Sorption

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Sorption

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ISSN: 0737-3937 print/1532-2300 online

DOI: 10.1080/07373930600775979

Santanu Basu,1 U. S. Shivhare,1 and A. S. Mujumdar2

1

Department of Mechanical Engineering, National University of Singapore, Singapore

This article presents basic concepts related to the thermodynamics of sorption of water and measurement of sorption isotherm

for food materials. A comprehensive review of the widely used sorption models is presented. Various statistical techniques used to

ascertain the effectiveness of a model to describe the sorption data

are discussed. It is anticipated that this article will provide useful

information to researchers pursuing work on sorption behavior of

food materials as well as modeling of drying processes.

Keywords Heat of sorption; Isosteric heat; Model; Sorption isotherm; Statistical analysis

INTRODUCTION

The state of water plays a crucial role in food preservation. The quality of preserved foods depends upon the

moisture content, moisture migration, or moisture uptake

by the food material during storage. Extent of sorption

of water by or desorption from a food product depends

on vapor pressure of water present in the food sample

and that in the surroundings. Moisture content at which

vapor pressure of water present in the food equals that of

the surroundings is referred to as equilibrium moisture content (EMC).[1] Relationship between EMC and corresponding relative humidity at constant temperature yields

the so-called moisture sorption isotherm. For a given

material the EMC increases with relative humidity but

decreases with increase in temperature. The phenomenon

where the EMC during the adsorption and that during

the desorption process is different is called hysterisis.

Water activity is commonly used to characterize the food

quality and is defined as

aw

P

ERH

P0

100

any given temperature (Pa), P0 is the vapor pressure of

pure water at that temperature (Pa), aw is the water activity

Correspondence: U. S. Shivhare, Department of Chemical

Engineering & Technology, Panjab University, Chandigarh,

160014 India; E-mail: usshiv@yahoo.com

humidity (%).

Five types of isotherms were described by Brunauer

et al.[2] (Fig. 1). Type 1 is the well-known Langmuir isotherm, obtained assuming monomolecular adsorption of

gas by the porous solids in a finite volume of voids. Type 2

is the sigmoid isotherm obtained for soluble products,

which exhibits asymptotic trend as water activity

approaches 1. Type 3, known as the Flory-Higgins isotherm, accounts for a solvent or plasticizer such as glycerol

above the glass transition temperature. Type 4 isotherm

describes adsorption by a swellable hydrophilic solid until

a maximum of hydration sites are reached. Type 5 is the

BET[3] multilayer adsorption isotherm, observed for

adsorption of water vapor on charcoal; it is related to types

2 and 3 isotherms. The two isotherms most commonly

found in food products are types 2 and 4.[4]

Water adsorption by foods is a process wherein water

molecules progressively and reversibly combine with the

food solids via chemisorption, physical adsorption, and

multilayer condensation.[5] An isotherm can typically be

divided into three regions as shown in Fig. 2. The water

in region A represents strongly bound water with enthalpy

of vaporization considerably higher than that of pure

water. The bound water includes structural water

(H-bonded water) and monolayer water,[6] which is sorbed

by hydrophilic and polar groups of the food components

(polysaccharides, proteins, etc.). Bound water is unfreezable and is not available for chemical reactions or as a plasticizer. In region B, water molecules bind less firmly than in

the first zone. The vaporization enthalpy is slightly higher

than that for pure water. This class of constituent water

can be looked upon as the continuous transition of the

bound to the free water. Properties of water in region

C are close to those of the free water that is held in

voids, capillaries, crevices, and loosely binds to the food

materials.[1,7]

Measurement and modeling of sorption isotherms of

food materials has attracted numerous researchers because

of their value in industrial practice. Comprehensive reviews

on sorption behavior of foods have been published.[813]

917

918

covering a very wide range of products. This article gives

a comprehensive review of the main theories of the sorption phenomenon in foods and different mathematical

models commonly used to describe the sorption behavior.

The article elaborately discusses various statistical analysis

tools that should be considered for drawing conclusions

from any set of experimental and predicted values. Note

that in drying it is the desorption isotherm that is of greater

interest than the adsorption isotherm. The word sorption covers both adsorption and desorption.

THERMODYNAMICS OF SORPTION

When water is removed from a food product, heat is

absorbed because water has to be removed against a water

activity gradient or against increasing osmotic pressure.

