Journal of Food Engineering 79 (2007) 481–493

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Moisture adsorption behaviour of oatmeal biscuit and oat flakes

Wendy A.M. McMinn *, David J. McKee, T. Ronald A. Magee
School of Chemistry and Chemical Engineering, Queen’s University Belfast, David Keir Building, Stranmillis Road, Belfast BT9 5AG, UK

Received 6 December 2005; received in revised form 8 February 2006; accepted 8 February 2006
Available online 22 March 2006

Abstract

Adsorption isotherms of oatmeal biscuit (convective-baked and microwave-baked) and oat flakes were determined using a gravimetric
static method at 5, 20, 40 and 60 C (relative humidity range 0.03–0.96). The oatmeal biscuits and oat flakes exhibited Type III and II
behaviour, respectively, with the sorption capacity decreasing with increasing temperature. The Ferro-Fontan model provided the best
description of the experimental sorption behaviour, followed by the Guggenheim–Anderson de Boer equation. Differential enthalpy
showed a power law relation with moisture content, with differential entropy also decreasing with increasing moisture content. The linear
relation between differential enthalpy and entropy confirmed the existence of compensation. Spreading pressure increased with increasing
water activity and decreasing temperature. Net integral enthalpy decreased with increasing moisture content. However, net integral
entropy increased with moisture content, but was negative with respect to the entropy of water.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Biscuit; Compensation theory; Entropy; Enthalpy; Isotherm; Oat flakes; Spreading pressure

1. Introduction lated with water activity (Rahman, Perera, & Thebaud,

The sorption behaviour of various foods, and the influ-
ence of temperature on equilibrium moisture content, have
been studied and modelled extensively over recent years
(Lewicki, 1998). Baked products, such as biscuits, are of
significant economic importance, however, limited mois-
ture sorption data are available in the literature (Tubert
& Iglesias, 1986), crackers and sugar coated crackers
(Tubert & Iglesias, 1986), cookies (Palou, López-Malo, &
Argaiz, 1997), cookies, crackers and jam (composites)
(Kim, Kim, Kim, Shin, & Chang, 1998), crackers (Kim &
Okos, 1999), biscuit containing processed mango kernel
flour (Arogba, 2001), and biscuit (Guillard, Broyart, Guil-
bert, Bonazzi, & Gontard, 2004). The quality of biscuits is
lost by the growth of micro-organisms and by changes in
sensory properties such as crispiness, hardness, colour
and flavour, with these deteriorative changes being corre-
*
Corresponding author. Tel.: +44 (0)28 9097 4065; fax: +44 (0)28 9097
4627.
E-mail address: w.mcminn@qub.ac.uk (W.A.M. McMinn).
1998). In general, sorption data are obtained at one tem-
perature (usually the storage temperature), however, for
thermodynamic analysis of sorption, and modelling of
the baking and storage stability processes, data at a range
of temperatures are necessary (Palou et al., 1997).
Food systems typically exhibit Type II or III (according
to the BET classification) isotherms (Brunauer, Deming,
Deming, & Troller, 1940). The former, sigmoidal shaped
curve, is typical for starchy foods, such as oat bran and
flour (Cadden, 1988; Durakova & Menkov, 2005; Erbas,
Ertugay, & Certel, 2005), while the latter form, normally
displaying an exponential increase in equilibrium moisture
content with water activity, is observed for foods with a
high sugar or salt content (Guillard et al., 2004; Kim
et al., 1998). Biscuits are a complex combination of ingre-
dient types, with both Type II and III isotherm forms being
reported in the literature for these confectionery products
(Arogba, 2001; Kim & Okos, 1999; Tubert & Iglesias,
1986). Therefore, as theoretical prediction of water sorp-
tion isotherms is not possible, experimental studies are
necessary.

0260-8774/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2006.02.009
482 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493
Nomenclature
A constant (isotherm model)
Am area of water molecule (1.06 · 1019 m2)
aw water activity
aw geometric mean water activity (at constant
spreading pressure)
B constant (isotherm model)
bi constant (related to properties of adsorbed
water)
b0 constant (related to properties of adsorbed
water)
C constant (isotherm model)
df degree of freedom (number of experimental data
points minus number of constants in model)
DG free energy at Tb (kJ mol1)
K constant (isotherm model)
KB Boltzmann constant (1.380 · 1023 J K1)
Dhd net isosteric heat of sorption (net differential en-
thalpy) (kJ mol1)
Dhin net equilibrium heat of sorption (net integral en-
thalpy) (kJ mol1)
Dhd average differential enthalpy (kJ mol1)
Numerous correlations have been proposed in the liter-
ature to represent the relationship between equilibrium
moisture content and water activity. The models can be
divided into several categories; kinetic models based on a
mono-layer (BET), kinetic models based on a multi-layer
and condensed film (GAB, Lewicki I, Lewicki II), semi-
empirical (Ferro-Fontan, Halsey) and empirical (Bizot,
1983). Each model has had relative success in representing
experimental sorption isotherm data, with the extent being
dependant on the water activity range and type of food-
stuff. Attempts to find a general isotherm equation have
been unsuccessful, primarily due to the fact that water
activity depends on food composition, and the interaction
of the constituents with water in thermo-dynamical equilib-
rium conditions. Thus, experimental sorption data are nec-
essary in order to assess the applicability of the isotherm
equations and determine the magnitude of the correlation
parameters for a specific product (Vullioud, Márquez, &
De Michelis, 2004).
Further analysis of the sorption phenomena can be
undertaken in terms of thermodynamic functions such as
differential enthalpy and entropy, integral enthalpy and
entropy, and spreading pressure. The net isosteric heat of
sorption, or differential enthalpy, is an indicator of the
state of water adsorbed by the solid particles, which in turn
is a measure of the physical, chemical and microbial stabil-
ity of biological materials under storage (Fasina, Sokhan-
sanj, & Tyler, 1997). Palou et al. (1997) evaluated the
heat of sorption of cookies and corn snacks, and observed
the values to increase to a maximum and then steadily
decrease with increasing moisture content. Kim et al.
m number of (Dhd, DSd) data pairs
MRE mean relative error (%)
Me experimental value
Mp predicted value
N number of experimental observations
ni total number of isotherms
R universal gas constant (8.314 J mol1 K1)
r2 coefficient of determination
RSS residual sum-of-squares
DSd differential entropy (J mol1 K1)
DSin net integral entropy (J mol1 K1)
DS d average differential entropy (J mol1 K1)
SEE standard error of estimate
t t value at (m  2) degrees of freedom
T temperature (K)
Tb isokinetic temperature (K)
Thm harmonic mean temperature (K)
X equilibrium moisture content (kg moisture/kg
dry solid)
X0 monolayer moisture content (kg kg1, dry basis)
p spreading pressure (J m2)
(1998) and Arogba (2001) determined the isosteric heat of
cookies and crackers, and biscuit (containing processed
mango flour), respectively, using the Clausius–Clapeyron
equation, and reported a decrease with increasing moisture
content. Differential entropy is proportional to the num-
ber of available sorption sites at a specific energy level
(Madamba, Driscoll, & Buckle, 1996). Rizvi and Benado
(1983) and Tolaba, Suarez, and Viollaz (1997) evaluated
the variation in differential entropy of grain sorghum,
and cereal grains and starchy materials, respectively, with
respect to moisture content. The isokinetic, or enthalpy–
entropy compensation, theory has also been used to
evaluate sorption processes. Madamba et al. (1996) and
Beristain, Garcia, and Azuara (1996) successfully applied
the enthalpy–entropy compensation to water adsorption
in garlic and starchy materials, respectively. Gabas, Telis-
Romero, and Menegalli (1999) and Gabas, Menegalli,
and Telis-Romero (2000) reported an enthalpy-controlled
mechanism in the adsorption isotherms of grape and plum,
respectively.
Integral entropy describes the degree of disorder and
randomness of motion of water molecules (Mazza &
LeMaguer, 1978). The net equilibrium heat of sorption,
or integral enthalpy, provides a measure of the strength
of moisture binding. Fasina et al. (1997) and Fasina,
Ajibola, and Tyler (1999) studied the thermodynamics of
moisture sorption in alfalfa pellets, winged bean seed and
gari, respectively. Tolaba et al. (1997) also determined the
dependence of the integral enthalpy and entropy of cereal
grains on moisture content. The thermodynamic functions
for melon and cassava, and cowpea were determined from
 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493 483

