Chapter 2

Adsorption Isotherms in Liquid Phase:

Experimental, Modeling, and Interpretations

Jeferson Steffanello Piccin, Tito Roberto Sant’Anna Cadaval Jr.,

Luiz Antonio Almeida de Pinto, and Guilherme Luiz Dotto

Abstract Adsorption is a fundamental unit operation used for several purposes in

the academy and industry. Particularly, adsorption in liquid phase is used to remove
recalcitrant compounds from effluents (dyes, heavy metals, phenols, pharmaceuti-
cals, and others), to recover valuable metals from leachates (gold, silver, cobalt, and
others), and to purify products during the industrial processing (fuels, juices,
liquors, wines, and others). For all these applications, the obtainment, modeling,
and interpretation of the equilibrium isotherms are a key and fundamental study.
Based on the abovementioned, this chapter presents the particularities of adsorption
equilibrium isotherms in liquid phase from scientific and technological viewpoints.
From the scientific viewpoint, the importance of adsorption isotherms will be
addressed. For example, the equilibrium isotherms provide parameters for
decision-making of the researcher in relation to the adsorption capacity of a
particular adsorbent, give an idea how the interaction of adsorbent–adsorbate
occurs, and provide means to find thermodynamic parameters, among others.
From technological viewpoint, the adsorption capacity of the material is a basic
parameter for the project. Thus, in this chapter the following points are highlighted:
experimental procedures to obtain equilibrium curves, isotherm analysis, models
used to correlate the equilibrium data and interpretation of its parameters, regres-
sion methods (comparison between linear and nonlinear regression methods), error
analysis, adsorption thermodynamics, and the use of these data for equipment
design.

J.S. Piccin
Food Engineering Department, Passo Fundo University, UPF, Br. 285, Km 171, 99052-900,
Passo Fundo, RS, Brazil
e-mail: jefersonpiccin@gmail.com
T.R.S. Cadaval Jr. • L.A.A. de Pinto
Industrial Technology Laboratory, School of Chemistry and Food, Federal University of Rio
Grande, km 08 Itália Avenue, 96203-900, Rio Grande, RS, Brazil
e-mail: titoeq@gmail.com; dqmpinto@furg.br
G.L. Dotto (*)
Chemical Engineering Department, Federal University of Santa Maria, 1000 Roraima Avenue,
97105-900, Santa Maria, RS, Brazil
e-mail: guilherme_dotto@yahoo.com.br

© Springer International Publishing AG 2017 19

A. Bonilla-Petriciolet et al. (eds.), Adsorption Processes for Water Treatment
and Purification, DOI 10.1007/978-3-319-58136-1_2
20 J.S. Piccin et al.

Keywords Adsorption • Equilibrium • Isotherms • Liquid phase • Modeling

Contents
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2 Experimental Procedures to Obtain Equilibrium Curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.3 Classification of the Equilibrium Isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.3.1 Subclasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.4 Adsorption Isotherm Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.4.1 Henry’s Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.4.2 Monolayer Adsorption and the Langmuir Isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.4.3 Multilayer Adsorption and the BET Isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.4.4 Other Isotherm Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.4.5 Statistical Physics Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.4.6 Typical Values of Isotherm Parameters for Different Adsorbate–Adsorbent
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.5 Regression Methods and Error Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.5.1 Model Accuracy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.5.2 Comparison Between Linear and Nonlinear Regression Methods . . . . . . . . . . . . . . . 42
2.6 Adsorption Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.7 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

2.1 Introduction

Adsorption is a unit operation that involves the contact of a solid phase with a fluid
phase (liquid or gas) (Ruthven 1984). In this work, only the solid–liquid adsorption
is addressed. The solid phase is known as adsorbent and the liquid phase (the
solvent, normally water) contains one or more compounds to be adsorbed (the
adsorbates). Due to unbalanced forces, the adsorbate is attracted to the adsorbent
surface, and consequently, the degrees of freedom and the surface free energy are
reduced (Suzuki 1993). The transference of the adsorbate from the liquid phase to
the solid phase continues until the equilibrium to be reached between the amount of
adsorbate linked in the adsorbent and the amount of adsorbate remaining in the
solution. The affinity degree between the adsorbent and adsorbate determines this
distribution in liquid and solid phases (Rouquerol et al. 2014).
In general, the adsorption can be classified according to the type of interaction
that occurs between the adsorbent and adsorbate. If there is an electron transfer
between the adsorbent and adsorbate, then, it is a chemical adsorption or chemi-
sorption. In this case, the adsorption involves electron transfer, and it is of high
energy, ranging from 40 to 800 kJ/mol and, consequently, desorption is difficult,
and thus the process is irreversible and only a monolayer is observed. In chemi-
sorption, the interactions can occur mainly by ionic or covalent bonds (Crini and
Badot 2008). Otherwise, if no electron exchange is observed, a physical adsorption
or physisorption occurs. In this case, the adsorption energies are low, ranging from
5 to 40 kJ/mol and, consequently, desorption is possible and the process can be
reversible and multilayer adsorption is possible. In physisorption, the interactions
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 21