The isosteric heat of sorption, also called differential

enthalpy, is an indicator of the state of water held by the

solid material. Net isosteric heat of sorption (DHS ) is the

difference of total heat of sorption (DHd ) in the food and

the heat of vaporization of water (DHvap ) associated with

the sorption process and can be computed from experimental data using Clausius-Clapeyron equation

dln aw

DHS

2

d1=T M

R

hysteresis.[1]

sorbed molecules at a particular moisture content (M).

Integrating Eq. (2) using the associated boundary conditions yields

Z aw2

Z

DHS T2 1

dln aw

d

T

R T1

aw1

3

aw2

DHS 1

1

ln

aw1

R T1 T2

where aw1 and aw2 represent water activities at temperatures T1 and T2, respectively, and R is the universal gas

law constant (8.314 kJ=molK)

Several assumptions are made implicitly in applying the

Clausius-Clapeyron equation. First, the heat of vaporization of pure water (DHvap ) and the excess heat of sorption

DHS are assumed not to change with temperature. Secondly, the equation applies only when the moisture content

of the system remains constant with respect to time.[14]

From the isotherms determined at least at 10C apart, aw

at any other temperature should be predictable from

Eq. (3) if the assumptions are correct. Plotting the experimental sorption isotherm in the form ln(aw) vs. 1=T for a

specific moisture content, DHS is determined from the

slope DHs =R.

An empirical relationship between the net isosteric heat

of sorption (DHS ) and the moisture content (M, dry basis)

is expressed as[14]

where DH0 is the net isosteric heat of sorption when moisture content (M) 0. The constant MC is a characteristic

moisture content (kg water per kg dry matter) of a food

material at which the net isosteric heat of sorption (DHS )

has been reduced by 63%. Due to the exponential decay,

the net isosteric heat of sorption becomes very small at high

moisture content; e.g., at M 3 MC, DHS is less than 5%

of DH0 .

The net heat of sorption of water Q (kJ per kg dry matter) from dryness (M 0) to moisture content M is

expressed as:[14]

Z M

Q

DHS dM

5

0

Substituting DHS from Eq. (4) into Eq. (5) and integrating

yields

Q DH0 MC 1 expbM=MC c

For very high moisture content (M ! 1), Eq. (6) gives the

total net isosteric heat in terms of heat of sorption of water

(QT).

QT DH0 MC

content from M1 to M2 (Q12) is expressed as

Q12 DH0 MC bexpM1 =MC expM2 =MC c

drying a food material from moisture content M1 to M2.

In drying, M1 > M2, and the net heat of desorption (Q12)

is negative, because an extra amount of energy is required,

in addition to heat of vaporization of water (DHvap ), to

remove the adsorbed water from the food product.

The relationship between the isosteric heat (DHd ) and

differential entropy (DSd ) of sorption is expressed as:[15]

lnaw M DHd =RT DSd =R

dependence of DHd and DSd on moisture may be

determined.[16,17]

The compensation theory proposes a linear relationship

between DHd and DSd [15,18]

DHd Tb DSd a

10

computed using linear regression of Eq. (10). Parameter a

may be neglected due to its negligible contribution to the

enthalpy change. The compensation theory may be further

used to evaluate the effect of temperature on the sorption

behavior by applying Eq. (11).[16]

lnaw DHd =R1=T 1=Tb

11

919

Many methods are available for determination of water

sorption isotherm. These methods may be classified into

three categories: (1) gravimetric, (2) manometric, and (3)

hygrometric. The gravimetric method involves the measurement of mass changes that can be measured both continuously and discontinuously in dynamic and static systems.

Manometric methods involve sensitive manometers to

measure vapor pressure of water in equilibrium with a food

material of given moisture content. Hygrometric methods

measure the equilibrium relative humidity of air in contact

with a food material at given moisture content. Dew point

hygrometers detect the condensation of cooling water

vapor. Electronic hygrometers measure the change of

conductance or capacitance of hygrosensors.[19]

The most common technique, for which a recommended

procedure has been defined in the European project COST

90, uses thermostatted jars filled at the bottom with supersaturated salt solutions to maintain the desired air relative

humidity.[20] However, this method encounters some problem at high humidity ranges due to (a) excessive equilibration times and (b) its inability to produce and control

high relative humidities.

Baucour and Daudin[20] developed a rapid but accurate

method to measure moisture sorption isotherms of solid

foods in the water activity range 0.91. This method avoids

the drawbacks of saturated salt solution method by blowing calibrated air along thin slices of material at a high

velocity to impose an intensive water vapor exchange

between air and samples.