experimental sorption data by Aviara and Ajibola (2002) Table 1

and Ajibola, Aviara, and Ajetumobi (2003), respectively. Water activity of sulphuric acid solutions at selected concentrations and
temperatures (Ruegg, 1980)
The spreading pressure, or surface potential, represents
the surface excess free energy, and provides an indication H2SO4 solution Water activity (aw)
(%, v/v)
of the increase in surface tension of bare sorption sites 5 C 20 C 40 C 60 C
due to sorbed molecules (Fasina et al., 1999). Tolaba, 10 0.9554 0.9558 0.9565 0.9574
Suarez, and Viollaz (1995) reported a non-linear relation- 20 0.8771 0.8796 0.8831 0.8882
ship between the spreading pressure and water activity of 30 0.7396 0.7491 0.7604 0.7711
40 0.5417 0.5599 0.5816 0.5989
cereal grains and starchy materials. Fasina et al. (1999) 50 0.3238 0.3442 0.3702 0.3936
observed that temperature had little affect on the spreading 60 0.1420 0.1573 0.1781 0.1988
pressure values for gari and bean seeds in the range 40– 70 0.0355 0.0422 0.0521 0.0611
70 C. However, Aviara and Ajibola (2002) reported the
spreading pressure of cassava to increase with increasing
water activity and decreasing temperature. temperature and acid concentration on the equilibrium rel-
The objectives of this study were to (i) undertake an ative humidity of sulphuric acid is presented in Table 1
experimental examination of the moisture adsorption (Ruegg, 1980).
behaviour of convective-baked oatmeal biscuit, micro- The prepared desiccators were then placed in either a
wave-baked oatmeal biscuit and oat flakes; (ii) evaluate refrigeration unit at 5 ± 1 C, left at room temperature
the ability of selected mathematical models to represent (20 ± 1 C), or kept in a temperature controlled cabinet
the experimental data; (iii) determine the thermodynamic maintained at 40 or 60 ± 1 C. The samples were allowed
functions (differential enthalpy and entropy, spreading to equilibrate until there was no discernable weight change,
pressure, integral enthalpy and entropy), and (iv) evaluate as evidenced by constant weight values (±0.001 g). This
the application of the enthalpy–entropy compensation the- involved a period of approximately 3 weeks for the refrig-
ory to the sorption phenomena. erated samples and 9 days for the samples at higher tem-
peratures. The total time required for removal, weighing
2. Materials and methods and replacing the samples in the desiccators was approxi-
mately 30 s. This minimized the degree of atmospheric
2.1. Preparation of oatmeal biscuit moisture sorption during weighing. Each experiment was
carried out on triplicate.
Oatmeal biscuit dough (38.3% (w/w) oat flakes, 30.6% The bone dry mass was determined gravimetrically by
margarine, 15.3% flour, 15.3% sugar, 0.4% baking soda drying samples of crushed oatmeal biscuit or oat flakes in
and 0.1% salt) was prepared by a two-stage mixing method a convection oven at 105 ± 1 C for 8–10 h (AOAC, 1980).
using a domestic mixer (Kenwood, model KM199). Firstly,
the sugar and margarine were mixed for 2 min at high 2.3. Data analysis
speed (level 3) and then the remaining dry ingredient mix-
ture was added and mixed for a further 4 min (level 1.5). 2.3.1. Isotherm models
The dough was then flattened to a thickness of 11 ± Many models are detailed in the literature for descrip-
0.5 mm using a rolling pin. From this dough sheet, samples tion of experimental moisture sorption characteristics.
were cut using a circular cutter of diameter of 91 mm. Selected two-parameter (Brunauer–Emmett–Teller,
Dough samples (77 ± 0.5 g) were then placed in glass Halsey, Lewicki I) and three-parameter (Ferro-Fontan,
dishes, and baked in either a fan-assisted convective oven Guggenheim–Anderson–de Boer, Lewicki II) correlations
(GENLAB 75) at 200 ± 1 C for 18 min, or a standard were chosen to fit the experimental isotherm data of the
domestic microwave oven (Panasonic, model NNT543W) oatmeal biscuits and oat flakes. The equations are detailed
at 900 W for 3 min. in Table 2. The parameter values of the selected equations
were obtained by non-linear regression analysis, using
2.2. Experimental determination of moisture sorption TableCurve 2D software (Systat Software Inc.).
isotherms Three criteria were used to evaluate the goodness-of-fit
of each isotherm model; mean relative error (MRE), stan-
The adsorption isotherms were determined by a stan- dard error of estimate (SEE) and residual sum-of-squares
dard static gravimetric technique, in which the weight of (RSS):
 
the sample was measured discontinuously within a system 100 X M e  M p 
of thermally stabilised desiccators. Triplicate samples of MRE ¼  M  ð1Þ
N e
crushed bone dry convective-baked oatmeal biscuit, micro- sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P 2
wave-baked oatmeal biscuit or oat flakes (6 ± 0.001 g) were ðM e  M p Þ
placed in petri-dishes inside desiccators, in which sulphuric SEE ¼ ð2Þ
df
acid solutions were used to maintain the specified relative X 2
humidity (aw between 0.0355 and 0.9565). The effect of RSS ¼ ðM e  M p Þ ð3Þ
484 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493

