Chapter

Moisture Sorption Isotherms and

Isotherm Model Performance
Evaluation for Food and
Agricultural Products
Ndubisi A. Aviara

Abstract

Moisture sorption characteristics of agricultural and food products play impor-

tant roles in such technological processes as drying, handling, packaging, storage,
mixing, freeze-drying and other processes that require the prediction of food sta-
bility, shelf life, glass transition and estimation of drying time and texture and
prevention of deteriorative reactions. They are useful in the computation of ther-
modynamic energies of moisture in the products. An understanding of moisture
sorption phenomena in products, moisture sorption isotherm (MSI) determination
techniques and moisture sorption isotherm model evaluation procedures would be
useful in the development or selection, modeling and controlling as well as optimi-
zation of appropriate processes to make for enhanced efficiency. The phenomena
addressed in this chapter are equilibrium moisture content (EMC)-water activity
(aw) relationships and MSI types, temperature influence on isotherms and occur-
rence of moisture sorption hysteresis. MSI measurement techniques highlighted are
the gravimetric, vapor pressure manometric (VPM), hygrometric and inverse gas
chromatographic and the use of AquaLab equipment. Commonly used moisture
sorption isotherm models (BET, GAB, modified GAB, Hailwood-Horrobin, modi-
fied Hailwood-Horrobin, modified Halsey, modified Henderson, modified Chung-
Pfost and modified Oswin) were selected, and their evaluation procedures using
moisture sorption data were outlined. Static gravimetric technique involving the
use of saturated salt solution appears to be the most widely used and recommended
method of determining the EMC of agricultural and food products. Most of the MSI
models can be fitted to moisture sorption data thorough linearization by logarithmic
transformation, while others can be solved using such expression as second-order
polynomial. Model goodness of fit can be determined using standard (SE) error of
estimate, coefficient of determination (R2), mean relative percentage deviation (P)
and fraction explained variation (FEV). The acceptance of a model depends on the
nature of its residual plots. A model is considered acceptable if the residual plots
show uniform scatter around the horizontal value of zero showing no systemic
tendency towards a clear pattern. A model is better than another model if it has
lower SE, lower P, higher R2 and higher FEV. Although it appears as if a generalized
MSI model is yet to exist, it is recommended that the Ngoddy-Bakker-Arkema
(NBA) model should be given thorough going and extensive testing on the MSI of
different categories of food as it could prove true to its generalized model posture
due to the fundamental nature of its derivation.

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Keywords: adsorption, desorption, equilibrium moisture isotherm,

moisture sorption isotherm models, moisture sorption isotherm hysteresis

1. Introduction

A fundamental characteristic of biological materials, which influence virtually

every aspect of handling, storage, manufacturing and consumption of food prod-
ucts [1], including every aspect of the dehydration process and storage stability of
the dried products [2], is their basic hygroscopicity. By this, it is meant that when
biological materials are exposed to water vapor of a definite pressure, sorption of
the water vapor by the product will occur. This chapter discusses the phenomena at
play, their technological applications, factors that influence the characteristics,
measurement techniques, models that are commonly used to predict them and
models’ predictive performance evaluation procedures.

2. Sorption phenomena in biological materials

Biological materials at constant moisture content and temperature display

characteristic vapor pressure and would tend to approach equilibrium with the
temperature and vapor pressure of the surrounding gaseous atmosphere. To attain
this equilibrium, the material either gains moisture from the environment or loses
moisture to the environment depending on whether the vapor pressure of the
surrounding is higher or lower than its vapor pressure [3]. The former process is
called adsorption and the latter desorption. If the conditions of the surrounding are
not changed for a sufficiently long period of time (theoretically for infinitely long
time), the temperature at which the vapor pressure of the material and its sur-
rounding is the same is established. At equilibrium, no further change in moisture
content of the product occurs, and the moisture content of the material at that point
is called equilibrium moisture content (EMC), while the relative humidity is known
as equilibrium relative humidity. Water activity (aw) is another term used to denote
the ERH in decimal unit. The definition of water activity is based on the concept of
thermodynamics and refers to the availability of moisture in biomaterials for phys-
ical, chemical and biological changes [4, 5], and it is a property of the material.

2.1 Moisture sorption isotherm

When equilibrium is attained, the moisture content is termed adsorption EMC

or desorption EMC depending on whether the equilibrium was reached thorough
the adsorption or desorption process. The EMC obtained thorough the desorption
process usually lies above the one obtained thorough the adsorption process in the
isotherm plots and leads to formation of the hysteresis loop (MSI) when graphically
expressed [6]. Brunauer et al. [7] classified moisture sorption isotherms into five
general types (Figure 1). The type I is the Langmuir, while the type II is the sigmoid
or S-shaped isotherm. The type III is known as the Flory-Huggins isotherm and is
usually influence by the presence of solvent or plasticizer such as glycerol above the
glass transition temperature, and type IV is due to the presence of swellable hydro-
philic solid that influence the moisture sorption process until a maximum site
hydration is reached, while the type V is the BET multilayer adsorption isotherm.
Moisture sorption isotherms of most foods are nonlinear, generally sigmoidal in
shape, and of the type II classification [1, 6].

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Figure 1.
Types of moisture sorption isotherm for food. Source: Rizvi [6].

2.2 Applications of moisture sorption isotherm

In drying operation, it is the removal of water which is important, and hence the
desorption equilibrium moisture relationship is required to determine the lowest
attainable moisture content at the process temperature and relative humidity [8].
Labuza and Hyman [9] applied the changing of water activity of food ingredients
and effective diffusivity to control moisture migration in multidomain foods, when
temperature changes occur. The moisture sorption isotherms of food and agricul-
tural products are therefore of special interest in the design of storage and preser-
vation processes such as packaging, drying, mixing, freeze-drying and other
processes that require the prediction of food stability, shelf life and glass transition
and estimation of drying time [10], texture and deteriorative reactions in agricul-
tural and food products. The precise determination of equilibrium moisture con-
tents of dehydrated foods provides valuable information for the accurate
computation of thermodynamic energies from existing theories [1].