MATHEMATICAL MODELS OF ISOTHERMS

Numerous attempts have been made to describe the

sorption isotherms mathematically. While some models

have been derived theoretically based on thermodynamic

concepts, others are an extended or modified form of these

models. Some of the widely used mathematical models are

presented in the following paragraphs.

LANGMUIR EQUATION

On the basis of monomolecular layers with identical,

independent sorption sites, Langmuir[21] proposed the following physical adsorption model:

1

1

1

12

aw

M M0

CM0

where M0 is monolayer sorbate constant and C is a constant.

The relation described by Eq. (12) yields the type I isotherm.

BRUNAUER-EMMETT-TELLER (BET) EQUATION

The BET isotherm equation[3] is one of the most widely

used models and gives good fit for a variety of foods over

the region 0.05 < aw < 0.45.[22] It provides an estimate of

920

BET equation is expressed as

M

Caw

M0 1 aw 1 C 1aw

13

or

aw

1

C1

aw

1 aw M M0 C M0 C

14

kg dry matter), M0 is the monolayer moisture content on

the internal surface (kg water=kg dry matter), and C is a

dimensionless parameter related to heat of sorption of

monolayer region.

The theory behind the development of the BET equation

has been questioned due to the assumptions that (a) the

rate of condensation on the first layer is equal to the rate

of evaporation from the second layer, (b) binding energy

of all of the adsorbate on the first layer is same, and (c)

binding energy of the other layers is equal to that of pure

adsorbate. The assumptions of uniform adsorbent surface

and absence of lateral interactions between adsorbed

molecules are incorrect in view of the heterogeneous food

surface interactions.[9]

MODIFIED OSWIN EQUATION

The Oswin[23] equation is a mathematical series expansion for a sigmoid-shaped curve and is represented as

MK

aw

1 aw

N

15

The parameter K was found to be a linear function of

temperature.[24] The Oswin equation may be modified as

N

aw

M A BT

16

1 aw

or

"

aw

M

A BT

#1

C

1

17

with C 1=N.

MODIFIED HALSEY EQUATION

Halsey[25] developed an equation to describe condensation of multilayers, assuming that the potential energy

of a molecule varies inversely as the Cth power of its

distance from the surface. The equation is

AM C

aw exp

18

RT

Because the use of the term RT does not eliminate the temperature dependence of constants A and C, Iglesias and

Chirife[26] simplified it to the form

aw expA0 M C

19

Iglesias and Chirife[27] analyzed the parameter A of the

Halsey equation and found that it could be related to temperature by an empirical exponential function. A new

modified Halsey equation was therefore proposed:

expA BT

aw exp

20

MC

where A, B, and C are constants.

Iglesias and Chirife[28] reported that the Halsey equation

described 220 experimental sorption isotherms of 69 different foods in the range of 0.1 < aw < 0.8.

MODIFIED HENDERSON EQUATION

Henderson[29] presented an equation of the form

aw 1 expbATM Cc

21

adding another constant to the temperature term. The

modified Henderson equation becomes

aw 1 expbAT BM Cc

22

Hendersons equation has been applied to many

foods,[3134] but compared to the Halsey equation, its applicability has been rather limited.

CHUNG-PFOST EQUATION

Chung and Pfost[35,36] developed a model based on the

assumption that the change in free energy for sorption is

related to the moisture content

A

expBM

23

aw exp

RT

Later, in order to obtain a better fit, Pfost et al.[37] added a

new parameter to the temperature term and combined the

R parameter in constant term. The modified Chung-Pfost

equation is expressed as:

A

expBM

24

aw exp

T C

FERRO FONTAN EQUATION

The Ferro Fontan equation[38] is represented as

c

ln

aM r

aw

25

921

sorbed water, a is a constant, and r is a constant that

involves net isosteric heat with moisture content adjustable

parameters. Iglesias and Chirife[39] compiled sorption data

for 156 food items and documented that Ferro-Fontan

equation is an accurate tool for the mathematical description of food isotherms. The Ferro-Fontan equation accurately represents the sorption isotherm in the range of

water activity 0.10.9 with only 24% error in the predicted moisture content.

GAB EQUATION

van den Berg[40] refined the Langmuir and BET theories

and proposed a new equation with three parameters having

physical meanings

M

CKaw

26

M

C 1Kaw

Kaw

27

of sorption of monolayer region and K is a dimensionless

GAB parameter related to heat of sorption of multilayer

region.

