Journal of Food Engineering 48 (2001) 103±107

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Sorption isotherms and heat of sorption of pineapple

M.D. Hossain a,*, B.K. Bala a, M.A. Hossain b, M.R.A. Mondol a
a
Department of Farm Power and Machinery, Bangladesh Agricultural University, Mymensingh 2202, Bangladesh
b
F.M.P. Engineering Division, Bangladesh Agricultural Research Institute, Gazipu 1701, Bangladesh
Received 5 April 2000; accepted 25 July 2000

Abstract
Sorption isotherms of pineapple were determined at 20°C, 30°C, 40°C and 50°C temperatures by using dynamic method. Six two-
parameter and one three-parameter isotherm models were selected to ®t the observed data, and the modi®ed BET model was found
to be the best-®tted model for pineapple. The heat of sorption of pineapple decreased with an increase in moisture content and the
heat of sorption was found to be a power function of moisture content. Ó 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Dynamic method; Equilibrium moisture content; Heat of sorption; Isotherm model; Pineapple; Sorption isotherm

1. Introduction
Sorption isotherms of foodstu€s are essential for de-
sign, modelling and optimisation of many processes
such as drying, aeration and storage (Labuza, 1968;
Bala, 1991). Knowledge of sorption isotherms is also
important for predicting stability and quality changes
during packaging and storage of dried foods. Many
researchers have developed mathematical equations to
describe the sorption isotherms of food materials. Chi-
rife and Iglesias (1978) reviewed 23 isotherm equations,
both theoretical and experimental, and their use for
®tting sorption isotherms of foods and food products.
None of these equations described accurately the sorp-
tion isotherm over the whole range of relative humidity
and for di€erent types of food materials. Labuza (1975)
noted that no sorption isotherms model could ®t data
over the entire range of relative humidity because water
is associated with the food matrix by di€erent mecha-
nisms in di€erent activity regions. Lomauro, Bakshi,
and Labuza (1985) evaluated two two-parameter equa-
tions and one three-parameter equation for 163 food
materials including fruits, vegetables, spices and starchy
foods. They found that the three-parameter Guggen-
heim, Anderson and den Boer (GAB) equation (Van den
Berg, 1984) described the sorption isotherms for most
foods better than two-parameter equations. The BET
equation developed by Brunauer, Emmett, and Teller
(1938) is the most popular due to its thermodynamic
base. But this equation is valid only from 10±50% rela-
tive humidity (Labuza, 1968; Coulson & Richardson,
1975). Many researchers modi®ed the BET equation and
the modi®ed equation gave a good ®t up to 90% relative
humidity (Dincer & Esin, 1996). The Smith equation
(1947) is useful in describing the sorption isotherm of
biological materials such as starch and cellulose. Hen-
derson (1952) proposed a semi-empirical model for the
equilibrium moisture content of cereal grains. Day and
Nelson (1965) modi®ed the Henderson equation to de-
scribe wheat up to 70% relative humidity. The Chung and
Pfost (1967) equation ®ts grain equilibrium moisture
content data well over the 20±90% relative humidity range.
Knowledge of the heat of sorption is important in
understanding the mechanism of sorption. It is a valu-
able tool in designing equipment for drying (Iglesias &
Chirife, 1976, 1978; Balaban, Zurith, Singh, & Hayak-
awa, 1987). Iglesias and Chirife (1976) calculated and
constructed heat curves from sorption isotherms of
several foods, including fruits, protein foods, vegetables
and spices. They found that, with a few exceptions, the
heat curves showed a regular decrease with increasing
moisture content. So this study was undertaken to de-
termine sorption isotherms to ®t the experimental data
to the isotherm models, and to calculate the heat of
sorption of pineapple (Annas comosus L.).
2. Materials and method

The experiment was conducted at the Process Engi-

*
Corresponding author. neering Laboratory, in the Department of Farm Power
0260-8774/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 6 0 - 8 7 7 4 ( 0 0 ) 0 0 1 3 2 - 1
104 M.D. Hossain et al. / Journal of Food Engineering 48 (2001) 103±107

Notations Qst net isosteric heat of sorption, KJ/mole

rh relative humidity (decimal)
a, b, c parameters of isotherm equations RMSE root mean square error
K constant R universal gas constant (8.315 kJ/kg mol K)
Me equilibrium moisture content, % (dry basis) T temperature, °C
Mo observed moisture content, % (dry basis) Tab absolute temperature, K
Mp predicted moisture content, % (dry basis)