2.3 Factors influencing moisture sorption characteristics

The adsorption and desorption characteristics of agricultural and food products

are affected by numerous factors [11], and these include composition, origin,
postharvest history and methodology of measurement. In general, polymers sorb
more water than sugars and other soluble components at lower water activities [12].
However, the soluble components sorb more water above certain water activity.
The MSIs for the same material from different sources usually differ and are com-
parable only with qualification. The type of treatments given to the product may
change the polar and other groups that bind water, along with changes in the
capillary and other configurations of the food structure [13]. Greig [14] showed that
the denaturation of native cottage cheese whey had no effect on the sorption
isotherm at low water activities but significantly increased sorption at high water
activities. Yu et al. [15] studied the moisture sorption characteristics of freeze-dried,
osmo-dried, osmo-freeze-dried and osmo-air-dried cherries and blue berries and
found that the EMC of osmo-air-dried cherries was generally higher than that of the
osmo-freeze-dried and freeze-dried cherries at the lower temperature of 10°C, but
at higher temperatures of 25 and 40°C, the difference was not significant. Similar
result was reported for blue berries. San Jose et al. [16] showed that the drying

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method (freeze- and spray-drying) of lactose-hydrolyzed milk did not affect the
adsorption isotherms but had profound effect on the desorption isotherms. Tsami
et al. [17] investigated the effect of drying method on the sorption characteristics of
model fruit powder and reported that freeze-dried gel adsorbed more vapor at 25°C
than microwave-dried gel, which had a higher sorption capacity than vacuum- and
conventionally dried product. Mittal and Usborne [18] determined the moisture
sorption isotherms of meat emulsions and showed that their EMC was affected by
the fat-protein ratio. Mazza [19] reported that at 40°C and in the monolayer region
of the isotherm, the EMC of precooked dehydrated pea was higher than that of raw
pea but that at water activities above 0.5, the sorption capacity of precooked pea
was lower than that of raw pea. Aviara [20] noted that chemical modification
(cross-linking and hydroxypropylation) of cassava, maize and sorghum starches
had profound influence on their moisture adsorption and desorption characteristics.
While cross-linking lowered the sorptive capacity of the starches, hydroxypro-
pylation enhanced the ability of the starches to sorb or desorb moisture. Palou et al.
[21] studied the moisture sorption characteristics of three cookies and two corn
snacks whose main composition difference was in fat and total carbohydrate and
found the EMC difference at 5% level of significance. Igbeka et al. [22], Ajibola and
Adams [23] and Gevaudan et al. [24] studied the moisture sorption characteristics
of cassava and presented data that were fitted by different moisture sorption
isotherm models. The variance in EMC may be due to the source of the material,
product’s postharvest and sorption history and varietal differences, methodology of
measurement, temperature range and limitations imposed by model selection.

3. Moisture sorption isotherm measurement techniques

Several methods of determining the moisture sorption isotherm of agricultural

and food products have been employed by investigators [25]. Gal [26–28] carried
out a thorough review of the methods and pointed out that the basic techniques
include the gravimetric, hygrometric, vapor pressure manometric and inverse gas
chromatography and special method involving the use of AquaLab.

3.1 Gravimetric method

There are two common gravimetric methods of determining the EMC of agri-
cultural and food products at different temperatures and water activities. One of
these methods is the static gravimetric method which involves the placement of the
product in an atmosphere with which it then comes into equilibrium (weight loss or
gain stops) without mechanical agitation of the air or product. For this method,
several weeks may be required for the product to come into equilibrium, and
because of the long period of time, mold usually develops on high and intermediate
moisture foods at water activities above 0.8. For data obtained at water activities
above 0.8 to be reliable, mold growth must be prevented during equilibration. At
the point of equilibration, the moisture content is then determined as the EMC. The
second one is the dynamic method in which the atmosphere surrounding the prod-
uct or the product itself is mechanically moved. The dynamic method is quicker but
presents the problem of design and instrumentation. The static method has been
used extensively and reported to be preferable for obtaining complete sorption
isotherms [27]. It has also been recommended as the standard method of determin-
ing the moisture sorption isotherms of agricultural and food products [29]. It
involves the placement of small sample (10–25 g) of agricultural and food material
in vacuum desiccators containing different concentrations of sulfuric acid

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(Figure 2a) to maintain the relative humidity (water activity) of the surrounding
air at different values from 0 to 100% (0.00–1.00) or saturated solution
(Figure 2b) of different salts to achieve different values of relative humidity at a
specified temperature. Usually a thermostatically controlled water bath or oven

Figure 2.
(a) Desiccator containing concentrated sulfuric acid: (1) locking clamp, (2) lid, (3) rubber seal ring,
(4) desiccator barrel, (5) sample basket or can, (6) sample basket mounting stand and (7) concentrated
sulfuric acid. Source: Spiess and Wolf [29]. (b) Desiccator containing saturated salt solution employed by
Kameoka et al. [32] in determining the EMC of brown and rough rice and hull.

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Sorption in 2020s

(Figure 3) is used to obtain the desired temperature. The water activity of sulfuric
acid at different concentrations and temperatures is presented in Table 1, and that
of saturated solutions of different salts at various temperatures are presented in
Table 2.

Figure 3.
Thermostatically controlled water bath or oven for moisture sorption isotherm determination. Source: Spiess and
Wolf [29].

Percent Density at 25°C Temperature (°C)

H2SO4 (g/cm3)
5 10 20 25 30 40 50

5.00 1.0300 0.9803 0.9804 0.9806 0.9807 0.9808 0.9811 0.9814

10.00 1.0640 0.9554 0.9554 0.9558 0.9562 0.9562 0.9565 0.9570

15.00 1.0994 0.9227 0.9230 0.9237 0.9241 0.9245 0.9253 0.9261

20.00 1.1365 0.8771 0.8779 0.8796 0.8802 0.8814 0.8831 0.8848

25.00 1.1750 0.8165 0.8183 0.8218 0.8218 0.8252 0.8285 0.8317

30.00 1.2150 0.7396 0.7429 0.7491 0.7509 0.7549 0.7604 0.7655

35.00 1.2563 0.6464 0.6514 0.6607 0.6651 0.6693 0.6773 0.6846

40.00 1.2991 0.5417 0.5480 0.5599 0.5656 0.5711 0.5816 0.5914

45.00 1.3437 0.4319 0.4389 0.4524 0.4589 0.4653 0.4775 0.4891

50.00 1.3911 0.3238 0.3307 0.3442 0.3509 0.3574 0.3702 0.3827

55.00 1.4412 0.2255 0.2317 0.2440 0.2502 0.2563 0.2685 0.2807

60.00 1.4940 0.1420 0.1471 0.1573 0.1625 0.1677 0.1781 0.1887

65.00 1.5490 0.0785 0.0821 0.0895 0.0933 0.0972 0.1052 0.1135

70.00 1.6059 0.0355 0.0377 0.0422 0.0445 0.0470 0.0521 0.0575

75.00 1.6644 0.0131 0.0142 0.0165 0.0177 0.0190 0.0218 0.0249

80.00 1.7221 0.0035 0.0039 0.0048 0.0053 0.0059 0.0071 0.0085

Source: Rizvi [6], Bell and Labuza [56].