Equation (27) is divided into two additive terms, the first

one describes the classical mono-molecular layer

expression in Langmuirs adsorption isotherms and the

second term describes the multilayer adsorption corresponding to Raoults law.[40]

Parameters K and C can be expressed by Arrhenius type

equations:

DHc

0

C C exp

28

RT

DHk

0

K K exp

29

RT

where DHc DHm DHq ; DHk DHl DHq (kJ mol 1);

DHl is the heat of condensation of pure water

(kJ mol 1); DHm is the total heat of sorption of mono layer

(kJ mol 1); DHq is the total heat of sorption of multilayer

covering the monolayer (kJ mol 1); and C 0 , K 0 are the

constants of entropic character.

The GAB model underestimates the water content values

at high water activities (aw > 0.93). The discrepancy underlines two facts: (a) this type of model is unsuitable for high

humidity range, and (b) the saturated salt solution method

does not afford sufficient information to get a complete sorption curve. The GAB model was refined for higher water

activities by Timmerman and Chirife;[41] and Viollaz and

Rovedo.[42] They modified the GAB model by inserting a

new parameter to add a third sorption stage without changing

the values of the usual parameters defined in the GAB model.

Equation (27) can be rewritten in one-parameter form:

w

1

1

1 X 1 1 CX

30

Equation (30) can be described for five conditions: (1) for

X 0, (2) for w 1 for the so-called mono-molecular

layer, (3) for X K (i.e., for aw 1), (4) at the point of

inflection w X, and (5) potential singular points. The

characteristic properties of the isotherm at these points give

the limits on the parameters K and C.[43]

1. For X 0; Eq. (30) gives the value w 0 identically.

The shape of the sigmoid sorption isotherm may be

obtained by differentiating Eq. (30) corresponding to

dw

dw

the condition

0:

K

daw

dX

dw

1

1C

2

dX 1 X

1 1 C X 2

31

so the mentioned condition leads to the final form

KC 0. It infers that both parameters K and C have

to be of the same sign.

2. The existence of a mono-molecular layer for w 1 leads

to the quadratic equation Xm2 1 C 2Xm 1 0

where Xm is the value of variable X in the monomolecular state. The equation has the following solution

for 0 < X < 1:

Xm

1

p

1 C

for C 0:

32

and K have to be non-negative.

3. Substituting X K into Eq. (31) and rearranging, the

following equation is obtained:

w

KC

1 K1 K1 C

for X K

33

both parameters K and C have to be greater than zero.

Moreover, the following condition

1 K1 K1 C > 0

has to be fulfilled. This inequality has two solutions:

K 1

; i:e:; C > 0

K

K 1

b=K > 1; 0 < C <

K

a=0 < K;

C>

34a

34b

922

4. Points of inflection: the point of inflection of the sorption isotherm is given by the zero point of the second

derivative of w X plot. The following equation is

obtained for the X coordinate (Xi) of such a point:

Xi3

3Xi

C2

0

C 1 C 1 2

35

where k1, k2, n1, and n2 are constants (n1 < 1) and n2 > 1).

The model expressed by Eq. (43) has no monolayer incorporated in it. However, plots of aw =M1 aw vs. aw used

to determine the monolayer value with the BET model are

still expected to be practically linear over a water activity

range of up to about 0.4. This is because at this range of

aw Eq. (43) can be approximated by

M k1 anw1

Z1

Xi

for C 2

36

Z2

p

where Z 3 C 1. The relative moisture content corresponding to the point of inflection wr is given by inserting Xi from Eq. (36) into Eq. (30)

wr

Z2 1

A

37

A Z2 Z 1

38

Eq. (30) for 0 < X < 1. This condition is fulfilled

for all K 1 but it is not fulfilled for K > 1.[43]

PELEG MODEL

Peleg[44] developed a two-parameter model to describe

the sorption curves

Mt Mi

t

k1 k2 t

39

Mi initial moisture content (% dry basis) and k1, k2 are

constants. According to this model, equilibrium moisture

content ME when t ! 1 is given by

M E Mi

1

k2

40

by

dMt

k1

dt

k1 k2 2

41

Equation (39) can be easily transformed to a linear

relationship

t

k1 k2 t

Mt Mi

Peleg

aw

aw

M1 aw k1 anw1 1 aw

42

M k1 anw1 k2 anw2

43

44

45

The plot of aw = anw1 1 aw vs. aw (k1 1) is linear in this

water activity range and for a range of n1 values. The intercept is positive when n1 is greater than 0.3.

aw

aw =k1

n1

M1 aw aw 1 k1 =k2 anw1 n2 1 aw

where

[45]

and

n1 < 1

46

tends to lower the magnitude of aw =M1 aw as the

magnitude of aw increases.

