=min. A higher heating rate is aban-
doned, because only a small amount of moisture is removed as the fur-
nace temperature increases from environmental temperature to a high
level (i.e., 393 K in this study). In addition, at high temperature the drying
mechanism may be changed. Figures 5 and 6 show the drying curves at
the two extremes of heating rate, only covering the drying period during
which the heating temperature rises from room temperature to 393 K.
The nonisothermal drying curves, which reflect the temperature

Figure 4. Practical heating profile under the isothermal condition at 393 K.

 1338 Li and Kobayashi
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Figure 5. Variation of the average moisture content with time under the
nonisothermal condition (a ¼ 1 K=min).

Figure 6. Variation of the average moisture content with time under the
nonisothermal condition (a ¼ 10 K=min).
 Determination of Moisture Diffusivity 1339

Table 1. Diffusivity parameters in Arrhenius-type equation obtained by the

nonisothermal procedure
a, K=m 1 1.5 2.5 5 7.5 10
D0  104, m2=s 3.186 1.297 0.1993 2.890 3.962 118.4
Ea  10 4, J=mol 4.331 4.024 3.657 4.363 4.650 5.679
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dependency of the drying process with respect to time, differ from the
isothermal ones in form (Figs. 1 and 2). In order to determine the para-
meters (i.e., Ea and D0) in the assumed Arrhenius-type equation by the
complex method, the ranges of Ea and d (a function of Ea and D0) were
set as 5.000  103–1.000  105 J=mol and 50 to 10, respectively, based
on the literature data of Ea and D0 for food materials.[17]. The numerical
results with minimal deviation to the experimental data are shown in the
corresponding figures. A pair of different optimal Ea and D0 was
obtained at each heating rate (see Table 1). One reason might be attrib-
uted to the dissimilarity in each sample of mung bean. It is found that all
the activation energy values (Ea) are in the same order, but the difference
in D0 is big especially for a ¼ 10 K=min.
The diffusivities calculated at several temperatures are shown in
Fig. 7 for various heating rates, while the diffusivities obtained under iso-
thermal conditions are also presented for comparison. Generally, the
diffusivities obtained by the isothermal procedure agree with those by
the nonisothermal procedure at lower heating rates. The slope of the iso-
thermal curve in Fig. 7 (i.e., Ea=Rg, Ea ¼ 2.328  104 J=mol) is lower
than that of the nonisothermal curve. At higher temperatures, the diffu-
sivities determined by the isothermal procedure approach the values
obtained under nonisothermal conditions at higher heating rates and vice
versa at lower temperatures. Therefore, under both isothermal and non-
isothermal conditions, the drying temperature plays an important role in
drying kinetics and consequently influences the diffusivity obtained.
When a kernel of mung bean is exposed to the environment of higher
temperature, it is postulated that the moisture evaporation rate at the
surface layer of the kernel is higher than the moisture migration rate from
the internal to the surface so that a crust is formed (case-hardening) due
to the transition of rubbery to glassy state at the surface layer.[18] Case-
hardening is a common phenomenon during drying of food materi-
als.[18–20] The crust leads to higher resistance to moisture diffusion, and
thus the drying rate is decreased. Consequently, the diffusivities determ-
ined from such drying curves are lower. It is clearly found that the diffu-
sivities obtained at a ¼ 7.5 and 10 K=min are lower than the others at
lower heating rates. The diffusivities are likewise underestimated in
isothermal conditions of higher temperatures due to the occurrence of
case-hardening. In addition, at high heating rate, the drying curve covers
 1340 Li and Kobayashi
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Figure 7. Comparison of the moisture diffusivities obtained under nonisothermal

conditions with those under isothermal conditions.

a range of higher moisture content (M ¼ 0.6698–1.000 in Fig. 6), and

hence it is not reasonable to extend the result to lower moisture contents
because the effect of moisture content on diffusivity is implicitly included
in Eq. (2). Therefore, high heating rate is not advisable for the non-
isothermal procedure.
From Figs. 5 and 6, as well as Figs. 1 and 2, it is found that the theor-
etical predictions are not in agreement with the experimental data at the
initial drying period. The difference is especially obvious for the noni-
sothermal drying at high heating rate and for the isothermal drying at
high temperature. In this study, we assumed the first kind of boundary
condition. In practice, the surface moisture content might not reach the
equilibrium (we ¼ 0) although the nitrogen gas flow was set to a high
level. Another possible explanation is that the kernel temperature might
not respond simultaneously to the gas temperature in TGA.

CONCLUSIONS

Moisture diffusivity of mung beans was determined in a TGA by applying

an isothermal and a nonisothermal procedure. The temperature depen-
dence of the diffusivity can be described by an Arrhenius-type equation
in terms of the activation energy, Ea, and the frequency factor, D0. Lower
diffusivities were obtained under both high-temperature drying conditions
(isothermal procedure) and nonisothermal conditions at high heating
 Determination of Moisture Diffusivity 1341

rates, due to the occurrence of case-hardening. The nonisothermal pro-

cedure at lower heating rate is considered to be preferable to determine
the temperature dependence of diffusivity with the complex optimization
method. The assumptions of the model and the boundary condition are
important for the accurate application of the nonisothermal procedure.

NOMENCLATURE
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D Diffusivity (m2=s)
D0 Preexponential factor or frequency factor (m2=s)
Ea Activation energy (J=mol)
M Dimensionless average moisture content of whole kernel,
(w  we)=(w0  we)
R Particle radius (m)
Rg Universal gas constant ( ¼ 8.314) (J=[mol K])
R2 Square of correlation coefficient
r Distance from the center in radial direction (m)
T Temperature (K)
t Time (s)
w Moisture content (kg=kg) (d.b.)
Greek Symbols
a Linear heating rate (K=min)
b Dummy variable (1=K)
d Dummy variable
Dt Time intervals (s)
Subscripts
0 Initial
av Average
e Equilibrium
R Time period

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