Table 1.
Water activity of sulfuric acid solution at different concentrations and temperatures.

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Salt Temperature (°C)

20 25 30 35 40 45 50 60 70

Sodium hydroxide 0.09 0.08 0.07 0.07 0.07 0.07 0.07 0.07 0.07

Lithium chloride 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11

Potassium acetate 0.23 0.22 0.22 — — — — — —

Calcium chloride — — — 0.22 0.22 0.22 0.21 0.21 0.20

Magnesium chloride 0.33 0.33 0.32 0.32 0.32 0.32 0.31 0.31 0.30

Potassium carbonate 0.43 0.43 0.43 — — — — — —

Magnesium nitrate 0.54 0.53 0.51 0.499 0.48 0.47 0.45 0.45 0.44

Manganese chloride — — — — 0.51 0.5 0.5 0.5 0.5

Sodium bromide 0.59 0.58 0.56 0.55 — — — — —

Sodium nitrite — — — — 0.61 0.61 0.6 0.6 0.6

Sodium chloride 0.75 0.75 0.75 0.75 0.75 0.74 0.74 0.74 0.75

Potassium chloride 0.85 0.84 0.84 0.83 0.82 0.82 0.81 0.8 0.8

Barium chloride — — — — — 0.89 0.89 0.88 0.88

Potassium nitrate 0.95 0.93 0.92 0.91 0.89 — — — —

Potassium sulfate 0.97 0.97 0.97 0.97 0.96 0.96 0.96 0.95 0.94
Source: Rizvi [6], Bell and Labuza [56].

Table 2.
Water activity of saturated salt solutions at different temperatures.

Acids are not used extensively because of the danger involved in its handling and
the changes that can occur in its composition—it is susceptible to dilution or
increase in concentration with time due to the release or absorption of water by the
product—thereby effecting a change in the air-water activity. Acids also easily
corrode and release fume that can be toxic in the food material. Saturated salts are
safer to use, and constant humidity can be maintained by leaving excess salt in the
solution. That way, the solution is made to remain saturated thoroughout the
duration of the experiment in spite of the release or absorption of water by the
product. The use of saturated salt solution, however, requires many salts in order to
go thorough the relative humidity (water activity) range of 0–100% (0.00–1.00),
whereas only one acid could be used for the same purpose.
The static gravimetric method involving the use of saturated salt solutions was
applied successfully to the determination of MSIs of Jerusalem artichoke [30];
uncooked meat emulsions [18]; ground and short-time roasted coffee [31]; rice
[32]; pigeon pea type-17 [33]; cassava [23]; plantain, winged bean seed and gari
[34–36]; freeze-dried, osmo-freeze-dried and osmo-air-dried cherries and blue
berries [15]; vetch seeds [37]; lupine [38]; high oleic sunflower seeds and kernels
[39]; quinoa grains [40]; soya bean [41]; red chillies [42]; chickpea flour [43]; black
gram nuggets [44]; sorghum malt [45]; IR-8 rice variety [46]; native and chemically
modified starches [20]; and castor seeds [47]. Young [48], Oyelade et al. [49, 50],
Al-Muhtaseb et al. [51], Bello [52] and Afkawa [53] applied the static gravimetric
method involving the use of different concentrations of sulfuric acid in determining
the MSIs of Virginia-type peanuts, maize flour, yam flour, potato, high amylopectin
and high amylose starch powders, groundnut and neem seeds and shea nut and
desert date kernels, respectively. Bosin and Easthouse [54] suggested the dynamic

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gravimetric method, and Igbeka et al. [22], Roman et al. [25] and Rahman and Al-
Belushi [55] utilized it in establishing the MSIs of cassava and potato, apple and
freeze-dried garlic powder, respectively.

3.2 Hygrometric method

Electric hygrometers are widely used for obtaining the MSIs of agricultural and
food products. There are quite a lot of commercially available and specially
designed hygrometers that are in use. The instrument (Figure 4) consists basically
of a sensor, sample chamber and potentiometer. The sensor could use a hygroscopic
chemical such as lithium chloride or an ion-exchange resin such as sulfonated
polysterne; the conductivity of which changes according to the water activity above
the sample. The sensor could be a humidity sensor which is based on capacitance
changes in a thin film capacitor. Electric hygrometers give rapid, relatively precise
results and are easy to operate. The main problems involved with the use of
hygrometers are:

i. Evaluation of the equilibration time between the sample and sensor

ii. Proper temperature control

iii. Need for recalibration for some instrument

Crapiste and Rostein [57], Fasina and Sokhansanj [58], Tsami et al. [17] and
Arslan and Togrul [59] employed the hygrometric method in studying the moisture
sorption behavior of potatoes, alfalfa pellets, model fruit powders and crushed
chillies, respectively.

Figure 4.
Diagram of moisture sorption isotherm apparatus utilizing the hygrometer. Source: Fasina and Sokhansanj [58].

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3.3 Vapor pressure manometric (VPM) method

The vapor pressure manometric method involves bringing air to equilibrium

with the agricultural or food product at a fixed temperature and moisture content
and the relative humidity of the air measured as the equilibrium relative humidity
(ERH). In this method, the vapor pressure exerted by the moisture in the product is
directly measured. As a result, it is taken as one of the best methods of determining
the MSI of food [60]. The equilibrium relative humidity is then obtained from the
ratio of the vapor pressure in the sample to that of pure water at the same temper-
ature. A schematic diagram of the apparatus and simplified diagram of the system
set-up is shown in Figures 5 and 6, respectively. The procedure for determining the
ERH of agricultural and food products using the method is as follows:

i. The prepared sample and VPM system are allowed to reach the desired
temperature.

ii. About 10–50 g of sample is put in the sample flask, and an equal amount of
desiccant (CaSO4, CaCl2) is placed in the desiccant flask and sealed on to the
apparatus using high vacuum grease.

iii. Keeping the sample flask isolated, the system is evacuated to less than 200
μmHg (Rizvi, 1986). The cold strap should be filled with nitrogen prior to
evacuation of the system to trap any moisture reaching the vacuum pump.

iv. The space in the sample flask is then connected to the evacuated air space by
opening the stopcock over the sample V4 (Figure 6), and the system is again
evacuated for 1 min.

Figure 5.
Schematic diagram of vapor pressure manometric apparatus. Source: Rizvi [6].

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Sorption in 2020s

Figure 6.
Schematic diagram of vapor pressure manometric system set-up. Source: Ajibola et al. [65].

v. The stopcock across the manometer V5 is closed causing the oil in the
micromanometer to respond to the vapor pressure exerted by the
sample. When the oil level reaches a steady value, the difference is
recorded as H1.

vi. The stopcock over the sample is then closed, and the desiccant stopcock is
opened to connect the system with the desiccant, causing a change in the
height of the manometric oil. After the oil reaches a constant height, the
micromanometer reading is recorded as H2.

vii. The sample is removed from the system, and the moisture content is
determined using a standard method.