TIMMERMANN GAB MODEL

Compared to the classical BET isotherm, the GAB

isotherm contains a third constant, K, which measures the

differences between the standard chemical potential of the

molecules in the second sorption stage and in the pure

liquid. Some researchers[46,47] noted that at very high water

activities some systems showed a sorption stage larger than

the predicted by the GAB model. Timmermann[41,47] suggested that the second sorption stage introduced by the

GAB model may be limited to a certain number of layers

and that, thereafter, a third stage becomes available

for the sorbate molecules, which has true liquid-like properties, as postulated by the original BET model. The

so-called third sorption stage isotherm developed by

Timmermann[47] is

M

CKaw HH 0

M0 1 Kaw 1 CH 1Kaw

47

1 K Kaw h

K 1 aw

H 1 1 Kaw

0

H 1

h 1 haw

H

1 aw

H 1

48

49

For h ! 1, H; H 0 ! 1 and with this result Eq. (47) transforms into a GAB equation.

923

Equation (27) was modified by Viollaz and Rovedo[42] in

an empirical way by adding a term

M

CKaw

CKK2 a2w

50

K2 is an additional dimensionless parameter.

The second term of the RHS allows the necessary flexibility to obtain a good fitting for high aw values. This term

has a very low weight for low values of aw, so the values of

M0, C, and K are not substantially affected by the addition

of this new term. It can be observed that if the value of K2

is equal to zero, the GAB isotherm is obtained. The predictive capacity of Eq. (50) was evaluated using the sorption

data for starch and gluten by Viollaz and Rovedo.[42]

LEWICKI MODEL

Lewicki[48] developed a model on the basis of Raoults

law. The model assumed that water present in food occurs

in two states, as free water with properties of the bulk

water and as water of hydration. The Lewicki model of

food sorption isotherm is

b1

1

MA

1

51

aw

where A and b are constants. Equation (51) described the

water sorption isotherms of 38 products and 31 model

mechanical mixtures.[48]

WATER ACTIVITY OF SOLUTION/MIXTURES

For water solution, Raoults law shows that the water

activity in ideal solution is equal to mole fraction of water

(xw); that is, aw xw.

For nonideal solutions, the activity coefficient c corrects

for deviation from nonideality.

aw xw c

52

law for the nonideal solution

aw xw kx2s

53

constant.

Ross[50] extended the Norrish equation for multi component systems by using the Gibbs-Duhem equation with the

assumption that the activity coefficient of individual components with water are equal to their activity coefficients

in binary mixtures in water.

The Ross equation is represented as:

lnaw

k

X

j1

lna0wj

54

Here, awj is the water activity of the binary mixture with the

j component.

The Ross equation has been applied by several researchers, e.g., Chirife et al.,[51] Herman et al.,[52] and Roman

et al.[34] The water activities of non-solute parts were also

evaluated with the Henderson equation based on literature

data for starch, protein, and fiber by Roman et al.[34]

ARTIFICIAL NEURAL NETWORK MODELING

Artificial neural network (ANN) modeling is a method

to describe relations between independent and dependent

variables when the explicit form of mapping is not known.

In recent years, the concept of ANN has gained wide

acceptance in food engineering for predictive modeling.

In case of sorption isotherm prediction, Myhara et al.,[53]

Myhara and Sablani,[54] and Kaminski and Tomczak[55]

used ANN modeling for different food materials. Myhara

et al.[53] demonstrated that when chemical composition

data is combined with physical data through an ANN

approach, significant improvements in the prediction of

water sorption behavior can be achieved.

COMPARISON OF BET AND GAB MODELS

The BET and the GAB isotherms are closely related as

they are derived from the same statistical model. The

GAB model represents a refinement over the BET model

and shares with it two original BET constants (M0, the

monolayer capacity, and C, the energy constant) and owes

its versatility due to the introduction of a third constant

(K). The regression of an experimental sorption data by

each of these two isotherms will give two sets of values of

M0 and C. The same type of differences between both sets

of values of M0 and C have always been observed:

M0B < M0G ;

CB > CG

55

respectively.