and Machinery, Bangladesh Agricultural University,
Mymensingh, Bangladesh, during the period of Janu-
ary±June, 1999. The dynamic method (Hossain, Bala,
Sarkar, & Sarkar, 1998) was used to measure the
adsorption equilibrium moisture content of pineapple
(A. comosus L.). Airtight cylindrical plastic containers,
115-mm diameter and 135-mm height, containing satu-
rated salt solutions were placed in an electric oven to
provide constant temperature and relative humidity
environments. The digital temperature controller (model
XMTJ) provided the desired temperature (accuracy
‹1°C). A mini fan of 60-mm (3 V, 0.25 A) was ®tted
inside the plastic container to provide continuous stir-
ring of the air inside the container. The values for rel-
ative humidity of the saturated salt solutions were
obtained from the works of Wexler and Hasegawa
(1954) and Young (1967) and these are listed in Table 1.
About 10 g of dried sample from fully ripe pineapple
(sugar content about 10.50%) was placed inside the cy-
lindrical nylon box (50-mm diameter and 40-mm height)
and suspended over the saturated salt solutions in the
container and the container was made airtight with a
plastic cover. The container was then placed in the oven
at a desired constant temperature and allowed to
equilibrate with the environment inside the containers.
The selected temperatures were 20°C, 30°C, 40°C and
50°C with an accuracy of ‹1°C variation. The experi-
ment was conducted in the months of December±Janu-
ary when the ambient temperature was 9±18°C. The
weight of each sample was recorded at 6-h intervals by
taking out the sample from the container very fast and
then replacing the sample in the container. The weight
recording period was about 15±20 s. This procedure was
continued until the weight was constant. About 1.5±5.0
days were required for adsorption equilibrium of the
pineapple with the environment maintained by saturated
salt solutions. No visible mould growth was observed
during the experiments. The moisture content of each
sample was then determined by the oven-drying method
at 80°C for 24 h.

Table 1
Percent relative humidity of the saturated salt solutions at various temperature

Salts Temperature (°C) Reference

20 30 40 50

Lithium chloride (LiCl) 11.4 11.2 11.2 11.1 Young (1967)

Magnesium chloride 33.0 32.4 31.8 31.2 Wexler and Hasegawa (1954)
(MgCl2 á 6H2 O)
Sodium dichromate 55.2 52.5 49.8 46.3 Wexler and Hasegawa (1954)
(Na2 Cr2 O7 á 2H2 O)
Sodium chloride (NaCl) 75.5 75.6 75.4 74.5 Wexler and Hasegawa (1954)
Potassium nitrate (KNO3 ) 93.2 90.7 87.9 85.0 Wexler and Hasegawa (1954)
Potassium sulphate (K2 SO4 ) 97.2 96.6 96.2 95.8 Wexler and Hasegawa (1954)

Table 2
Selected isotherm equations for experimental data ®tting

Name of models Mathematical expression

1. Smith (1947) Me ˆ a ÿ b ln …1 ÿ rh†

2. Chung and Pfost (1967) ln…rh† ˆ ÿa=…RTab † exp…ÿb Me †
3. Henderson (1952) 1 ÿ rh ˆ exp…ÿa Tab Meb †
4. Modi®ed BET (1996) Me ˆ a=…1 ÿ b rh†
5. Iglesias and Chirife (1981) Me ˆ a ‡ b …rh=…1 ÿ rh††
6. Day and Nelson (1965) 1 ÿ rh ˆ exp…ÿa=Meb †
7. GAB (Van den Berg, 1984) Me ˆ a b c rh=…1 ÿ c rh†…1 ÿ c rh ‡ b c rh†
 M.D. Hossain et al. / Journal of Food Engineering 48 (2001) 103±107 105

8.77E)03
50°C

7.92E)03
40°C

7.09E)03
30°C

8.24E)03
20°C
C
Fig. 1. ln(rh) vs 1/Tab graphs for calculating the heat of sorption of

0.9917
0.120
34.36

1.42
0.79
1.24
2.84
pineapple.

50°C

0.1101

1.0862
38.91

2.52
0.78
1.22
3.03
40°C

0.1033

1.4402
0.756

3.234
42.90

2.62

1.19
30°C

0.1015

3.4723
45.72

2.85
0.73
1.05
3.66
20°C
Estimated parameters of di€erent models for the sorption isotherm of pineapple at di€erent temperatures

1.52E)07

4898.123
38.31

10.39
16.91
17 666.10

2316.6
50°C

7.74E)07

Fig. 2. Experimental sorption isotherms of pineapple at di€erent

5026.911
temperatures.
44.15

12.48
20.50
20 701.50

6558.5
40°C

2.1. Model selection

4.05E)07

Six two-parameter and one three-parameter (GAB)

5012.690
23 083.49
49.35

14.48
23.53

isotherm equations were selected for ®tting the experi-

18 456.8

mental data for sorption isotherms for pineapple. The

30°C

selected equations are given in Table 2.