[Link] the data obtained, the equilibrium relative humidity is calculated using
Eq. (1):


ðH1  H2 Þ Ts
To
ERH ¼ (1)
Ps

where ERH is the equilibrium relative humidity (%), H1 is the micromanometer

reading with sample flask connected to the system (mm of manometric oil), H2 is
the micromanometer reading with desiccant flask connected to the system (mm of
manometric oil), Ts is the temperature of the environment surrounding the water
bath taken as the temperature of sample (K), To is the temperature of the environ-
ment surrounding the micromanometer (K) and Ps is the saturated vapor pressure
at sample temperature (mm of manometric oil).
The VPM method is rapid and precise but requires the use of vacuum pump, an
accurate manometer and closed glass tube system. Proper temperature control is
critical to this method, and volatile constituents other than water may contribute to
the pressure exerted by the food.
The VPM method has been used to obtain the MSI of cereal grains and rape [61],
dry milk [62], sesame seed [63], cowpea [64] and palm kernels [65].

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3.4 Inverse gas chromatography

The inverse gas chromatography (IGC) is a rapid and effective system for
studying the thermodynamic properties of a solid taken as the stationary phase in
relation to a mobile gas phase containing selected solutes such as water. It is partic-
ularly suitable for the study of the lower region of water activity and for products
with very low equilibrium moisture contents [66, 67]. With IGC the sorbed solute is
injected into the carrier gas stream, and its linear transport is retarded owing to
interaction with the product under study, which constitutes the stationary phase.
Moisture sorption isotherms are then determined using the chromatographic data
obtained and the following equations, which relate chromatograph operating
parameters and peak data to the sorption isotherm:

ma Iads
a¼ (2)
mIpic

and

ma hRT
p¼ (3)
Ipic W

where a is the uptake of sorbed water (g/g stationary phase), ma is the mass of
water injected (g), m is the mass of stationary phase (g) and Iads/Ipic is the ratio of
the areas (A + B)/B calculated from the chromatogram (Figure 7), p is the partial
pressure (atm), h is the peak height (detector units), R is the gas constant
(82.0567 cm3 atm mole1 Kl), T is the absolute temperature (K), W is the flow rate
of carrier gas (cm3/min) and Ipic is the area B in Figure 7.
It has been used successfully to determine the MSIs of homogeneous solid food
ingredients like sucrose, glucose and starch [68] and complex heterogeneous foods
like bakery products [69], wheat flour [66] and wheat and soy flour [70].

Figure 7.
Typical gas chromatogram obtained by IGC: 1 = point of injection; 2 = point of emergence of unadsorbed peak
(air); 3 = point of emergence of probe peak (water), Ipic = area B; and Iads = area A + B. Source: Manuel Sa
and Sereno [67].

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Figure 8.
4TE model AquaLab moisture content—water activity measuring instrument. Source: METER Group,
Inc. [71].

3.5 AquaLab instrument

AquaLab is the fastest, most accurate and most reliable instrument available for
measuring water activity, giving readings in 5 min or less [71]. It is easy to use and
provides accurate and timely results. Its readings are reliable, providing 0.003 aw
accuracy. The instrument is easy to clean and checking calibration is simple. The
photograph of 4TE model of the equipment is shown in Figure 8.

4. Influence of temperature on moisture sorption isotherms

Temperature affects the mobility of water molecules and the dynamic equilib-
rium between the vapor and the adsorbed gases [13]. If water activity is kept
constant, an increase in temperature causes a decrease in the amount of sorbed
water [20] (Figure 9). This indicates that the food becomes less hygroscopic.
Iglesias and Chirife [72] pointed out that increase of temperature represents a
condition unfavorable to water sorption.
An exception to this rule is shown by certain sugars and other low molecular
weight food constituents, which become more hygroscopic at higher temperature
because they dissolve in water. Temperature shifts can have an important practical
effect on the chemical and microbiological reactivity related to quality deterioration
of a food in a closed container [73]. An increase of temperature at constant moisture
content causes increase in water activity (Figure 10). This increases the rate of
reactions and leads to deterioration [74–76]. Weisser [31] studied the effect of
temperature on the sorption isotherms of roasted coffee and reported that the
product showed consistent separation of the isotherms at different temperatures.
However, not all foods exhibit such consistency. In the work reported by Saravacos
et al. [12], crossing over occurred at high water activity (aw = 0.78) in the 20 and
30°C adsorption isotherms of sultana raisins and 5, 20 and 45°C adsorption and
desorption isotherms of Chilean papaya shown in Figure 11 [77]. Such crossing over
has earlier been observed by Saravacos and Stinchfield [78] on model systems of
starch-glucose, Audu et al. [79] on sugars, Weisser et al. [80] on sugar and alcohols

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Figure 9.
Adsorption EMC of hydroxypropylated cassava starch showing variation of MSI with temperature. Source:
Aviara [20].

Figure 10.
Changes in water activity at constant moisture content and in moisture content at constant water activity with
changes in temperature. Source: Rizvi [6].

and Silverman et al. [81] on 20 and 37°C isotherms of precooked bacon. These
substances contain large amounts of low molecular weight constituents in a mixture
of high molecular weight biopolymers. At lower water activity values, the sorption
of water is due mainly to the biopolymers, and an increase of temperature has the
normal effect of lowering the isotherms [13]. As water activity is raised beyond the
intermediate region, moisture begins to be sorbed primarily by the sugars and other
low molecular constituents leading to the swinging up of the isotherm. Dissolution,
which is favored by higher temperature, offsets the opposite effect of temperature
on higher molecular weight constituents. The net result is an increase of moisture
content (crossing over) of the isotherms. This has bearing on the sign and magni-
tude of the binding energy [13]. The binding energy of sultana raisin decreased as
the temperature increased from 22 to 32°C in the low moisture region [12], but the
effect of temperature showed a crossing over of the lines at higher moisture

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Figure 11.
Moisture desorption isotherms of Chilean papaya showing isotherm crossing at higher water activities with
increase in temperature. Source: Vega-Galvez et al. [84].

contents due to the endothermic dissolution of fruit sugars. Iglesias and Chirife [82]
studied the equilibrium moisture contents of air-dried beef and found that the
higher the drying temperature, the lower the sorption capacity of the dried beef.
Similar results were reported for cookies and corn snacks [21] and apples [25].
Temperature changes also have effects on the water activity of saturated salt solu-
tions, which are used in the determination of sorption isotherms. Labuza et al. [83]
used experimental data and thermodynamic analysis to demonstrate that water
activity of saturated salt solutions should decrease with increase in temperature.