Table 2
Isotherm equations for experimental data fitting
Model Mathematical expression
Brunauer–Emmett–Teller (BET) (Brunauer et al., 1938) X = X0Aaw/[(1  aw)(1 + (A  1)aw)]
h i1=C
B
Ferro-Fontan (Ferro-Fontan et al., 1982) X ¼ lnðA=aw Þ
Guggenheim–Anderson–de Boer (Van den Berg & Bruin, 1981) X = X0CKaw/[(1  Kaw)(1  Kaw + CKaw)]
h i1=B
A
Halsey (Halsey, 1948) X ¼ T lnða wÞ
h iB1
Lewicki I (Lewicki & Wolf, 1995) X ¼ A a1w  1
 
Lewicki II (Lewicki, 1998) X ¼ A ð1a1 ÞB  1þa1
C
w w

A MRE value less than 10% is indicative of the correlation
providing a good representation of the data (Lomauro,
Bakshi, & Chen, 1985). The SEE value accounts for the
number of constants in the model, with the magnitude of
this parameter giving a measure of the reliability of the
model to describe the experimental data, irrespective of
the number of parameters. The lower the calculated values
of MRE and SEE, the better the ability of the models to rep-
resent the experimental data (Chen & Morey, 1989). The
residual sum-of-squares (RSS) is important in the non-lin-
ear regression process, with the fitting procedure being
designed to achieve the minimum value (Sun & Byrne,
1998). The aforementioned statistical parameters have been
widely used as the primary criterion to select the best equa-
tion to represent the sorption behaviour of materials
(Durakova & Menkov, 2005; Sun & Byrne, 1998).
2.3.2. Isosteric heat of sorption
The isosteric heat of sorption gives a measure of the
water-solid binding strength. The net isosteric heat of sorp-
tion, or differential enthalpy (Dhd), as the amount of energy
above the heat of vaporization of water associated with the
sorption process, was determined from the experimental
data using the Clausius–Clapeyron equation (Tsami,
Maroulis, Marinos-Kouris, & Saravacos, 1990):
 
dðln aw Þ
Dhd ¼ R ð4Þ
dð1=T Þ X
Re-plotting the experimental sorption isotherm in the form
ln(aw) versus 1/T, for a specific moisture content, the slope
of the regression line (Dhd/R) provided a measure of the
net isosteric heat of sorption. This procedure is based on
the assumption that Dhd is invariant with temperature, with
measurement of the sorption isotherms at more than two
temperatures being required for application of the method
(Tsami et al., 1990).
2.3.3. Enthalpy–entropy compensation theory
The differential entropy (DSd) of a material is propor-
tional to the number of available sorption sites correspond-
ing to a specific energy level (Madamba et al., 1996). By
fitting the relation:
ð ln aw ÞX ¼ Dhd =ðRT Þ  DS d =R
to the equilibrium data (ln(aw) versus 1/T), the differential
entropy of sorption (DSd), at a specific moisture content,
was determined from the intercept (DSd/R). Further appli-
cation of Eq. (5), at different moisture contents, allowed the
variation in Dhd and DSd with moisture content to be deter-
mined (Aguerre, Suarez, & Viollaz, 1986).
The enthalpy–entropy compensation theory proposes a
linear relationship between Dhd and DSd (Leffer & Grun-
wald, 1963):
Dhd ¼ T b DS d þ DG ð6Þ
From a plot of Dhd versus DSd, the isokinetic temperature
(Tb) and free energy at Tb (DG) were calculated using linear
regression.
To corroborate the existence of true compensation a sta-
tistical analysis test, proposed by Krug, Hunter, and
Greiger (1976a, 1976b) was applied to the data. This
involved comparison of the isokinetic temperature with
the harmonic mean temperature (Thm):
n
T hm ¼ Pn ð7Þ
1 ð1=T Þ
An approximate (1  a)100 percent confidence interval for
Tb may be calculated from:
pffiffiffiffiffiffiffiffi
T b ¼ Tb b  tm2;a=2 VarðT b Þ ð8Þ
where
P
ðDhd  Dhd ÞðDS d  DS d Þ
b
Tb ¼ P ð9Þ
ðDS d  DS d Þ2
P
ðDhd  DG  Tb b DS d Þ
2
VarðT b Þ ¼ P 2
ð10Þ
ðm  2Þ ðDS d  DS d Þ
The compensation theory only applies if Tb 5 Thm. If Thm
is within the Tb interval, the observed distribution of data
in the (Dhd, DSd) plane solely reflects experimental error,
and not chemical factors (Beristain et al., 1996). In this
work a 95% confidence interval for Tb was calculated for
all data sets.
2.3.4. Integral enthalpy and integral entropy
The variation in net equilibrium heat of sorption, or
integral enthalpy (Dhin), with moisture content indicates
the level to which water/substrate interaction is greater
ð5Þ than the interaction of water molecules (Fasina et al.,
 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493 485

