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Application of the probabilistic Weibull model to rehydration kinetics:

relationship between the model parameters and the underlying physical
mechanisms of the process

Conference Paper · October 1997

DOI: 10.13140/RG.2.1.4275.2728

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 Application of the probabilistic Weibull model to rehydration kinetics: relationship
between the model parameters and the underlying physical mechanisms of the process

L. M. Cunha1, F. A. R. Oliveira1, L. A. Ilincanu2 & M. C. Drumond1

1
Escola Superior de Biotecnologia, U.C.P., Rua Dr. António Bernardino de Almeida, 4200 Porto, Portugal
2
Universitatea “Dunãrea de Jos”, Str. Domneascã 47, 6200 Galati, Romania

Summary

The Weibull distribution is one of many probability distribution functions used to predict the behaviour of
systems and events that have some degree of variability. In this work the usefulness of the probabilistic Weibull
model to describe rehydration processes controlled by (i) internal diffusion, (ii) external resistance to mass
transfer or (iii) relaxation mechanisms was assessed. The study was developed considering three different
experimental designs: equally spaced sampling times (ET); equally spaced concentration values (EC) and
equally spaced logarithmic sampling times (ELN). The effect of departure from the equilibrium value (Minf) was
also studied, using the ET design. It was concluded that the Weibull model adequately describes the three
mechanisms under study. The diffusional mechanism can be clearly identified from the shape parameter of the
Weibull model (app. 0.6), while the other two models are more difficult to differentiate from each other (values
between 0.9 and 1.3 were found, with a significant overlap). This identification of the diffusional mechanism is
clearer when using the ELN and EC designs. When departing from equilibrium, but assuming that Minf is known,
one can still clearly identify the diffusional process, even if only 30% of Minf is reached.

Introduction

When studying a particular rehydration process, it is often difficult to identify the underlying physical
mechanism(s), that is, one cannot clearly state if the system follows an internal diffusion, an external resistance
to mass transfer (lumped system), a relaxation or any other type of model. Empirical models are therefore often
used, and it has been observed that the Weibull probabilistic model usually yields good results, due to its
flexibility (Ilincanu et al., 1995; Machado et al., 1997). This model involves two parameters: the scale parameter
(α), which is a process rate parameter, and the shape parameter (β), that depends on the mechanisms controlling
the process (Hahn and Shapiro, 1967):

Mt   t β 
M* = = 1 − exp−   
M inf   α  

By changing the shape parameter, the Weibull model can describe well processes in which the underlying
physical mechanisms are quite different, and it would be of great interest if one could infer these mechanisms
from the value of β. Special care should be taken when describing systems that show a concentration increase up
to an equilibrium value (Minf), because major problems arise from the estimation of the model parameters when
the maximum attainable value of concentration (Mmax) is much smaller than Minf (Cunha et al., 1996). The main
objectives of this work were: (i) to analyse whether the Weibull probabilistic model might be applied to describe
processes controlled by internal diffusion, external resistance to mass transfer or relaxation phenomena; (ii) to
identify the value of the shape parameter for the different situations tested and (iii) to study the effect of the
experimental design (equally spaced sampling times -ET-; equally spaced concentration values -EC- and equally
spaced logarithmic sampling times -ELN) and the effect of the departure from equilibrium on the estimates of
the model parameters. A spherical sample geometry was considered.

Mathematical Methods

To allow for a better comparison between the different mechanisms, the rate parameters (ki) of each model were
chosen in such a way that a conversion value (M*) equal to 1-e-1 would occur at t = 103.5 min (value of the
scale parameter for modelling of apple rehydration, Ilincanu et al., 1995).

Table I
Rehydration kinetics models and respective rate parameters used for data generation.

