Wood Science

Wood Sci. Technol. 23:251 258 (1989) and Technology

9 Springer-Verlag 1989

Evaluation of "three-variable" models for the prediction

of equilibrium moisture content in wood
St. Avramidis*, Vancouver, C a n a d a

Summary. Four sorption isotherm models that express moisture content as a function of both
relative humidity and temperature were evaluated by fitting them to a set of sorption data
between 21.1 and 71.1 ~ with the help of a nonlinear curvefitting program. All of them
predicted the sigmoid shape of the sorption isotherms and the shift towards the x-axis as the
temperature increased. The calculated root mean square error was used as an indication of the
goodness of the fit.

Introduction

Sorption isotherms of w o o d are graphical representations of the relationship between

the equilibrium moisture content ( E M C ) and the relative humidity (H) at a given
temperature (T). These are o f great importance in wood drying technology as well as
in the prediction of the dimensional behavior of b o t h solid wood and composite
panels under the influence o f a changing ambient environment.
The p h e n o m e n o n of adsorption has been investigated extensively in the past and
numerous mathematical models have been derived to describe the relationships be-
tween E M C , T, and H. M o s t o f them have been derived for hygroscopic polymers and
some have been applied to w o o d with success (Simpson 1973). The reader who is
interested in the derivation and development o f the sorption theories applied to wood,
is referred to the publications by Venkateswaran (1970), Skaar (1972), and Simpson
(1980).
Simpson (1971, 1973), by using a nonlinear regression technique, fitted nine
theoretically derived models to the W o o d H a n d b o o k sorption d a t a at different tem-
peratures. In all models, except that of A n d e r s o n and M c C a r t h y (1963), the indepen-
dent variable was the relative humidity whereas the dependent one was the E M C .
Such a model requires fitting to a set o f E M C - H d a t a at the same temperature; as a
result, the curvefitting must be repeated for every sorption isotherm producing pa-
rameter sets which are different for each temperature. Then, in order to obtain the
a p p r o p r i a t e set of parameters at a particular temperature, a second degree p o l y n o m i a l

* The author would like to thank Dr. John F. Siau, Professor Emeritus, State University of
New York, College of Environmental Science and Forestry, for reviewing this manuscript
252 St. Avramidis

regression was required. Here, temperature was the independent variable and each o f
the parameters the dependent one. Therefore, every time the E M C was needed for an
H - T set of values, the parameters had to be calculated from the second degree
polynomials and then used in the models. This procedure resulted in additional error
due to the nonlinear and polynomial regression, as well as repeated curvefitting of
each models to the sets o f E M C - H d a t a at each temperature.
The purpose o f this communication is the presentation and evaluation, using
w o o d sorption data, o f four sorption models that have been used in the past to predict
E M C s of hygroscopic biopolymers. The advantage in these models is the existence o f
the temperature factor as an independent variable, therefore, only one curvefitting
run is required for a set of sorption isotherms, each at a different temperature.

Materials and methods

The models evaluated are the following,

(a) Henderson (/952),

I - h = exp ( A M B) (1)

where A = - a ~ T; B = a2; h is the relative v a p o r pressure; T the Kelvin temperature;

M the percent moisture content; and a t a 2 are the parameters for evaluation. This
empirical model was established rigorously by a thermodynamic procedure which
included the effect o f temperature u p o n the moisture sorption isotherms. The two
parameters have been evaluated for sorption isotherms of numerous agricultural
products, resulting in observed and calculated d a t a points that were in close agree-
ment.
(b) D a y and Nelson (1965),
I -- h = exp (A M B) (2)
where A = b 1Tb2; B = b 3 Tb4; b 1 , b 2 , b 3 , and b 4 are the parameters for evaluation.
This model was derived from the basic Henderson's model as described above, due
to the need for a more adequate mathematical representation of the wheat desorption
isotherms to be used in grain drying computations.

(c) Zuritz et al. (1979),

h = 1 - exp (A M B) (3)

where A = - ( c 2/T) ( 1 - (T/To))~ B = c 3 T~ Tc is the critical absolute temperature

o f water, 647.1 K; c 1 , c 2 , c 3 and c 4 are the parameters for evaluation. This model was
also derived from Henderson's model with the help o f an empirical relation p r o p o s e d
by Van der Waal (1894). The resulting model showed a very good fit to desorption
d a t a obtained for rice at different temperatures.
(d) Chung and Pfost (/967),
h = exp [d 1 T a2 exp (d 3 T a4 M)] (4)
Evaluating models for prediction of wood EMC 253