5. Moisture sorption hysteresis

A product which attains its moisture equilibrium with the surrounding by losing
moisture at a given temperature is said to have reached the desorption EMC. When
the relatively dry material absorbs moisture from a high humidity environment at
the same temperature, it will eventually reach the adsorption EMC. The isotherm
plots may indicate a significant difference at certain water activities and tempera-
tures between desorption and adsorption EMC values, with the desorption values
being higher than the adsorption counterpart. This difference is called moisture
sorption hysteresis [13, 45]. A typical hysteresis loop presented in Figure 12 could
occur within the region of monolayer moisture but could begin at a higher water
activity and extend down to zero water activity, depending on its class according to
Kapsalis [13] classification.
Moisture sorption hysteresis has important theoretical and practical implications
in foods. These include the general aspects of the irreversibility of moisture sorption
process and the question of validity of thermodynamic parameters derived from a
particular arm of the isotherm. Moisture sorption hysteresis has effect on chemical
and microbiological deterioration of low and intermediate moisture foods.

5.1 Hysteresis classification

The hysteresis phenomenon in agricultural and food products varies in magni-

tude, shape and extent, depending on the type of food and temperature [13].
Hysteresis size or magnitude is depicted by the area enclosed by the loop, while the
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Moisture Sorption Isotherms and Isotherm Model Performance Evaluation for Food…
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Figure 12.
Moisture sorption hysteresis loop. Source: Kapsalis [13].

span or extent is denoted by the water activity range covered. Kapsalis [13] grouped
moisture sorption hysteresis into three general types as follows:
Type I hysteresis: This type of hysteresis is normally pronounced mainly in the
lower moisture content region, below the first inflection point of the isotherm.
Although the total hysteresis may be large, no occurrence is normally observed
above the 0.65 water activity or in the intermediate moisture range. The type I
hysteresis is normally exhibited by high-sugar and high-pectin foods, exemplified
by air-dried apple.
Type II: In this type, moderate hysteresis begins at high water activity, in the
capillary condensation region, and extends over the rest of the isotherm to zero
water activity. In both desorption and adsorption arms, the isotherm’s sigmoidal
shape is retained. This type of hysteresis is normally exhibited by high-protein
foods exemplified by freeze-dried pork.
Type III: In this type, large hysteresis loop occurs with a maximum at about 0.70
water activity, which is within the capillary condensation region. This type of
hysteresis normally occurs in starchy foods such as freeze-dried rice.

5.2 Effect of temperature on hysteresis

Increasing temperature decreases the total hysteresis and limits the span of the
loop along the isotherm [84]. Iglesias and Chirife [85] studied the effect of temper-
ature on the magnitude of moisture sorption hysteresis of foods and reported that
increasing temperature decreased or eliminated hysteresis for some foods, while for
others, the total hysteresis size remained constant, or even increased. In the case
where the hysteresis loop decreased, it did so more appreciably at high tempera-
tures. The effect of temperature was found to be more pronounced on the desorp-
tion isotherms than the adsorption isotherms.

5.3 Theories of moisture sorption hysteresis

Several theories have been proposed to explain hysteresis phenomena in agri-

cultural and food products. The most prominent of the theories are the ink bottle
15
Sorption in 2020s

theory, the incomplete wetting theory, the open-pore theory, the shrinkage theory
and the capillary condensation-swelling fatigue theory.
Ink bottle theory: This theory assumes that an agricultural and food product is a
porous body having capillaries consisting of narrow, small-diameter necks with
large bodies resembling ink bottles (Figure 13). It explains hysteresis on the basis of
difference in the radii of the porous sorbent. During desorption, the small radii of
necks control the emptying of the capillaries and result in a lowering of the relative
humidity above the product; whereas during adsorption, the large area for the
bodies needs to be filled, thus requiring higher relative humidity. The explanation
can be better understood using the Kelvin equation which states that
 
P 2σVcosθ
Ln ¼ (4)
Po RTrm

where P is the vapor pressure of liquid over the curved meniscus (Pa), Po is the
saturation vapor pressure (Pa) at temperature T (K), σ is the surface tension (N/m),
θ is the angle of contact (in complete wetting, θ is 0 and cosθ = 1), V is the molar
volume of liquid (m3/mol) and rm is the mean radius of curvature of meniscus.
For desorption, by substituting r1 in Figure 13 for rm in Eq. (4) with cosθ = 1
(complete wetting), Eq. (4) becomes transformed into Eq. (5):
 
2σV
Pd ¼ Po exp (5)
RTr1

In adsorption with condensation first taking place in the large diameter cavity,
Eq. (4) becomes
 
2σV
Pa ¼ Po exp (6)
RTr2

From the above, it follows that for a given amount of water sorbed, the pressure
will be higher during adsorption than during desorption.
Incomplete wetting theory: This theory is also dependent on capillary condensation
based on Eq. (4), but it notes that due to the presence of impurities, the contact

Figure 13.
Ink bottle neck theory of moisture sorption hysteresis (left, schematic representation and, right, actual pore).
Source: Kapsalis [13].

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angle of the receding film upon desorption is smaller than that of the advancing film
upon adsorption. Therefore, condensation along the adsorption branch of the iso-
therm will be at a higher vapor pressure resulting in open hysteresis as illustrated in
Figure 14. However, in foods the most common type of hysteresis is the closed-end,
retraceable loop showing that this theory is limited in its application to foods.
Open-pore theory: this theory extends the ink bottle theory by including consid-
erations of multilayer adsorption. It is based on the difference in vapor pressure
between adsorption Pa and desorption Pd as affected by the shape of the meniscus.
During adsorption, the meniscus is considered cylindrical and the Cohan equation
(not presented here) applies, whereas during desorption, the shape is considered to

Figure 14.
Incomplete wetting theory of hysteresis (A) contact angle and (B) open hysteresis. Source: Kapsalis [13].

Figure 15.
Open-pore theory of hysteresis. Source: Kapsalis [13].