1999). This integral quantity was calculated in a similar presented in Table 3. The sorption data for a typical sys-
manner to the differential enthalpy of sorption, but at a tem, microwave-baked oatmeal biscuit, are also shown in
constant spreading pressure, p: Fig. 1. The equilibrium moisture content at each water
  activity represents the mean value of three replications.
dðln aw Þ
Dhin ¼ R ð11Þ The equilibrium moisture content of the convective-baked
dð1=T Þ p
and microwave-baked oatmeal biscuits increased exponen-
The spreading pressure (p) was calculated by adopting an tially with increasing water activity, following the form of a
analytical procedure proposed by Iglesias, Chirife, and Type III isotherm according to the BET classification (Bru-
Viollaz (1976) nauer et al., 1940). At lower water activities (aw < 0.75), a
Z aw gradual increase in equilibrium moisture content with
KBT h
p¼ daw ð12Þ increasing water activity was observed. This reflected water
Am 0 a w
sorption by the starch-based components (oat flakes and
X
h¼ ð13Þ flour) of the dough mixture. At high water activities
X0 (aw > 0.75), however, the sugar component of the biscuit
A value of aw = 0 will make the integral of Eq. (12) indeter- (15.4% w/w) rendered the most significant influence on
minate. Therefore, calculation of the integral changes from the sorption behaviour, resulting in a high equilibrium
a numerical procedure to assume an empirical relationship water uptake. For example, the equilibrium moisture con-
between water activity and moisture content (Li, Nanri, tent of microwave-baked biscuit at 0.75aw was 6.75 ±
Douglas, & Vera, 1994). In this work, the Dent model 0.42 g/100 g (dry basis, db) (20 C), while at 0.96aw this
was used (Dent, 1977): increased in magnitude to 26.5 ± 0.91 g/ 100 g (db). Guil-
lard et al. (2004) reported dry biscuit to exhibit Type III
aw 1 b0  2bi bi ðb0  bi Þ 2
¼ þ aw  aw ð14Þ behaviour, with an uptake of water of 10 g/100 g (wet
X b0 X 0 b0 X 0 b0 X 0 basis, wb) at 0.7aw increasing significantly above this value
At aw = 0, Eq. (14) predicts a finite value of to 37 g/100 g (wb) at 0.97aw. Similar results were observed
aw/X = (b0X0)1, therefore avoiding the previously men- by Palou et al. (1997) for various cookies and corn snacks,
tioned numeric instability. Thus, the spreading pressure and by Arogba (2001) for biscuit, with equilibrium mois-
of adsorbed water per sorption site can be represented as ture contents of between 23 g/100 g (wb) (‘Tostitos’) and
  43 g/100 g (w.b.) (‘Animalitos’) at 25 C (0.97aw) and
1 þ b0 aw  bi aw
p ¼ K B T ln ð15Þ 59 g/100 g (wb) at 31 C (0.97aw), respectively. As shown
1  bi aw
in Table 3 and Fig. 2, the adsorption behaviours of the con-
The Dent model was utilized in a different form by Skaar vective-baked and microwave-baked biscuits were compa-
and Babiak (1982), whereby spreading pressure was ex- rable. For example, at 0.58aw and 40 C, the equilibrium
pressed in terms of surface area per sorption site, or area moisture content of the respective biscuits was 3.18 ±
per water molecule (i.e. one molecule of water on each 0.11 and 3.38 ± 1.37 g/100 g (db). This would suggest that
sorption site, that is, complete monolayer coverage). The the baking technique did not have an impact on the prod-
area of a water molecule (Am) was determined as uct shelf-life.
1.06 · 1019 m2 (Mazza, 1980). Thus, the spreading pres- As the main component (38.3% w/w) of the oatmeal bis-
sure on the basis of surface area is cuit dough, the sorption characteristics of oat flakes were
  also examined. In contrast to the oatmeal biscuits, the iso-
KBT 1 þ b0 aw  bi aw
p¼ ln ð16Þ therms of the oat flakes were of sigmoidal form, reflecting
Am 1  bi aw
Type II behaviour (Fig. 2). This is typical of products with
The integral enthalpy was further used to determine the a high starch content. At lower aw (<0.75), the equilibrium
integral entropy (DSin), which describes the degree of disor- moisture content gradually increased with increasing water
der and randomness of motion of water molecules, and activity, however, at aw > 0.75 a more sharp increase was
quantifies the mobility of the adsorbed water molecules observed. Cadden (1988) also reported a Type II increase
(Mazza & LeMaguer, 1978). The integral entropy of sorbed in the equilibrium moisture content of oat bran with
water, DSin, was calculated using (Fasina et al., 1997) increasing water activity, with the ‘condensed water region’
being observed at aw > 0.7.
DS in ¼ ðDhin =T Þ  R lnðaw Þ ð17Þ
In general, the oat flakes had a higher sorption capacity
than that of the oatmeal biscuits at all water activities and
3. Results and discussion temperatures. This may be attributed to the significant fat
content (30.6% w/w) of the biscuits. Iglesias and Chirife
3.1. Adsorption isotherms (1982) also reported the presence of fat or oil to contribute
to lower sorption capacity in agricultural crops.
The experimental adsorption isotherm data for convec- The moisture sorption behaviour of the biscuits and
tive-baked oatmeal biscuits, microwave-baked oatmeal bis- oat flakes was temperature dependent, as indicated by a
cuits and oat flakes, in the aw range 0.0035–0.957, are decrease in equilibrium moisture content, at a given aw, with
486 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493

Table 3
Experimental equilibrium moisture sorption data for convective-baked and microwave-baked oatmeal biscuits and oat flakes
5 C 20 C 40 C 60 C
1 1 1
aw a
X (kg kg db) aw X (kg kg db) aw X (kg kg db) aw X (kg kg1 db)
Convective-baked biscuit
0.00350 0.0009 ± 0.0001 0.00480 0.0002 ± 0.0001 0.00710 0.0004 ± 0.0001 0.0103 0.0050 ± 0.0007
0.0355 0.0112 ± 0.0002 0.0422 0.0055 ± 0.0003 0.0521 0.0045 ± 0.0004 0.0611 0.0081 ± 0.0008
0.142 0.0147 ± 0.0002 0.157 0.0093 ± 0.0001 0.178 0.0146 ± 0.0004 0.199 0.0120 ± 0.0100
0.324 0.0248 ± 0.0017 0.344 0.0188 ± 0.0010 0.370 0.0160 ± 0.0006 0.394 0.0144 ± 0.0012
0.542 0.0386 ± 0.0008 0.560 0.0365 ± 0.0008 0.582 0.0318 ± 0.0011 0.599 0.0308 ± 0.0237
0.740 0.0588 ± 0.0053 0.749 0.0547 ± 0.0075 0.760 0.0517 ± 0.0066 0.771 0.0504 ± 0.0031
0.877 0.1240 ± 0.0212 0.880 0.1180 ± 0.0174 0.883 0.0948 ± 0.0042 0.888 0.0864 ± 0.0077
0.955 0.2841 ± 0.0066 0.956 0.2521 ± 0.0211 0.957 0.2474 ± 0.0091 0.958 0.2373 ± 0.0059
Microwave-baked biscuit
0.00350 0.0011 ± 0.0002 0.00480 0.0022 ± 0.0003 0.00710 0.0036 ± 0.0004 0.0103 0.0020 ± 0.0002
0.0355 0.0110 ± 0.0003 0.0422 0.0058 ± 0.0008 0.0521 0.0041 ± 0.0006 0.0611 0.0040 ± 0.0009
0.142 0.0153 ± 0.0003 0.157 0.0113 ± 0.0002 0.178 0.0110 ± 0.0003 0.199 0.0090 ± 0.0003
0.324 0.0269 ± 0.0017 0.344 0.0194 ± 0.0019 0.370 0.0174 ± 0.0005 0.394 0.0200 ± 0.0008
0.542 0.0424 ± 0.0192 0.560 0.0385 ± 0.0113 0.582 0.0338 ± 0.0137 0.599 0.0327 ± 0.0227
0.740 0.0713 ± 0.0084 0.749 0.0675 ± 0.0042 0.760 0.0635 ± 0.0063 0.771 0.0600 ± 0.0010
0.877 0.1541 ± 0.0218 0.880 0.1482 ± 0.0132 0.883 0.1353 ± 0.0089 0.888 0.1263 ± 0.0083
0.955 0.2963 ± 0.0123 0.956 0.2652 ± 0.0091 0.957 0.2533 ± 0.0061 0.958 0.2424 ± 0.0104
Oat flakes
0.00350 0.0056 ± 0.0005 0.00480 0.0032 ± 0.0005 0.00710 0.0025 ± 0.0004 0.0103 0.0027 ± 0.0008
0.0355 0.0176 ± 0.0004 0.0422 0.0138 ± 0.0005 0.0521 0.0099 ± 0.0004 0.0611 0.0112 ± 0.0008
0.142 0.0228 ± 0.0005 0.157 0.0264 ± 0.0007 0.178 0.0231 ± 0.0007 0.199 0.0210 ± 0.0006
0.324 0.0422 ± 0.0137 0.344 0.0408 ± 0.0016 0.370 0.0455 ± 0.0012 0.394 0.0356 ± 0.0006
0.542 0.0757 ± 0.0008 0.560 0.0736 ± 0.0026 0.582 0.0659 ± 0.0016 0.599 0.0610 ± 0.0032
0.740 0.1072 ± 0.0017 0.749 0.0993 ± 0.0048 0.760 0.0954 ± 0.0050 0.771 0.0943 ± 0.0042
0.877 0.1722 ± 0.0077 0.880 0.1661 ± 0.0182 0.883 0.1553 ± 0.0770 0.888 0.1462 ± 0.0053
0.955 0.2721 ± 0.0087 0.956 0.2601 ± 0.0101 0.957 0.2233 ± 0.0092 0.958 0.1972 ± 0.0047
a
Mean and standard deviation based on n = 3 replicates.