where d l , d2, d 3 and d 4 a r e the parameters for evaluation. This model is based on the
dipole attractive forces between sorption sites and water molecules and the formation
on the surface of many adsorbed water layers under compression. Comparison of this
model to that derived by Bradley (1936), reveals that its form is practically equivalent
to that of the latter, however, its derivation is simpler and the functional behavior of
d 3 T a4 part is different from the K 1 in Bradley's equation.
Before fitting, the models were rearranged in terms of moisture content, as fol-
lows,
Henderson M = [ - in (i - h)/(a 1 T)] 1/a2 (5)
Day-Nelson M = [ln (1 - h ) / ( b 1 Tb~)]1/(b3rb4) (6)
Zuritz et al. M = [ - T i n (1 -- h)/(c 2 (1 - T/T c)~1)] 1/(taro4) (7)
Chung-Pfost M = in (ln (h)/(dt Td~)/(d3 T d4) (8)
It is interesting to evaluate the models at the points of maximum and minimum
relative humidity. When h tends to zero, M also tends to zero if models (5), (6) and
(7) are used, but in model (8) M becomes negative. When h tends to 1 (100% relative
humidity), then M in all models approaches infinity, in other words, the isotherm
curve becomes asymptotic to the normal at point h = i. This means that all four
models break down at this point since an equilibrium at 100% relative humidity will
result in total saturation of wood (Siau 1984).
Since in all four models the parameters are raised to other than the first power,
they are of a nonlinear form and therefore, a nonlinear regression technique was used
for the parameter estimation. A state-of-the-art general nonlinear data-fitting routine
was utilized (Moore 1984). The possibility of real convergence was greatly enhanced
because the first order partial derivatives of the function with respect to each param-
eter were used. This is of great advantage in a routine when it is compared to a routine
using numerical approximations of the derivatives.
Each model was fitted to five isotherms at 21.1, 35, 43.3, 51.6 and 71.1 ~
obtained from the U S D A Wood H a n d b o o k (1955). For the evaluation of the good-
ness o f the fit, the Root Mean Square Error (RMSE) for each curve was calculated.
Since R M S E estimates the difference between actual and calculated values, the crite-
rion used was that the best fit of the data is obtained with the model that shows the
smallest R M S E value. Additionally, the Residual Sum of Squares (RSS) for each fit
were calculated and also used as an indication of the goodness of the fit. The absolute
values of the difference between actual and calculated data were obtained as well as
their maximum, minimum, and average values. Curves generated by the models were
plotted with the experimental points in order to visually identify a possible false
convergence.

Results and discussion

The values of the estimated parameters and of the residual sum of squares for the four
models are listed in Table 1. The RSSs ranged from 4.27 for the Zuritz et al. model
to 64.04 for the Henderson model. These values compare very favorably to the RSSs
reported by Simpson (1973), regarding the curvefitting of a set of one independent
254 St. Avramidis

Table 1. Estimated parameters and residual sum of squares (RSS) for the four models

Henderson Day-Nelson Zuritz et al. Chung-Pfost

a1 = 0.10E-3 b1 =-0.34E-16 c1 =--6.46 d1 = - 0 . 1 9 E 5

a2 = 1.46 b2 = 5.98 c2 = 0.13 d2 = - 1 . 5 1
b 3 = 0.30E3 c3 = 0.lIE3 d3 = - 0 . 3 9 E - 3
b4 = -0.93 c4 = -0.75 d4 = 1.07
RSS = 64.04 RSS = 7.25 RSS = 4.27 RSS = 13.79