The M0 value given by BET isotherms is always lower

than the monolayer value derived from GAB and, reversibly, the BET value of energy constant is always higher than

the GAB value. It has been demonstrated that there exist

mathematical and physical reasons for the inequalities set

by Eq. (55).[56,57]

The BET equation may be rewritten as

M

CB aw M0B

1 aw 1 CB 1aw

56

To obtain the two characteristic constants, the BET equation is linearized by the following function

F BET

aw

1

CB 1

aw

1 aw M CB M0B CB M0B

57

924

at low activities (0.05 < aw < 0.30.5), after which always

an upward curvature is observed. This deviation shows that

at higher activities, less gas or vapor is sorbed than that

indicated by the BET equation using the values of the constants corresponding to the low activity range.

The GAB equation is rewritten as

M

CG Kaw M0G

1 Kaw 1 CG 1Kaw

where

1

CGG M0G

64a

CGG 1 21 K

CGG M0G

64b

1 KCGG 1 K

CGG M0G

64c

A

B

58

and

CG K CGG

59

analogue of this formulation to the BET energy constant

CB. The constant (K) is a measure of the difference of free

enthalpy of the sorbate molecules in the pure liquid and

the second sorption stage, the layer above the monolayer.

It is always found that K < 1. Finally, with K 1, the

GAB isotherm reduces to the original BET equation

(M0B M0G; CB CG(G)).

To determine the three constants of the GAB equation,

it is linearized like the BET equation and the function

F(GAB) is introduced:

F GAB

aw

1

CG 1

aw

1 Kaw M CG KM0G CG M0G

60

used. From the two linear regression coefficients, M0G

and CG are obtained.

Equation (57) can be rewritten in a modified form by

incorporating F(GAB)

aw

1 Kaw

F BET

F GAB

1 aw M

1 aw

A C B Caw

C

1 aw

65

n

X

F BETi a0 a1 awi

2

minimum

66

i1

are given by the solutions of the system of normal equations

associated to the extreme condition (Eqs. (67a) and (67b).

The least square estimates of a0 and a1 , a00 and a01 are

given directly by the BET relations by which the BET constants are usually computed.

BET: a00

a01

1

CB M0B

CB 1

CB M0B

67a

67b

and hereafter

F (BET) will not be linear in aw but will present a hyperbolic behavior.

Caw

1 aw

PBET a0 a1 awi

61

Eq. (61) a new relationship represented by F (BET) is

obtained, in terms of the three constants of the GAB

isotherm:

1

CG 1

1 Kaw

F BET

aw

CG KM0G CG M0G

1 aw

CGG 1 21 K

1

aw

CGG M0G

CGG M0G

1 KCGG 1 K

aw

62

CGG M0G

1 aw

F BET A Baw

The experimental values of F(BET) are adjusted by the

linear polynomial

63

M0B

CB

1

a00 a01

a00 a01

a00

68a

68b

proportional to the intercept a00 of the linear regression

polynomial P(BET) of Eq. (68b) and therefore CB is highly

sensitive to the value of a00 , which is usually very low.

The second expression of F (BET) may also be adjusted

by the same linear polynomial (Eq. (65)), but now using an

analytical formulation as F (BET) is known as a function

of aw and not by a set of numerical data. The calculation

implies the adjustment of a function of a known functional

dependence of a higher degree than one to a straight line.

In the discrete procedure, F (BET) given by Eq. (63) is put

into condition (Eq. (66)), which becomes

925

n

X

fA C B Cawi C=1 awi a0 a1 awi g2

i1

minimum

69

a1 using the least squares technique. Coefficients a0 and

a1 become functions of the constants A, B, and C of

Eq. (63) on one side, and of regression sums over the values

of the independent variable awi on the other.

The final expressions are the following:

a0

A C Cd=d0

70a

a1 B C Cd1 =d

70b

terms of F (BET). The functions d, d0 , and d1 contain only

the regression sums of aw over the employed regression

interval with the following signs: d0 =d < 0, d1 =d < 0, and

d0 =d d1 =d < 0 for aw < 1.[56,57]

The corresponding relations where Gaussian brackets

have been used are

d0 1=1 aw a2w aw =1 aw aw

71a

d1 aw =1 aw n 1=1 aw aw

71b

d na2w aw 2

71c

As Eqs. (65) and (66) remain valid, the BET constants

are now given by

M0B

1

1=fA B C d0 d1 =d 2g 72a

a00 a01

and

CB

These functions are always greater than unity.[56] Therefore, Eqs. (73a) and (73b) reproduce the inequalities

(Eq. (55)) if K<1.