0.35 0.30
5°C Biscuit (Conv-baked)
0.3 20°C 0.25 Biscuit (Mw-baked)
40°C Oat flakes
0.25 60°C
g kg -1, db)

0.20
X (kg kg -1, db)

Ferro-Fontan Model
0.2
0.15
0.15
X (kg

0.10
0.1

0.05 0.05

0 0.00
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
aw
aw
Fig. 1. Experimental and predicted (Ferro-Fontan Model) adsorption
isotherms for microwave-baked oatmeal biscuit. Fig. 2. Experimental adsorption isotherms for convective-baked oatmeal
biscuits, microwave-baked oatmeal biscuits and oat flakes at 40 C.

increasing temperature. This was indicative of a lowering of
the hygroscopic nature of the biscuit. This trend is generally
ascribed to a reduction in the number of active sites for
water binding due to chemical and physical changes
induced by temperature, e.g. gelatinisation of starch and
denaturation of protein (Erbas et al., 2005). The increased
temperature may also have led to activation of the water
molecules to higher energy levels, which caused them to
become less stable and break away from the water-binding
sites of the food, thus decreasing the equilibrium moisture
content (Palipane & Driscoll, 1992). From a practical
standpoint this has many implications, for example, at a
given moisture content, the increase in water activity with
increasing temperature can lead to increased chemical and
microbiological reaction rates and thus, enhanced quality
degradation (Van den Berg & Bruin, 1981). Palou et al.
(1997) and Kim and Okos (1999) reported the sorption
capacity of cookies and crackers, respectively, to decrease
 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493 487

with increasing temperature. Cadden (1988) also found that
oat bran became less hygroscopic when the temperature was
increased from 25 to 37 C.
3.2. Model application
The isotherm correlations of the models included in this
work (Table 2) were selected based on factors including
agreement between the experimental data and model, range
of applicability, theoretical basis of the parameters, and
simplicity. Although additional models were initially con-
sidered including Modified-Brunaeur–Emmett–Teller,
Henderson, Modified-Henderson, Modified-Oswin, Peleg,
Ratti and Smith, following preliminary data analysis these
were excluded. The parameters for the sorption models are
shown in Tables 4–6, together with the corresponding
MRE, SEE and RSS values used to determine the perfor-
mance of each equation.
Examination of the results indicated that the Ferro-
Fontan model gave the closest fit to the experimental
adsorption data in the water activity range 0.03–0.96.
Mathematical comparison of the observed and predicted
results gave MRE values ranging from 2.08% to 12.9%
(average 7.66%), SEE values between 0.0029 and 0.014
(average 0.0075) and RSS values ranging from 1.89–
13.3 · 105 (average 7.34 · 105). It should be noted that
the Ferro-Fontan equation is a three-parameter semi-
empirical model (Ferro-Fontan, Chirife, Sancho, &
Iglesias, 1982). The second best model to describe the
experimental data was the kinetic GAB model. Compari-
son of the goodness-of-fit parameters for the Ferro-Fontan
and GAB models indicated those obtained for the latter
correlation were slightly higher. Statistical data for the
GAB correlation were; MRE from 4.68% to 16.7% (aver-
age 7.09%), SEE between 0.0032 and 0.012 (average
0.007) and RSS ranging 2.39–15.9 · 105 (average
6.47 · 105). Further analysis of the data showed the
BET correlation to provide an adequate description of
the experimental data, within a limited water activity range
(0.03–0.45). Average MRE, SEE and RSS values of 8.40%,
0.0026 and 0.986 · 105, respectively, were observed.
The Halsey equation provided the worst representation
of the data, with the MRE value for 92% of the experimen-
tal conditions being greater than 10%. The Lewicki I and

Table 4
Estimated values of coefficients (A, B, C, X0, C, K), mean relative error (MRE), standard error of estimate (SEE) and residual sum-of-squares (RSS) of
models for adsorption of convective-baked oatmeal biscuit at various temperatures
Model Parameter 5 C 20 C 40 C 60 C
BET (aw = 0.03–0.45) X0 0.0117 0.0148 0.0118 0.009
A 34.9 8.26 11.1 110
MRE (%) 10.2 14.0 3.78 4.43
SEE 0.0019 0.0013 0.0004 0.0008
RSS (·105) 0.76 0.39 0.04 0.15
Ferro-Fontan (aw = 0.03–0.96) A 0.00942 0.0158 0.00631 0.00319
B 1.00 1.02 0.992 0.981
C 1.26 1.05 1.25 1.42
MRE (%) 6.65 8.75 12.9 9.35
SEE 0.0074 0.0086 0.0058 0.014
RSS (·105) 5.81 10.9 3.49 3.83
GAB (aw = 0.03–0.96) X0 0.0171 0.0167 0.0121 0.0132
C 37.5 6.59 13.7 12.8
K 0.984 0.978 0.994 0.957
MRE (%) 6.07 9.82 8.06 8.16
SEE 0.0047 0.0059 0.0064 0.0032
RSS (·105) 2.74 4.21 4.97 2.39
Halsey (aw = 0.03–0.96) A 2.60 2.35 2.85 2.92
B 1.26 1.26 1.13 1.11
MRE (%) 6.36 21.6 14.4 16.1
SEE 0.0056 0.014 0.021 0.031
RSS (·105) 3.97 23.2 96.3 227
Lewicki I (aw = 0.03–0.96) A 0.0307 0.0278 0.0197 0.0169
B 0.275 0.283 0.185 0.155
MRE (%) 24.3 12.3 22.3 28.2
SEE 0.015 0.007 0.011 0.016
RSS (·105) 22.8 6.49 14.5 28.0
Lewicki II (aw = 0.03–0.96) A 0.0283 0.0276 0.0172 0.0139
B 0.758 0.727 0.860 0.906
C 0.128 0.634 0.381 0.0208
MRE (%) 5.31 8.17 9.00 9.39
SEE 0.0052 0.0067 0.010 0.011
RSS (·105) 3.78 5.61 11.3 12.6
488 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493