17
Sorption in 2020s

be hemispherical in which the Kelvin equation is applied. The open-pore theory is

illustrated in Figure 15.
Shrinkage theory: This states that while agricultural and food product is drying
out, the force of attraction causes water-holding spaces to shrink (molecular
shrinkage). This permanent shrinkage reduces the water-binding polar sites and
water-holding capacity of the material; hence less amount of water is absorbed
during the adsorption process.
Capillary condensation and swelling fatigue theory: In this theory proposed by
Ngoddy-Bakker-Arkema [86], the sorption hysteresis is considered linked with
condensation and evaporation in irregular voids (capillary condensation) and
influence of adsorbed water molecules on such physical properties of agricultural
and food products as strength, elasticity, rigidity, swelling and evolution of heat
(swelling fatigue). The above combination was simulated by adopting the Cohan
theory of capillary condensation with modifications and combining it with the ink
bottle theory in the first approximation. The theory presented expressions for
calculating the desorption isotherms of biomaterials from corresponding adsorption
isotherm using bulk moduli determined as a function of moisture content.

6. Moisture sorption isotherm models

Equations for fitting the moisture sorption isotherms are of special importance
in many aspects of crop and food preservation by drying. These include the predic-
tion of the drying times, shelf life of the dried product in a packaging material and
the equilibrium conditions after mixing products with varying water activities [87].
Others are the analytical determination of control for undesirable chemical and
enzymatic reactions [88] and control of moisture migration in multidomain foods
[9]. Moisture sorption isotherm models, therefore, not only constitute an essential
part of the overall theory of drying but also provide information directly useful in
the accurate and optimum design of drying equipment [1]. They are needed in the
evaluation of the thermodynamic functions related to moisture sorption in biologi-
cal materials [89].
Several theoretical, semi-theoretical and empirical models have been proposed
and used by investigators to fit the equilibrium moisture content data of food and
agricultural products. Chirife and Iglesias [87] reviewed part of the isotherm equa-
tions and presented a discussion of 23 common models, while Van den Berg and
Bruin [5] presented a more comprehensive list. Ngoddy-Bakker-Arkema [1] devel-
oped a generalized moisture sorption isotherm model for biological materials based
primarily on the BET and capillary condensation theories and indirectly on Polanyi’s
potential theory. This model appears to possess very high versatility but needs to be
modified to reduce the number of parameters and incorporate the temperature
term. A thorough going and extensive testing of the model on various categories of
food is also necessary to confirm its versatility and prove the generalized posture.
Ferro Fontan et al. [2] and Chirife et al. [90] presented a new model, which Iglesias
and Chirife [91] compared with the GAB model and reported to be an alternative.
Chen [92] derived a new moisture sorption isotherm model from a reaction engi-
neering approach. The Brunauer-Emmett-Teller (BET) [87] and Guggenheim-
Anderson-de Boer (GAB) [56, 91, 93] models have been used for estimating the
monolayer moisture content of agricultural and food products. Boquet et al. [94]
noted that the Hailwood and Horrobin model has a remarkably good ability to fit
the experimental data for most food types. A test of the model on moisture sorption
data of native cassava and sorghum starches [95] showed that it has good predictive

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performance with R2 ranging from 0.92 to 0.99. It, however, lacked the temperature
term and was modified to incorporate the term. Other commonly used models
include modified Henderson, modified Chung-Pfost, modified Halsey and modified
Oswin and the GAB. The modified Henderson [96] and modified Chung-Pfost [97]
models have been adopted as the standard equations by the American Society of
Agricultural and Biological Engineers (ASABE) for describing the EMC-aw data for
cereals and oil seeds [98]. The modified Halsey [85] has been reported as the best
model for predicting the EMC-aw relationships of several tropical crops [99] and
alongside with the modified Oswin [100] has been shown to describe the EMC-aw
data of many seed satisfactorily [101, 102]. The Guggenheim-Anderson-de Boer
(GAB) model has been recognized as the most satisfactory theoretical isotherm
Equation [103–106] and has been recommended as the standard model for use in
food laboratories in Europe [105] (1985) and the USA [107]. The GAB does not
incorporate a temperature term; therefore, the determination of the effect of tem-
perature on isotherms using the model usually involves the evaluation of up to six
constants. Jayas and Mazza [108], however, developed a modified form of the GAB,
which incorporates the temperature term. The MSI models considered in this study
were selected from the above list and presented as follows:

1. Brunauer-Emmett-Teller (BET) model

Mm Caw
M¼ (7)
ð1  aw Þ½1 þ ðC  1Þaw 

2. Guggenheim-Anderson-de Boer (GAB) model

CKMm aw
M¼ (8)
ð1  Kaw Þ½1  Kaw þ CKaw 

3. Modified GAB model

 
AB CT aw
M¼  (9)
ð1  Baw Þ 1  Baw þ CT Baw

4. Hailwood-Horrobin model
 1
A
M¼ þ B  Caw (10)
aw

5. Modified Hailwood-Horrobin model

   1
A C
M¼ T þ B  n aw (11)
aw T

6. Modified Chung-Pfost model

1 ðT þ BÞ
M¼ Ln  Lnaw (12)
C A

7. Modified Halsey model

1=C
Lnaw
M¼ (13)
exp ðA þ BT Þ

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Sorption in 2020s

8. Modified Henderson model

1=C
Lnð1  aw Þ
M¼ (14)
AðT þ BÞ

9. Modified Oswin model

1=C
aw
M ¼ ðA þ BT Þ (15)
1  aw

10. Ngoddy-Bakker-Arkema model

8 200 11=2 1η
>
ρε < 6B σV
C
1:75 A
M¼ 3:2η 4@@
 þ
A
η >
: P
Ln PþPm
o þP m P
Rg TLn PþPmo þP m

00 11=2 1η 3 9 (16)
>
=
B@
1:75 A σV C 7
@ þ
A 5
Ln PoPþPm Rg TLn PoPþPm >
;
m m

where M is the moisture content, (db); Mm is monolayer moisture content, (db);

aw is water activity; T is absolute temperature, (K); A, B, C and k are constants;
η is primary characteristic parameter of pore structure; ε is secondary characteristic
parameter of pore structure; σ is surface tension of sorbate in bulk liquid form,
(N/m); Rg is universal gas constant; V is molal volume of sorbate in its bulk liquid
condition, (m3/mol); Pm is vapor pressure corresponding to monolayer, (N/m2);
Po is saturated vapor pressure, (N/m2); and P is vapor pressure at the condition
under which the study is carried out, (N/m2).