Mechanism Model Rate parameter x 103 Reference

-1
(min )

6 ∞ 1
Internal
diffusion
M* = 1 − ∑
π 2 n =1 n 2
(
exp − n 2 k1 t ) 5.32
Crank (1975)

External resistance
6.99 Geankoplis (1978)
to mass transfer M* = 1 − exp(− k 2 t )
(lumped system)

Relaxation M* = 1 − (1 − k 3 t )3 2.74 Peppas and Brannon-

Peppas (1994)

Using the above parameters, exact model data (30 points including replicates) were generated for each
rehydration model and each experimental design, considering Mmax = 99% Minf. For the ET design several
curves were further generated for different values of the maximum attainable concentration (Mmax = 30%, 50%,
70% and 90% of Minf). To each set of model values a set of 30 normally distributed errors from a population
with zero mean and 5%Minf standard deviation were attributed, to generate sets of pseudo-experimental data (see
example in figure 1). The Weibull model was then fitted to the resulting data, by non-linear regression, using
STATA 3.0 (Computing Resource Center, 1992), yielding pseudo-experimental parameters.

ET EC ELN
1.2 1.2 1.2
1.0 1.0 1.0
0.8 0.8 0.8
M*

M*

M*

0.6 0.6 0.6

0.4 0.4 0.4
0.2 0.2 0.2
0.0 0.0 0.0
0 200 400 600 800 0 200 400 600 800 0 200 400 600 800

time (min) time (min) time (min)

Figure 1: Pseudo-experimental data describing internal diffusion according to different experimental designs:
ET-equally spaced sampling times; EC-equally spaced concentration values and ELN-equally spaced
logarithmic sampling times. (______) exact data, (♦) pseudo-experimental data.

Results
The Weibull model adequately described the three process mechanisms under study: internal diffusion, external
resistance to mass transfer and relaxation (see example in figure 2). For each process and each experimental
design, 50 pseudo-experimental data sets were generated and studied, yielding for any given situation (even for
Mmax = 30% Minf) an average R2adj, higher then 0.9, with a standard deviation lower than 0.03.

Di ffu s i o n Exte rn al re s i s ta n ce
1.2 1.2
1.0 1.0
0.8 0.8
M*

M*
0.6 0.6
R2adj = 0.9978 0.4 0.4 R2adj = 0.9978
Normality# = 0.69 0.2 0.2 Normality# = 0.83
Autocorrelation+ > 0.50 0.0 Autocorrelation+ = 0.30
0.0
0 200 400 600 800 0 100 200 300 400 500

time (min ) time (min )

Re l ax ati o n Di ff. u p to3 0% of M inf

1.2 0.4
1.0
0.3
0.8
M*

M*

0.6 0.2
R2adj = 0.9968 0.4 R2adj = 0.9978
Normality# = 0.64 0.1 Normality# = 0.71
0.2
Autocorrelation+ = 0.30 Autocorrelation+ > 0.50
0.0 0.0
0 75 150 225 300 0 3 6 9 12 15 18
time (min ) time (min )

Figure 2: Fitting of the Weibull model to pseudo-experimental data; data were generated according to different
process mechanisms assuming an ET experimental design. #Shapiro-Wilks P-value (STATA 3.0 - Computing
Resource Center, 1992); +RUNS test P-value (StatMateTM, GraphPad Software, San Diego, USA, 1995).

Figure 3 shows the estimates obtained for each situation studied and for each run. Two clusters are visible, one
including the estimates obtained from the regression of the internal diffusion model data, while the other
includes the estimates of both the external resistance to mass transfer and relaxation models. This effect is even
more clear with the EC and ELN designs that lead to more precise estimates of the parameters. The diffusion
mechanism is thus clearly identified by β values ranging from of 0.6 to 0.7. Values of β between 0.9 - 1.0
indicate an external resistance to mass transfer model, while values higher than 1.1 correspond to the relaxation
model. The first observation would indeed be expected, as the external resistance to mass transfer model is a
particular case of the Weibull model where β =1; deviations of the estimates from unit are therefore the result of
“experimental” errors only. When the estimates of β range from 1.0 to 1.1 it is impossible to differentiate
between the two mechanisms.
 ET EC ELN
125 125 125
115 115 115

(min)
(min)

(min)
105 105 105
95 95 95
85 85 85
75 75 75
0.5 0.7 0.9 1.1 1.3 1.5 0.5 0.7 0.9 1.1 1.3 1.5 0.5 0.7 0.9 1.1 1.3 1.5

β β β

Figure 3: Estimates of the Weibull model parameters obtained from model fitting to 50 different sets of 30
pseudo-experimental data points, generated according to different experimental designs (ET, EC and ELN) and
different process mechanisms: diffusion (♦); external resistance to mass transfer (*) and relaxation (o).