Table 5
Estimated values of coefficients (A, B, C, D, C, K), mean relative error (MRE), standard error of estimate (SEE) and residual sum-of-squares (RSS) of
models for adsorption of microwave-baked oatmeal biscuit at various temperatures
Model Parameter 5 C 20 C 40 C 60 C
BET (aw = 0.03–0.45) X0 0.0187 0.0141 0.0127 0.0179
A 26.9 13.9 10.8 3.14
MRE (%) 10.9 4.56 8.20 9.61
SEE 0.0036 0.0006 0.0005 0.0007
RSS (·105) 0.094 0.090 0.090 0.12
Ferro-Fontan (aw = 0.03–0.96) A 0.0242 0.0438 0.0371 0.0274
B 1.04 1.09 1.07 1.05
C 1.03 0.819 0.823 0.879
MRE (%) 8.18 6.43 6.65 7.67
SEE 0.0081 0.0066 0.0041 0.0043
RSS (·105) 6.73 4.92 1.89 2.09
GAB (aw = 0.03–0.96) X0 0.0231 0.0262 0.0226 0.0186
C 9.74 1.89 1.692 2.41
K 0.966 0.948 0.957 0.967
MRE (%) 9.98 16.7 14.8 9.36
SEE 0.0095 0.0095 0.0070 0.0058
RSS (·105) 10.5 10.5 5.34 3.42
Halsey (aw = 0.03–0.96) A 2.42 2.18 2.32 2.36
B 1.38 1.38 1.32 1.30
MRE (%) 12.2 40.2 51.8 53.6
SEE 0.015 0.028 0.031 0.036
RSS (·105) 29.9 79.3 12.3 205
Lewicki I (aw = 0.03–0.96) A 0.0408 0.0369 0.0311 0.0276
B 0.351 0.354 0.318 0.300
MRE (%) 15.1 12.4 9.03 6.67
SEE 0.013 0.015 0.012 0.0085
RSS (·105) 21.2 33.3 21.2 11.7
Lewicki II (aw = 0.03–0.96) A 0.0428 0.0691 0.0514 0.0407
B 0.647 0.470 0.534 0.546
C 0.522 5.48 5.46 7.75
MRE (%) 9.41 24.5 20.9 28.5
SEE 0.013 0.016 0.014 0.036
RSS (·105) 20.2 20.6 17.9 199

Lewicki II equations also gave a poor fit, with 67% and
42% of the isotherms, respectively, being inadequately
described. The aforementioned models exhibited corre-
sponding average MRE values of 14.7% and 12.7%.
Guillard et al. (2004) reported the Ferro-Fontan model
to adequately describe the experimental sorption data of
biscuit, in the aw range 0–0.97, at 20 C. Palou et al.
(1997) found that the relationship between the equilibrium
moisture content and aw (range 0.11 to 0.90) of cookies and
corn snacks, although best described by the Peleg model,
could also be adequately represented by the GAB equation
(parameters of comparable magnitude to those obtained in
this work) and the BET model (0.11 < aw < 0.45). Kim
et al. (1998) and Kim and Okos (1999) also considered
the GAB model to provide a good representation of the
sorption behaviour of cookies, crackers and jam compos-
ites, and crackers, respectively. Cadden (1988) adequately
represented the adsorption data for oat bran using the
GAB model.
The monolayer moisture content (X0) for each tempera-
ture, calculated using the BET and GAB equations, is
shown in Tables 4–6. In general, the X0 value calculated
using the GAB model was higher than that calculated using
the BET equation, as has been reported by other researchers
(Erbas et al., 2005; Palou et al., 1997). For oatmeal biscuits
(convective- and microwave-baked), the values were higher
than the corresponding value for oat flakes and, in general,
decreased as temperature increased. The X0 value of foods
has been shown to vary with composition (particularly
starch and protein content) and process (Lomauro et al.,
1985). Palou et al. (1997) reported BET monolayer values
for cookies between 0.0371 and 0.0449 kg kg1 and Arogba
(2001) values between 0.0448 and 0.0653 kg kg1 for biscuit
containing processed mango. Durakova and Menkov
(2005) also reported values of similar magnitude (0.0528–
0.0726 kg kg1) for chickpea flour. Cadden (1988) reported
GAB X0 values for oat bran of 0.0618–0.0652 kg kg1 in the
range 4–37 C.
3.3. Differential enthalpy and entropy
The differential enthalpy (isosteric heat of sorption) was
determined by applying the Clausius–Clapeyron equation
(Eq. (4)) to the experimental adsorption data (Table 3).
 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493 489

Table 6
Estimated values of coefficients (A, B, C, D, C, K), mean relative error (MRE), standard error of estimate (SEE) and residual sum-of-squares (RSS) of
models for adsorption of oat flakes at various temperatures
Model Parameter 5 C 20 C 40 C 60 C
BET (aw = 0.03–0.45) X0 0.0361 0.0340 0.0376 0.0244
A 11.3 11.0 5.22 10.5
MRE (%) 16.8 7.31 5.67 5.33
SEE 0.012 0.0055 0.0019 0.0017
RSS (·105) 7.77 1.90 0.270 0.160
Ferro-Fontan (aw = 0.03–0.96) A 0.0237 0.0231 0.0351 0.0607
B 1.08 1.08 1.14 1.23
C 1.24 1.21 1.06 0.873
MRE (%) 5.82 6.34 11.1 2.08
SEE 0.0092 0.0091 0.0099 0.0029
RSS (·105) 13.3 13.0 11.6 10.5
GAB (aw = 0.03–0.96) X0 0.0361 0.0336 0.0341 0.0348
C 16.6 15.4 8.98 4.87
K 0.909 0.912 0.889 0.868
MRE (%) 10.5 4.68 5.22 5.72
SEE 0.012 0.0086 0.0069 0.0046
RSS (·105) 15.9 10.4 4.80 2.44
Halsey (aw = 0.03–0.96) A 1.24 1.23 0.891 0.708
B 1.83 1.80 1.89 1.93
MRE (%) 21.7 23.1 35.8 38.0
SEE 0.027 0.025 0.028 0.036
RSS (·105) 67.4 69.6 124 174
Lewicki I (aw = 0.03–0.96) A 0.0667 0.0621 0.0577 0.0523
B 0.538 0.531 0.554 0.561
MRE (%) 9.67 5.61 14.2 17.2
SEE 0.012 0.011 0.014 0.021
RSS (·105) 13.6 13.6 28.3 48.3
Lewicki II (aw = 0.03–0.96) A 0.0952 0.0886 0.0956 0.1044
B 0.392 0.398 0.336 0.281
C 0.934 0.660 0.883 1.34
MRE (%) 10.7 6.42 5.61 15.0
SEE 0.012 0.011 0.011 0.016
RSS (·105) 12.8 11.5 13.4 29.1

As shown in Fig. 3, the energy required for sorption of highly active polar sites to form a surface monolayer,
increased with decreasing equilibrium moisture content. followed by the progressive filling of the less available sites
This reflects the water binding strength; initial occupation (with lower bonding activation energies) (Tsami et al.,
1990). At higher moisture contents (>0.1 kg kg1), the heat
25 of sorption tended to the latent heat of condensation,
Biscuit (Conv-baked) which suggested that the moisture exists in the free form.
Biscuit (Mw-baked) The magnitude of Dhd, however, indicated that the binding
20 Oat flakes energy between water molecules and sorption sites was
Power Law
greater than the energy holding the water molecules in
Δ h d (kJ mol -1)

15 the liquid phase (Masuzawa & Sterling, 1968).