variable (h) models to the Wood H a n d b o o k sorption data for the - 1 to 99~
temperature range.
Henderson's model, which showed the highest RSS value, had an average devia-
tion between experimental and calculated data for the five isotherms of 0.50% of
moisture content as shown in Table 2. The m a x i m u m deviation was 1.46% moisture
content, which appeared in the 71.1~ isotherm. A plot of the model generated
curves, revealed that the fit was very poor for the 21.1, 35 and 71.1 ~ isotherms,
which led to the conclusion that this model is unsuitable for representing sorption
isotherms of wood. The only reference to the application of this model to wood, is in
the International Critical Tables (1927), where the values of the parameters a~ and a 2
at 25 ~ were 5.34 x 10-5 and 1.41 respectively. The former is half the magnitude of
that obtained for the five isotherms, whereas the latter was almost the same.
The Day-Nelson model gave a fairly good fit with a RSS of 7.25. The average
deviation for the five isotherms was 0.17% and the largest deviation was 0.68%
moisture content, obtained in the 43.4~ isotherm. Values for the b 1 , b 2 , b 3 and b 4
parameters previously reported were 5.73 x 10-lo, 3.37, 14.86 and - 0 . 4 2 for wheat
and - 5 . 9 6 x 10 -sT, 21.59, 2.76x l06 and - 2 . 4 5 for rough rice, respectively. Both
these products exhibit a sigmoid shape (type II) sorption isotherm.
The Chung-Pfost model showed a RSS of 13.79 with an average and greatest
deviation of 0.21% and 1.38% of moisture content respectively. The latter was
observed in the 35 ~ isotherm. This model was fitted in the past to a set of rough rice
isotherms from 10 to 50~ resulting in - 3 . 8 8 x 109, - 3 . 5 2 , - 1 . 1 2 x 10 -4 and 1.3
as values for the estimated parameters.
Finally, the Zuritz et al. model yielded the lowest RSS value of 4.27, with an
average and m a x i m u m deviation of 0.13% and 0.53% at 21.1 ~ respectively. Past
curvefitting of this model to the same rice data mentioned above, resulted in - 23.44,
2.67 x 10 -v, 4 x 105 and - 2 . 1 2 as values for the estimated parameters. Plot of the
curves generated by this model for the set of wood sorption data used, are shown in
Fig. 1.
The R M S E values for each model at different temperatures are given in Table 3.
For the range of temperatures and relative humidities analyzed, the Zuritz et al. model
gave the lowest average R M S E value followed by the Day-Nelson, Chung-Pfost and
Henderson models, respectively.
Evaluation of the differences between actual and calculated data with the Zuritz
et al. model and the H a i l w o o d - H o r r o b i n for one hydrate model, as described by
Simpson (1973), revealed m i n o r deviations; the m a x i m u m being 0.2% moisture con-
Evaluating models for prediction of wood EMC 255

IIIll

e~

IIIII

IIIII

(D
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e4
~D
J
256 St. Avramidis

26
~ Temperature
22- 316K
+

~18- 2
~16- K
"E
o14-
312-
"GI0_
~E 8-
6-
4-
2-
D
0 [ i i i i L
0 012 0'.6 0'.8 1.0
Relative hum[dRy
Fig. 1. Actual Wood Handbook moisture content data and predicted curves using the Zuritz
et al. (1979) model. Temperatures are in Kelvin

Table 3. The goodness of fit as measured by "Root Mean Square Error" (RMSE)

T (~ Henderson Day-Nelson Chung-Pfost Zuritz et al.

21.1 0.32 0.20 0.23 0.21

35.0 0.26 0.18 0.30 0.16
43.3 0.17 0.15 0.24 0.15
51.6 0.15 0.14 0.17 0.15
71.1 0.25 0.14 0.13 0.11
Average 0.23 0.16 0.22 0.16

tent, approximately. It can be said, that the fit of the former was better at the medium
and high relative humidity ranges and at higher temperatures.
All models predicted the shift of the isotherm curve towards the x-axis as the
temperature increased. Additionally, they all predicted the sigmoid shape that charac-
terizes the sorption isotherms for wood.

Conclusion

F o u r models that express moisture content as a function of both relative humidity and
temperature were fitted to some of the U S D A W o o d H a n d b o o k sorption data. The
results revealed that the Zuritz et al. model gave the best fit for the sorption d a t a
between 21.1 and 71.1 ~ based on the value of the calculated Root M e a n Square
Error. The second best was the D a y - N e l s o n model, followed successively by the
Chung-Pfost and Henderson models.
Evaluating models for prediction of wood EMC 257

References

Anderson, N. T.; McCarthy, J. L. 1963: Two-parameter isotherm equation for fiber water
systems. Ind. Eng. Chem. Process Des. Develop. 2 : 1 0 3 - 1 0 5
Anonymous 1927: International Critical Tables, Vol. II, pp. 321-325, 1st Ed. New York:
McGraw-Hill Book Co.
Bradley, R. S. 1936: Polymolecular adsorbed films. Part II. The general theory of the condensa-
tion of vapors on finely divided solids. J. Chem. Soc. 16:1799-1804
Chung, D. S. ; Pfost, H. B. 1967: Adsorption and desorption of water vapor by cereal grains and
their products. Part II: Development of the general isotherm equation. Trans. ASAE. 10:
552 555
Day, D. L. ; Nelson, G. L. 1965: Desorption isotherms for wheat. Trans. ASAE. 8 : 293 297
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TN 174. University of British Columbia, Vancouver, B.C.
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Simpson, W 1973: Predicting equilibrium moisture content of wood by mathematical models.
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(Received April 27, 1988)

Dr. Stavros Avramidis

Asst. Prof. of Wood Physics
Department of Harvesting and Wood Science
Faculty of Forestry
The University of British Columbia
Vancouver, British Columbia V6T lW5
Canada