When covering shorter extensions of the process, this differentiation between the diffusion model and the other
models tested is still clear, even if Mmax is only 30% Minf (see figure 4), whereas differentiation between the
external resistance to mass transfer and the relaxation models becomes increasingly difficult. This departure
from equilibrium clearly decreases the precision of the parameters estimates and increases the colinearity
between the model parameters, as shown in figure 4.

125 125
Ma x. co n ve rs i on Ma x. co n ve rs i on
115 90 % Mi n f 115 70 % Mi n f
(min)

(min)

105 105

95 95

85 85
0.3 0.5 0.7 0.9 1.1 1.3 1.5 0.3 0.5 0.7 0.9 1.1 1.3 1.5

β β

165 650
Max . con ve rs i o n Ma x. con ve rs i o n
50 % Mi n f
550
145 30 % Mi n f
(min)

450
(min)

125 350
250
105
150
85 50
0.3 0.5 0.7 0.9 1.1 1.3 1.5 0.3 0.5 0.7 0.9 1.1 1.3 1.5
β β

Figure 4:Estimates of the Weibull model parameters obtained from model fitting to 50 different sets of 30
pseudo-experimental data points, generated according to different process mechanisms: diffusion (♦); lumped
(*) and relaxation (o), assuming an ET experimental design with different values of the maximum attainable
concentration (30%, 50%, 70% and 90% of Minf).

CONCLUSIONS
 The Weibull model adequately describes processes controlled by internal diffusion, external resistance to mass
transfer and relaxation phenomena. When fitting the Weibull model to rehydration data, the estimate of the
shape parameter may be seen as an indicator of the underlying physic mechanisms. If the process is controlled
by internal diffusion the shape parameter averages 0.6, whereas values close to unity were found when the
process was controlled by the external resistance to mass transfer or by the relaxation phenomena occurring in
the solid matrix.

REFERENCES

Computing Resource Center. 1992. Stata Reference Manual: Release 3. 5th ed. Santa Monica, CA.

Crank, J. 1975. The Mathematics of Diffusion, 2nd ed. Clarendon Press, Oxford.

Cunha, L. M. Oliveira, J. C. and Oliveira, F. A. R. 1996. Optimal design of experiments for determination of
kinetic parameters for a process following a Weibull decay model. Proceedings of the 5th AIChE World
Congress, July, 1996, San Diego, USA.

Geankoplis, C. 1978. Transport Processes and Unit Operations. Allyson & Bacon, Inc. New York

GraphPad. 1995. StatMateTM, GraphPad Software, Inc. San Diego. USA.

Hahn, G. J. and Shapiro, S. S. 1967. Statistical Models in Engineering. John Wiley and Sons, Inc.

Ilincanu, L. A., Oliveira, F. A. R., Drumond, M. C., Machado, M. F. and Gekas, V. 1995. Modelling moisture
uptake and soluble solid losses during rehydration of dried apple pieces. Proceedings of the Copernicus First
Main Meeting – “Process Optimisation and Minimal Processing of Foods”, December 1995, ESB, Porto,
Portugal.

Machado, M. F., Oliveira, F. A. R. and Gekas, V. 1997. Modelling water uptake and soluble solids losses by
puffed breakfast cereals immersed in water or milk. Proceedings of the Seventh International Congress on
Engineering and Food, Brighton, England

Peppas, N. A. and Brannon-Peppas, L. 1994. Water diffusion and sorption in amorphous macromolecular
systems and foods. J. Food Eng. 22: 189-210.

ACKNOWLEDGMENTS

Authors acknowledge financial support from EU projects AIR3-CT94-2254 and AIR1-CT92-0746. The first
author acknowledges financial support from Fundação para a Ciência e a Tecnologia (FCT) trough “Sub-
programa Ciência e Tecnologia do 2º Quadro Comunitário de Apoio”.

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