The isosteric heats of sorption of convective-baked and
10 microwave- baked biscuits, at a specific moisture content,
were comparable, with values of 10.8 and 16.1 kJ mol1,
5 respectively, at 0.01 kg kg1 (db). At a higher moisture
content of 0.23 kg kg1 (db), respective steady state values
0
of 0.216 and 0.301 kJ mol1 were observed. Therefore, it
0 0.05 0.1 0.15 0.2 0.25 would appear that the method of baking had a limited
X (k g k g -1, db) effect on the sorption behaviour. Irrespective of the mois-
Fig. 3. Differential enthalpy of adsorption of convective-baked oatmeal ture content, the oat flakes exhibited a higher net isosteric
biscuits, microwave-baked oatmeal biscuits and oat flakes as a function of heat of sorption than that of the oatmeal biscuits, with this
equilibrium moisture content. being particularly evident at moisture contents less than
490 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493

0.05 kg kg1 (db). For example, at 0.025 kg kg1 net isos-
teric heats of 4.90, 5.28 and 12.6 kJ mol1 were observed
for convective-baked biscuit, microwave-baked biscuit
and oat flakes, respectively. The presence of fat and gelati-
nization of starch during the baking process may have a
lowering effect of the binding energy of sorbed water
(Aviara & Ajibola, 2002).
Kim et al. (1998) also observed a decrease in the net isos-
teric heat of sorption for cookies (25–<1 kJ mol1) and
crackers (42–<1 kJ mol1) with increasing moisture con-
tent (0.01–0.20 kg kg1, db). Palou et al. (1997) reported
comparable maximum net isosteric heats of adsorption
for cookies and corn snacks; 6.7–10.1 kJ mol1 and
7.5 kJ mol1 (approx.), in the moisture content range
5–7% (db), respectively. Arogba (2001) reported the net
isosteric heat of sorption for a biscuit containing processed
mango flour to decrease with decreasing moisture content,
with a maximum value of 18.2 ± 1.6 kJ mol1, in the mois-
ture content range 10.2–12.4% (fat-free, dry basis), being
observed. The comparatively higher values were attributed
to less damage to the active sorption sites during process-
ing. Cadden (1988) reported the heats of sorption of oat
bran at the monolayer to be higher than the corresponding
energy values for condensed water.
The variation in isosteric heat with moisture content was
adequately represented by a power law relation (Fig. 3):
Convective-baked biscuit Dhd ¼ 0:054X 1:17 ;
Microwave-baked biscuit Dhd ¼ 0:040X 1:31 ;
Oat flakes Dhd ¼ 0:056X 1:45 ; r2 ¼ 0:980
the oatmeal biscuits, irrespective of moisture content, with
this being particularly evident at moisture contents less
than 0.05 kg kg1 (db). For example, at 0.025 kg kg1 the
differential entropies of convective-baked biscuit, micro-
wave-baked biscuit and oat flakes were 9.98, 10.7 and
26.8 kJ mol1, respectively. Madamba et al. (1996) also
reported a decrease in the entropy of desorption of garlic
with increasing moisture.
3.4. Enthalpy–entropy compensation theory
The differential enthalpy (Dhd) and entropy (DSd), at a
given moisture content, were determined by linear regres-
sion analysis (Eq. (5)). It was assumed that, at a specific
moisture content, Dhd and DSd are invariant with tempera-
ture (Aguerre et al., 1986). Using this data, a plot of Dhd
versus DSd was developed, as shown in Fig. 5. As a linear
relation between Dhd and DSd was exhibited for the oat-
meal biscuits (convective- and microwave-baked biscuit
results considered as a single data set) and oat flakes (coef-
ficients of determination, r2 P 0.996), the compensation
theory was assumed to exist. The isokinetic temperature
(Tb) and free energy at Tb (DG) were determined by linear
regression (Eq. (6)) for all data within a 95% confidence
interval, and the values are detailed in Table 7. The isoki-
netic temperature was observed to vary with material com-
position. The isokinetic temperatures agree well with the
r2 ¼ 0:980 results of Beristain et al. (1996), Ferro-Fontan et al.
r2 ¼ 0:999
25

A power law was also reported to be a good fit for the data

20
for chickpea flour (Durakova & Menkov, 2005).
The differential entropy is plotted as a function of mois-
Δ h d (kJ mol -1)

ture content in Fig. 4. Once again the entropy data dis- 15

played a strong dependence on moisture content. The oat Biscuit (Conv-baked)

flakes exhibited a higher differential entropy than that of 10 Biscuit (Mw-baked)
Oat flakes
Linear (Biscuit)
5
Linear (Oat flakes)
60
Biscuit (Conv-baked) 0
50 Biscuit (Mw-baked) 0 10 20 30 40 50 60

Oat flakes Δ Sd (Jm ol K )

-1 -1
Δ Sd (kJ mol -1 K-1)

40
Fig. 5. Differential enthalpy versus differential entropy relationship for
30 adsorption in convective- and microwave-baked oatmeal biscuits and oat
flakes.
20

10 Table 7
Characteristic parameters for differential enthalpy versus differential
0 entropy relationship
0 0.05 0.1 0.15 0.2 0.25 Tb (K) DG (kJ mol1) r2
-1
X (k g k g , db) Oatmeal biscuit 430.9 ± 1.88 0.280 0.996
(convective- and
Fig. 4. Differential entropy of adsorption of convective-baked oatmeal
microwave-baked)
biscuits, microwave-baked oatmeal biscuits and oat flakes as a function of
Oat flakes 443.4 ± 0.909 0.325 0.997
equilibrium moisture content.
 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493 491

(1982) and Aguerre et al. (1986) who reported isokinetic 0.3

5°C
temperatures for starchy food products of 382.5 K, 327 K
20°C
and 380.5 K, respectively. 0.25
Comparison of the calculated harmonic mean tempera- 40°C

ture (302.8 K) with the Tb values, confirmed the suitability 0.2 60°C
of the isokinetic theory for the sorption phenomena of oat-