The marked differences between the BET and GAB constants are noteworthy. The GAB isotherm, is an improved

version of the BET model, by the introduction of the third

parameter, K, characterizing the state of sorbed molecules

beyond the first layer.

RESEARCH RESULTS FOR SORPTION ISOTHERMS

OF FOOD MATERIALS

Modeling of sorption behavior of a variety of food

materials has been carried out by many researchers. A list

of recent research done after 2000 on different types

of food materials is presented in Table 1. This list is

not exhaustive; comprehensive information of sorption

isotherms for different food materials has been

published.[39,5860]

STATISTICAL TESTING OF SORPTION MODELS

Statistical analysis of an isotherm may be quantified

through five standards: the coefficient of determination

(R2), the residual sum of squares (RSS), the standard error

of the estimate (SE), the mean relative deviation (MRD),

and the plot of residuals. The coefficient of determination

is a statistical measure of how closely two variables are

related. The coefficient of determination is a dimensionless

index that ranges from 0 to 1 and reflects the extent of linear relationship between two data sets.

The residual sum of squares (RSS) is defined as

RSS

n

X

M MCal 2

75

i1

a00 a01

a00

72b

and an algebraically explicit expression for M0B and CB

in terms of the three GAB constants are obtained:

M0G

M0B

121K=CGG Rm

21K

CB CGG 1

RC

CGG

73a

73b

Rm 11K CGG 1K=CGG 21K

d0 d1 =d2

RC Rm = 11KCGG 1Kd0 =d1

74a

74b

through the fitting equation and n is the number of data

points.

The standard error of estimate (SE) is the conditional

standard deviation of the dependent variable and has the

form

s s

Pn

2

RSS

i1 M MCal

SE

76

df

df

Here, df represents the degrees of freedom of the fitting

equation. If a large data set is available, Eq. (76) is simplified to

r

RSS

SE

77

n

The mean relative deviation (MRD) is an absolute value

because it gives the mean divergence of the estimated data

from the measured data

926

TABLE 1

Recent works on sorption isotherms of food materials

Temperature (C)

Food product

Berries

Mushroom

4, 13, 27

4, 13, 27

3070

25, 30, 35

Cocoa beans

Starch, potato

Pumpkin seed flour

Cured beef and pork

Chicken meat

Hazelnuts

Rough rice

3060

3060

10, 25, 40

10, 20, 25, 35, 49

430

25

0, 5, 10, 15, 20, 25, 30, 35

Yogurt powder

Gelatine gel

Crystalline lactose powder

35

20

12, 20, 30, 40

MRD

n

1X

jM MCal j

M

n i1

aw

Reference

0.110.87

0.120.75

0.200.80

0.080.94

GAB

GAB

Chung-Pfost

BET (aw < 0.5)

Harkins-Jura (aw > 0.5)

GAB, Halsey

GAB, Ferro-Fontan, Peleg

GAB

Peleg, GAB

Ferro-Fontan, GAB

GAB

Modified Chung-Pfost,

modified Henderson

Modified Chung-Pfost

Ferro-Fontan

Timmermann-GAB, GAB

63

63

64

65

0.110.83

0.050.95

0.110.85

0.100.94

0.250.94

0.110.90

0.2590.935

0.40.99

0.750.98

0.110.98

78

Plotting of the residuals (MMCal) against the independent variable is also used as a measure of the distribution of errors. If the model is correct, then the

residuals should be only random independent errors with

a zero mean, constant variance and arranged in a normal

15

66

67

68

69

70

71

72

20

73

the model should not be accepted.

In general, low values of the correlation coefficient, high

values of RSS, SE, and MRD, and clear patterns in the

residual plots mean that the model is not able to explain

the variation in the experimental data. It is also evident

that a single statistical parameter cannot be used to select

the best model and the model must always be assessed

based on multiple statistical criteria.[61]

TABLE 2

Data on goodness of fit of selected models for sardine sheet at selected temperatures (25, 40, and 50C) and water activity

(0.110.84)

Coefficients of linear regression

Isotherm

BET

Oswin

Smith

Hasley

Henderson

Chung and Pfost

Iglesias and Chirife

GAB

Peleg

Modified Oswin

Modified Henderson

Modified Chung-Pfost

0.9390.978

0.9630.984

0.9540.974

0.9590.994

0.9310.974

0.8850.906

0.9900.993

S.E.

R2

S.E.