1.38E)07

The parameters of the equations were estimated by

regression analysis using Microsoft Excel 97 software.
4087.847
54.606

17.27
27.28
30 313.75

116 504.8

The value of root mean square error (RMSE) represents

20°C

the ®tting ability of a model in relation to the number of

A

data points. The smaller the RMSE value, the better the
®t of the model.
GAB (Van den Berg, 1984)
Iglesias and Chirife (1981)

v
!
Chung and Pfost (1967)

Day and Nelson (1965)

u n
Modi®ed BET (1996)

uX …Mp ÿ Mo †2
RMSE ˆ t : …1†
Henderson (1952)

iˆ1
n
Smith (1947)

Heat of sorption phenomena can be explained by the

Clausius±Clayperon equation (Iglesias & Chirife, 1976;
Models
Table 3

Okos, Narsimhan, Singh, & Weitmauuer, 1992) as fol-

1.
2.
3.
4.
5.
6.
7.

lows:
106 M.D. Hossain et al. / Journal of Food Engineering 48 (2001) 103±107

o ln …rh† Qst content of pineapple, followed by the Chung and Pfost

ˆ : …2† equation and the GAB equation. The observed and
oT RT 2
predicted sorption isotherms using the modi®ed BET
Integrating Eq. (2), assuming that the net isosteric heat equation at temperatures of 20°C, 30°C, 40°C and 50°C
of sorption (Qst ) is temperature independent, gives the are shown in Fig. 3. The agreements between the ob-
following equation: served and predicted results were excellent for the rela-
  tive humidity range 11±97%. The parameters a and b are
Qst 1
ln …rh† ˆ ÿ ‡ K: …3† found to be linearly dependent on temperature and the
R Tab
following equation was developed to predict the sorp-
The value of Qst was calculated from the slope of the tion isotherms of pineapple for the temperature range
plot between the values of ln(rh) and 1/Tab at constant 20±50°C and relative humidity range 11±97%.
moisture content as shown in Fig. 1. The relative hu-
Me ˆ …21:579 ÿ 0:2264  T †=‰1 ÿ …0:6809 ‡ 0:0024
midities at di€erent temperatures and at constant
moisture content were obtained from the Fig. 2.  T † rhŠ: …4†
The net isosteric heats of sorption for di€erent moisture
contents are shown in Fig. 4. The net isosteric heat of
3. Results and discussion sorption decreased with an increase in moisture content.
A steep slope of the curve is observed at low moisture
Sorption isotherms of pineapple at temperatures of content. At low moisture contents, the heat of sorption
20°C, 30°C, 40°C and 50°C in the relative humidity is higher than at high moisture contents. Tsami (1991)
range of 11±97% are presented in Fig. 2. Higher equi- suggested that the rapid increase in the heat of sorption
librium moisture contents were found at the lower at low moisture content was due to the existence of
temperature at the same relative humidity. The reason highly active polar sites on the surface of the food ma-
may be that with the increase in temperature, water
molecules get activated due to their energy level, causing
them to become less stable and to break away from the
water-binding site of the food materials, thus decreasing
the mono-layer moisture content. Labuza (1968);
Hossain et al. (1998) and Rahman and Labuza (1999)
have presented similar results. Isotherm curves were
found to be sigmoid in shape and all curves followed
similar patterns. Statistically computed parameters for
di€erent isotherm models and their coecients of deter-
mination for sorption of pineapple are given in Tables 3
and 4. For all the models, parameters a, b and c are
found to be temperature dependent. In the case of the
modi®ed BET model, the values of the coecient of
determination were highest. Minimum RMSE value was
found for the modi®ed BET equation and maximum
values were obtained for the Iglesias and Chirife equa-
tion. So, the modi®ed BET equation was found to be the Fig. 3. Observed (Mo ) and predicted (Mp ) sorption isotherms of
best estimator for predicting the equilibrium moisture pineapple by modi®ed BET method at di€erent temperatures.

Table 4
Estimated coecient of determination and RMSE values of di€erent models for the sorption isotherm for pineapple at di€erent temperatures

Models R2 RMSE

20°C 30°C 40°C 50°C

1. Smith (1947) 0.909 0.914 0.914 0.902 3.938

2. Chung and Pfost (1967) 0.957 0.975 0.988 0.903 2.332
3. Henderson (1952) 0.944 0.938 0.946 0.935 3.352
4. Modi®ed BET (1996) 0.999 0.999 0.999 0.998 0.614
5. Iglesias and Chirife (1981) 0.771 0.755 0.763 0.804 7.942
6. Day and Nelson (1965) 0.978 0.972 0.996 0.976 3.521
7. GAB (Van den Berg, 1984) 0.965 0.984 0.983 0.981 3.126
 M.D. Hossain et al. / Journal of Food Engineering 48 (2001) 103±107
,
Fig. 4. Net isosteric heat of sorption for di€erent moisture contents.
terial which are covered with water molecules forming a
mono-molecular layer. The net isosteric heat of sorption
of water in pineapple can be expressed mathematically
as power function of moisture content,
Qst ˆ 29:765Meÿ1:1656 …R2 ˆ 0:9967†: …5†
This mathematical relationship may be used to calculate
the heat of sorption of pineapple for various moisture
contents.
4. Conclusions
Higher sorption isotherms were observed at lower
temperatures. The experimental data was ®tted to seven
isotherm models. The modi®ed BET model was found
to be the best-®t model to describe the sorption iso-
therms of pineapple in the temperature range 20±50°C
and relative humidity range 11±97.5%. So the modi®ed
BET model may be used to estimate sorption isotherms
of pineapple. The heat sorption of pineapple decreases
with an increase in moisture content and is found to be a
power function of moisture content.
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