7. Isotherm model predictive performance evaluation

Sun and Byrne [109], Sun [110] and Sun [111] evaluated the predictive perfor-
mance of the moisture sorption isotherm models that have been reported for fitting
the EMC and ERH data of rapeseed, rice, other grains and oilseeds and selected the
models that gave the best fits.
Coefficient of terms in the moisture sorption isotherm equations is usually
determined using nonlinear regression procedure, and the predictive performance
of an equation on sorption data is evaluated using such goodness of fit parameters as
standard error of estimate (estimate of the residual mean square), residual sum of
square, coefficient of determination, mean relative percent error, fraction explained
variation and residual plots. Several investigators used these parameters to evaluate
the fitting ability of EMC-aw equations. For instance, Ajibola [35–37], Ajibola and
Adams [34], Ajibola [112], Gevaudan et al. [24], Talib et al. [8], Pezzutti and
Crapiste [113], Tsami et al. [17] and Ajibola et al. [64] used the standard error of
estimate, and Young [48] and Jayas et al. [114] used the residual sum of squares to
compare the fitting ability of different models. Boquet et al. [94], Chirife et al. [90],
Weisser [31], Saravacos et al. [12], Pollio et al. [115], Iglesias and Chirife [91] and
Khalloufi et al. [10] used the mean relative percent deviation (MRE), while Shep-
herd and Bhardwaj [33], Demertzis et al. [116], Diamante and Munro [117] and
Sopade et al. [118] employed coefficient of determination in evaluating the fitting
ability of several models. Pappas and Rao [119] used the fraction explained

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variation, Chen [92] used both coefficient of determination and mean relative
percent error and Sun [110] and Sun [111] employed the residual sum of squares,
standard error of estimate and mean relative percent error in comparing moisture
sorption isotherm models for food. Other combinations of parameters that have
been used include standard error of estimate and mean relative percent error [120],
coefficient of determination and residual sum of squares [18] and standard error
of estimate, mean relative percent deviation and residual plots [15, 41, 65, 101, 102].
A model is considered acceptable for predictive purpose, if the residuals are
uniformly scattered around the horizontal value of zero showing no systematic
tendency towards a clear pattern [41, 45, 64, 65]. A model is considered better
than another if it has lower standard error of estimate and mean relative
percent deviation and higher fraction explained variation and coefficient of
determination.
Menkov [37] reported that of five moisture sorption isotherm models fitted to
the experimental data on the EMC of vetch seeds, the modified Oswin model
proved the best for describing the adsorption and desorption branches. Aviara et al.
[41] and Oyelade [121] reported that the modified Oswin model gave the best fit to
the EMC of soya bean and lafun, respectively. Santalla and Mascheroni [39] in a
similar study on the EMC of sunflower seeds and kernels reported that the GAB
model gave the best fit to the experimental data. Other crops whose moisture
sorption isotherms have recently been studied include quinoa grains [40], crushed
chillies [59], amaranth grains [122] and black gram nuggets [44].

7.1 Model parameter evaluation procedures

The procedure followed in evaluating a moisture sorption isotherm model

depends on the nature of the model. For the selected models (Eqs. (7)–(16)), the
procedures are as follows:

a. BET model: the BET model (Eq. (7)) can be linearized thorough algebraic
manipulations to yield Eq. (17):
 
aw 1 C1
¼ þ aw (17)
Mð1  aw Þ Mm C Mm C
aw
A plot of Mð1a wÞ
against aw within the water activity range of 0.01–0.5 at each


C1
temperature yields a straight line with the slope as M m C and intercept on the y-
axis as M1m C, and from these, the values of Mm and C can be obtained and used as the
starting values in nonlinear regression. The nonlinear regression analysis procedure
minimizes the sum of deviation in the evaluation of a model using a series of
iterative steps. The procedure could require that initial parameter estimates be
chosen close to the true values.

b. GAB model: the GAB model (Eq. (8)) can be transformed to a quadratic form
by algebraic manipulation to yield Eq. (18):
aw
¼ Aaw 2 þ Baw þ C (18)
M

Eq. (18) can be solved by plotting aMw against aw at each temperature and fitting a
polynomial of the second order to the plots. This will yield the following functions
from Eq. (8):

21
Sorption in 2020s

   
k 1 1 2 1
A¼  1 ,B ¼ 1 ,C ¼ (19)
Mm C Mm C Mm Ck

The values of Mm, C and k obtained at each temperature are then used as the
initial values of the parameters in the nonlinear regression procedure of Eq. (8) to
evaluate the model.

c. Modified GAB model: the modified GAB model (Eq. (9)) like the original
GAB model can be transformed to a quadratic form by algebraic manipulation
to yield Eq. (20):
aw
¼ Xaw 2 þ Yaw þ Z (20)
M

Plotting aMw against aw and fitting a polynomial of the second order to the plot
yield the following functions from Eq. (9):
   
B T 1 2T 1
X¼  1 ,Y ¼ 1 ,Z ¼ (21)
A C A C ABC

The average values of A, B and C are obtained and used as initial parameter
estimates in the nonlinear regression analysis to evaluate the model.

d. Hailwood-Horrobin model: The Hailwood-Horrobin model (Eq. (10)) is

mathematically similar to the GAB and can after algebraic manipulations be
represented in the form
aw
¼ Caw 2 þ Baw þ A (22)
M

Plotting aMw against aw and fitting a polynomial of the second order to the plot at
each temperature yield the values of C, B and A for use as initial parameter esti-
mates in the nonlinear regression procedure for the model evaluation.

e. Modified Hailwood-Horrobin model: this model (Eq. 11) also has

mathematical similarity with the GAB. It can be transformed algebraically to
yield Eq. (23):
aw
¼ λaw 2 þ μaw þ φ (23)
M

Plotting aMw against aw and fitting a polynomial of the second order to the plot
yield the following functions from Eq. (11):

C
λ¼ , μ ¼ BT and φ ¼ TA (24)
Tn

The average values of A, B and C are obtained and used as initial parameter
estimates in the nonlinear regression analysis to evaluate the model.

f. Modified Chung-Pfost model: the modified Chung-Pfost model (Eq. (12)) is

transformed by algebraic manipulations to yield Eq. (25):
 
A
aw ¼ exp exp ðCMÞ (25)
ðT þ BÞ

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Linearizing Eq. (25) by logarithmic transformation is carried out as follows:

A
Lnðaw Þ ¼ exp ðCMÞ (26)
ðT þ B Þ
A
Lnðaw Þ ¼ exp ðCMÞ (27)
ðT þ BÞ
A
Ln½Lnðaw Þ ¼ Ln  CM (28)
ðT þ BÞ

A plot of Ln½Lnðaw Þ against M at each temperature

h i yields a straight line with
A
slope as -C and intercept on the y-axis as Ln ðTþBÞ .
With the expression for the slope, further algebraic manipulation is carried out
as follows in order to solve for the temperature-related parameters of the model:

A A
exp ðbÞ ¼ , implying that T þ B ¼ ¼ AexpðbÞ (29)
ðT þ BÞ exp ðbÞ

From the above, T ¼ AexpðbÞ  B.