π (Jm )
-2
meal biscuits and oat flakes (Krug et al., 1976a, 1976b). If 0.15
Tb > Thm the process is enthalpy driven, while if Tb < Thm,
the process is entropy controlled (Leffler, 1955). As the 0.1

former condition was observed, this suggested that the

0.05
sorption mechanism was enthalpy-driven. Beristain et al.
(1996) and Aguerre et al. (1986) reported the sorption
0
behaviour of starch materials to be enthalpy-controlled. 0 0.2 0.4 0.6 0.8 1
Moreover, only one mechanism was evident in the entire aw
temperature and moisture content range studied. This sug-
Fig. 6. Spreading pressure adsorption isotherms for microwave-baked
gested that the microstructure of the starchy foods was sta- oatmeal biscuit.
ble and did not suffer any changes during moisture sorption
(Gabas et al., 2000). Beristain et al. (1996) also reported
one straight line to represent the data for potato at mois- 0.3
5°C
ture contents above 3.5 g water/100 g dry solid. From a
20°C
thermodynamic viewpoint, the free energy change (DG) 0.25
40°C
can be considered as indicative of the affinity of the sorbent
for water, and further provide a criterion as to whether the 0.2 60°C

moisture sorption behaviour is spontaneous (DG), or

π (Jm )
-2

non-spontaneous (+DG) (Apostolopoulos & Gilbert, 0.15

1990). The positive values of DG (Table 7) suggest that
adsorption in oatmeal biscuits and oat flakes was non- 0.1
spontaneous.
0.05

3.5. Integral enthalpy and entropy

0
0 0.2 0.4 0.6 0.8 1
The spreading pressures (p) for convective- and micro- aw
wave-baked biscuits and oat flakes were calculated using
Fig. 7. Spreading pressure adsorption isotherms for oat flakes.
Eqs. (12), (14) and (16). The values of b and b0 were eval-
uated using non-linear regression analysis Eq. (14) and the
spreading pressures at different temperatures subsequently
60
determined using Eq. (16). The monolayer moisture con- Biscuit (Conv-baked)
tent (X0) in Eq. (14) was determined using the BET equa- 50 Biscuit (Mw-baked)
tion (Tables 4–6). This correlation is mostly applicable in Oat flakes
the monolayer range between 0.05 and 0.4aw, and therefore 40
Δ h in (kJ mol )

provides a good estimation of constants of interest in the

-1

monolayer region (Fasina et al., 1997). The spreading pres- 30

sure isotherms for microwave-baked oatmeal biscuit and
oat flakes are detailed in Figs. 6 and 7, respectively. As 20
shown, the spreading pressure increased with increasing
water activity (irrespective of temperature) and, at a given 10
water activity, decreased with increasing temperature. The
magnitude of the spreading pressure and the trend with 0
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14
respect to water activity and temperature were similar to X (k g k g -1, db)
that reported for starchy materials and maize, rough rice
and wheat (Tolaba et al., 1995, 1997), alfalfa pellets and Fig. 8. Integral enthalpy of adsorption of convective- and microwave-
baked oatmeal biscuits and oat flakes as a function of equilibrium
winged bean, and gari (Fasina et al., 1997, 1999) and cow-
moisture content.
pea (Ajibola et al., 2003).
The net integral enthalpy (Dhin) was then obtained by
applying Eq. (11) to the experimental data at a specific baked oatmeal biscuits and oat flakes is shown in Fig. 8.
spreading pressure. The variation in net integral enthalpy For all materials, a decrease in enthalpy was observed with
with the moisture content for convective- and microwave- increasing moisture content. This thermodynamic
492 W.A.M. McMinn et al. / Journal of Food Engineering 79 (2007) 481–493
X (k gk g -1, db)
0 and Ajibola et al. (2003) for cowpea.
0.00 0.02 0.04 0.06 0.08 0.10 0.12
-20
-40
-60
Δ Sin (J mol K )
-1
-80
-1
-100
-120 Biscuit (Conv-baked)
-140
Biscuit (Mw -baked)
Oat flakes
-160
-180
Fig. 9. Net integral entropy of adsorption of convective- and microwave-
baked oatmeal biscuits and oat flakes as a function of equilibrium
moisture content.
behaviour was indicative of the location of the bound water
and the extent to which the solid-water interaction was
greater than the interaction of the water molecules. At
low moisture contents, the high enthalpy values indicated
the covering of the strongest binding sites and the greatest
water-solid interactions, as water was adsorbed on the
most accessible locations on the exterior surface of the
material. The subsequent decrease in net integral enthalpy
reflected the covering of less favourable locations and the
formation of multiple layers of sorbed water. The magni-
tude of the enthalpy a high moisture contents reflected
the presence of free water (Rizvi & Benado, 1983). A sim-
ilar relationship between net integral enthalpy and mois-
ture content was reported by Rizvi and Benado (1983)
for grain sorghum, Tolaba et al. (1997) for maize, rough
rice and wheat and Ajibola et al. (2003) for cowpea.
Further application of Eq. (17) allowed the net integral
entropy (DSin) to be determined as a function of moisture
content. As shown in Fig. 9, irrespective of material, the
net integral entropy of sorbed moisture increased as mois-
ture content increased (but remained negative), tending
towards that of free water (0 J mol1 K1) as saturation
was approached. During moisture adsorption in foods
there are two opposing entropic contributions; a loss of
entropy from localization of water and an increase in
entropy due to structural transformation arising from sol-
ubilization and swelling (Rizvi & Benado, 1983). The
observed trends in integral entropies can be attributed to
a combination of chemical adsorption, structural modifica-
tion in the foods, the presence of fat and strongly binding
polar groups (Aviara & Ajibola, 2002). The large magni-
tude of DSin at low moisture contents collaborated the
notion that the first few percent of water was tightly bound
(Rizvi & Benado, 1983). The subsequent decrease in mag-
nitude reflected the presence of more freely held water mol-
ecules and the formation of multi-layers. The relation
between net integral entropy and moisture content was
comparable to that observed by Rizvi and Benado (1983)
for grain sorghum, Tolaba et al. (1997) for cereal grains
0.14
4. Conclusions
On the basis of this work the following conclusions can
be drawn.
• Adsorption characteristics of convective-baked and
microwave-baked oatmeal biscuits exhibited Type III
sorption characteristics, and oat flakes show Type II
behaviour.
• Equilibrium moisture content, at a given water activity,
decreased with increasing temperature.
• Experimental adsorption isotherm data for oatmeal bis-
cuits and oat flakes, within the temperature range 5–
60 C and water activity range 0.03–0.96, were best
described by the three-parameter, semi-empirical
Ferro-Fontan model, followed by the kinetic three-
parameter GAB.
• Net isosteric heats of sorption for oatmeal biscuits and
oat flakes, calculated using the Clausius–Clapeyron
equation, showed a power law relation with moisture
content.
• Isosteric heat versus entropy data satisfied the enthalpy–
entropy compensation theory.
• Spreading pressure increased with increasing water
activity, and decreased with increasing temperature.
• Net integral enthalpy decreased with increasing mois-
ture content.
• Net integral entropy increased with increasing moisture
content, but was negative with respect to the entropy of
water.
• Adsorption process was enthalpy-controlled (isokinetic
temperature (Tb) > harmonic mean temperature (Thm))
and non-spontaneous (+DG).
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