0.6480.968

0.1010.139

0.0120.022

0.0650.164

0.1520.237

0.250.299

0.0060.008

0.9830.996

0.9860.997

0.9540.974

0.9700.994

0.9480.978

0.9310.953

0.990.993

0.9890.996

0.9360.968

0.8130.995

0.9480.978

0.9310.953

0.0040.009

0.0040.009

0.0120.021

0.0200.042

0.360.054

0.060.067

0.0060.008

0.0040.007

0.0140.026

0.0050.029

0.0360.054

0.0600.067

927

TABLE 3

Pattern of residual plots of selected models

Model

BET

Peleg

Oswin

Hasley

GAB

Modified Henderson

Modified Chung-Pfost

Iglesias and Chirife

Patterned

Patterned

Scattered

Patterned

Scattered

Scattered

Patterned

Patterned

FIG. 4. Residual plot of sorption data for sardine fish at 40C (GAB

isotherm).

AN EXAMPLE

Published sorption data[62] (water activity range 0.11

0.84) of freeze-dried sardine fish at 25, 40, and 50C

was selected for comparison of the different sorption isotherm models. Both linear and nonlinear approaches were

used to estimate the model coefficients. Standard error

and R2 values of different isotherm models for both linear

and nonlinear forms are given in Table 2. The R2 values

of the nonlinear models were always higher than that of

the linear equations. Similarly, standard error values were

also lower in nonlinear cases compared to the linearized

form, which suggests that nonlinear forms should be used

for estimation of model parameters. After choosing few

sorption models with higher R2 and lower SE values, their

residual plots were checked. Residual plot patterns of different models are presented in Table 3. Among all the

TABLE 4

Calculated GAB parameters at selected temperatures

Temperature

(C)

25

40

50

Monolayer moisture

content

(kg water=kg

dry matter)

2.0699

0.6834

7.3495

1.1172

1.0697

1.2121

0.0768

0.1857

0.1857

of their high correlation coefficient values and low standard error values. Both these models gave a scattered

residual plot. Although the Oswin model gave higher R2

(0.9860.997) and lower SE (0.0040.009) values, it does

not include temperature parameter. It may therefore be

inferred that GAB isotherm describes the sorption data

best over the experimental range of temperature and

water activity among all the isotherm models considered.

The monolayer moisture content (M0) and dimensionless

GAB parameters related to heat of sorption for the

monolayer and multilayer region (C and K) determined

from GAB equation are reported in Table 4. Figure 3

represents the sorption isotherm for sardine fish based

on GAB model and Fig. 4 shows a typical residual plot

of sorption data at 40C.

CONCLUSION

Theoretical aspects of sorption of water and commonly

used mathematical models to describe sorption isotherms

are discussed. Statistical criteria for selection of a model

have also been presented. Both the GAB and Oswin equations presented high R2 and low standard error values and

scattered residual pattern for freeze-dried sardine fish. But

because of lack of a temperature term in the Oswin equation, the GAB model is recommended for fitting the sorption data. From this discrimination approach based on

statistical measures, it is possible to select the best model

equation for describing experimental sorption data.

NOMENCLATURE

aw

A, A0 , B, r, k1, k2, n1, n2

C

FIG. 3. Sorption isotherm for sardine fish at 25, 40, and 50 C (GAB

isotherm).

df

ERH

Water activity

Constants

Dimensionless parameter

related to heat of sorption

of monolayer region

Degrees of freedom

Equilibrium relative

humidity

928

H and H0

K2

M, M1, M2

MC

MCal

MRD

M0

M0B(B), M0G(G), CB(B), CG(G)

P

P0

Q

Q12

R

RSS

SE

T

w

X

Greek Letters

a, a0

c

DHd

DHS

DHvap

d; d0 ; d1 ; a0 ; a1 ; a0 ; a1

Functions containing a

fourth dimensionless

parameter h

Dimensionless GAB

parameter related to heat of

sorption in multilayer

region

Dimensionless parameter

Moisture content

Characteristic moisture

content

Estimated value

Mean relative deviation

Monolayer moisture content on the internal surface

Constants

Water vapor pressure in the

food material at any given

temperature

Vapor pressure of pure

water at that temperature

Net heat of sorption of

water

Net heat of desorption

Universal gas constant

Residual sum of squares

Standard error of the

estimate

Absolute temperature

M=M0

Kaw

Constants

Parameter which accounts

for the structure of sorbed

water

Total heat of sorption in

the food

Net isosteric heat of sorption

Heat of vaporization of

water

Functions

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