A plot of T against exp ðbÞ yields a straight line with A as slope and intercept
on the y-axis as -B.
In the nonlinear regression procedure, the avC as C and A and B are used as the
initial parameter estimates in the equation.

g. Modified Halsey model: the modified Halsey model (Eq. (13)) can be
transformed by algebraic manipulations to yield Eq. (30):

aw ¼ exp  exp ðA þ BT ÞMC (30)

Linearizing Eq. (30) by logarithmic transformation yields

Lnðaw Þ ¼  exp ðA þ BT ÞMC (31)

Lnðaw Þ ¼ exp ðA þ BT ÞMC (32)

So

Ln½Lnðaw Þ ¼ ðA þ BT Þ  CLnM (33)

A plot of Ln½Lnðaw Þ against LnM at each temperature yields a straight line

with slope as –C and intercept on the y-axis as A + BT. Using the intercept on y-axis
for different temperature plots of the above, the values of the intercepts are then
plotted against temperature to yield another straight line with slope as B and
intercept on y-axis as A. In the nonlinear regression analysis, the avC as C and A and
B values are used as the starting values in parameter estimates for the model.

h. Modified Henderson model: the modified Henderson model (Eq. (14)) is

transformed to yield Eq. (34):

aw ¼ 1  exp AðT þ BÞMC (34)

Eq. (34) is linearized by logarithmic transformation as follows:

23
Sorption in 2020s


1  aw ¼ exp AðT þ BÞMC (35)
Lnð1  aw Þ ¼ AðT þ BÞM C
(36)
Lnð1  aw Þ ¼ AðT þ BÞM C
(37)
Ln½Lnð1  aw Þ ¼ Ln½AðB þ T Þ þ CLnM (38)

A plot of Ln½Lnð1  aw Þ against LnM at each temperature yields a straight line

with slope a1 = C and intercept on the y-axis b1 = Ln½AðB þ T Þ. To solve for the
temperature-related parameters, intercept on the y-axis is used.

Therefore, exp ðb1 Þ ¼ AðT þ BÞ ¼ AT þ AB: (39)

A plot of exp ðb1 Þ against T yields a straight line with slope a2 as A and intercept
on y-axis b2 as AB. In the nonlinear regression procedure, avC and A and B are used
as initial parameter estimates for the model.

i. Modified Oswin model: the modified Oswin model (Eq. (15)) can be
manipulated algebraically to yield Eq. (40):

1
aw ¼ h iC (40)
ðAþBT Þ
M þ1
C C
1 ðA þ BT Þ 1 ðA þ BT Þ
¼ þ 1 and 1¼ (41)
aw M aw M

Linearizing Eq. (41) by logarithmic transformation yields

 
1  aw
CLnðA þ BT Þ  CLnM ¼ Ln (42)
aw


A plot of Ln 1a
aw
w
against LnM at each temperature yields a straight line with
slope as –C and intercept on the y-axis as CLnðA þ BT Þ.
The expression for intercept on the y-axis is solved further to evaluate the
temperature-related parameters of the model and yield Eq. (43),

exp ðb=c Þ ¼ ðA þ BT Þ (43)

A plot of exp ðb=c Þ against T yields a straight line with slope as A and intercept on
the y-axis as B. In the nonlinear regression procedure, avC as C and A and B are
used as the initial parameter estimates in the model evaluation.

j. Ngoddy-Bakker-Arkema model: the Ngoddy-Bakker-Arkema model, which

has been postulated to be a generalized model, has the following parameters
(unknowns): σ, V, Pm, ρ, ε and η.

Evaluating the model requires a lot of care. The starting values of parameters for
application in the nonlinear regression procedure can be obtained as follows:
σ, V, ρ and Po can be obtained at different temperatures from the steam table P
can be calculated using the expression P = aw, ε can be taken as having a typical
value of 0.1 though its value can be less, Pm is the monolayer value of P and η can be
assumed to lie between 1 and þ1 in the form of 1 ≤ η ≤ þ1 with 0.1 as a typical
starting value.

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7.2. Moisture sorption isotherm model predictive indicators

After values of model constants have been determined using the nonlinear
regression analysis, the suitability of a model for predictive purpose or its goodness
of fit is determined using the following indices:

a. Residual plots: these are plots of residuals (difference between measured and
predicted values of the EMC) against the measured values.

b. Standard error of estimate given as

"P #1=2
ðY  Y 0 Þ
2
SE ¼ (44)
df

c. Mean relative percent deviation given as

100 X Y  Y 0
MRE ¼ (45)
N Y

d. Fraction explained variation given as

SSM
FEV ¼ (46)
SST
e. Residual sum of squares (RSS) given as
P
ðY  Y 0 Þ
2
RSS ¼ (47)
N
f. Coefficient of determination, R2.

where Y is the measured EMC value, Y 0 is the EMC value predicted by the
model, N is the number of data points, df is the degree of freedom, SSM is the sum
of squares due to the model and SST is the total sum of squares.

8. Conclusions

Moisture sorption phenomena govern several technological processes (drying,

storage, mixing and packaging to mention a few) involving agricultural and food
products. Moisture sorption isotherms of these products are generally of the type II,
sigmoidal in shape and temperature dependent. The isotherms can be determined
using the static or dynamic gravimetric, vapor pressure manometric, hygrometric
and inverse gas chromatographic methods. Desorption isotherm path could differ
from that of adsorption leading to moisture sorption hysteresis.
Commonly used moisture sorption isotherm models include the BET, GAB,
modified GAB, Hailwood-Horrobin, modified Hailwood-Horrobin, modified
Chung-Pfost, modified Halsey, modified Henderson and modified Oswin models.
Ngoddy-Bakker-Arkema model which was proposed as a generalized model was
considered. While some of the models can be evaluated by fitting polynomial
functions of the second order to them and applying nonlinear regression procedure,
others can be solved thorough linearization by logarithmic transformation and
nonlinear regression. For the Ngoddy-Bakker-Arkema model, the initial parameter

25
Sorption in 2020s

estimates for use in nonlinear regression have to be obtained from the steam table.
A model is considered acceptable for predictive purpose, if the residuals are uni-
formly scattered around the horizontal value of zero showing no systematic ten-
dency towards a clear pattern. Model goodness of fit is determined using standard
error of estimate, mean relative percent deviation, fraction explained variation,
coefficient of determination and residual sum of squares.

Conflict of interest

This chapter has no conflict of interest.

Author details

Ndubisi A. Aviara
Department of Agricultural and Environmental Resources Engineering, Faculty of
Engineering, University of Maiduguri, Maiduguri, Nigeria

*Address all correspondence to: nddyaviara@[Link]

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms
of the Creative Commons Attribution License ([Link]
by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.

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DOI: [Link]

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