can be electrostatic, hydrogen bonds, van der Waals, or dipole–dipole (Bergmann

and Machado 2015). It should be highlighted that this classification between
physical and chemical adsorption is a general behavior, but is not a dogma. Each
case should be examined separately.
Several advantages have been cited regarding the adsorption operation. For
example, in comparison with other unit operations, the adsorption in liquid medium
has a low energetic requirement and its implementation and operation are easy.
Many materials can be used as adsorbents, which can be regenerated and reused
several times. This practice becomes the adsorption in a low-cost operation. Also,
adsorption is efficient since it can remove or recover all the adsorbate from the
solution, providing a perfect separation. After, the adsorbent and adsorbate could be
reused. In some cases, adsorption is also selective (Do 1998). On the other hand,
after the adsorption, an additional operation can be necessary to provide a good
solid–liquid separation, for example, filtration, sedimentation, or centrifugation.
Another drawback is high cost of activated carbon, the adsorbent most commonly
used, mainly due its high surface area. In some cases, a secondary problem can
occur with the disposal of the generated sludge (Bansal and Goyal 2005).
To develop an adequate adsorption system, the adsorbent choice is the first and
fundamental aspect. A good adsorbent should have the following characteristics:
low cost; availability; efficiency; high surface area and pore volume; mechanical,
chemical, and thermal stability; ease of desorption and reuse; and able to provide a
fast kinetics and, mainly, present a high adsorption capacity (Rodrigues 2015). For
this proposal, the activated carbon is the adsorbent most utilized (Bansal and Goyal
2005). Other common adsorbents are clays, silica, and zeolites (Rouquerol et al.
2014). However, in the last years, several researches have been focused on the
preparation, characterization, and application of nonconventional adsorbents. Some
examples are powdered agro-wastes, powdered industrial wastes, chitosan, chitin,
fungi, bacteria, and algae (Dotto et al. 2015a). Surely, these studies are relevant,
but, to choose an adequate adsorbent, among other information, the following
question is fundamental: in which process the adsorbent will be used?
In operational terms, some configurations are possible for an adsorption process,
for example, discontinuous batch adsorption, continuous stirred-tank reactor
(CSTR), fixed bed adsorption, expanded bed adsorption, fluidized bed adsorption,
simulated moving bed adsorption, and others (Rouquerol et al. 2014; Dotto et al.
2015a; Rodrigues 2015). In this chapter, the discontinuous batch adsorption and the
fixed bed adsorption will be addressed, since they account for about 90% of the
scientific literature.
Figure 2.1 shows a schematic representation of a discontinuous batch adsorption
operation. In this case, a certain amount m of a pure adsorbent is put in contact with
a solution with an initial volume V0 and an initial concentration of adsorbate C0.
The solution is stirred at temperature constant until the end of operation (e.g., the
equilibrium). During the operation period, the adsorbate is transferred to the
adsorbent surface, decreasing its concentration in the solution until Ce and increas-
ing its quantity in the solid phase until qe (Crini and Badot 2008).
22 J.S. Piccin et al.

Stirring at
constant T until
the equilibrium

m, C0, m, Ce,
V0, q0 Vf, qe

Fig. 2.1 Schematic representation of a discontinuous batch adsorption operation

In discontinuous batch operations, a simple mathematic treatment is normally

performed to obtain the amount of adsorbate adsorbed into the adsorbent at
equilibrium (qe). A global mass balance of the adsorbate is given by Eq. (2.1)
(Geankoplis 1998):

C0 V 0 þ q0 m ¼ Ce V f þ qe m ð2:1Þ

For a virgin adsorbent, the amount of adsorbate at the beginning is equal to 0,

leading to Eq. (2.2):

C0 V 0 ¼ Ce V f þ qe m ð2:2Þ
or
C0 V 0  Ce V f
qe ¼ ð2:3Þ
m

In the majority of the experimental cases, the aliquot removed for quantification
of the adsorbate is negligible regarding the total volume of the solution, leading to
V0 ¼ Vf ¼ V. So, the amount of adsorbate adsorbed into the adsorbent at equilibrium
is given by Eq. (2.4):

ðC0  Ce ÞV
qe ¼ ð2:4Þ
m

The discontinuous batch adsorption systems are useful and fundamental to verify
the quality of an adsorbent and define some operational parameters, such as pH,
temperature, amount of adsorbent, and operation time, in laboratory scale. Also it is
used for industrial applications for small volumes (Piccin et al. 2009, 2011).
Figure 2.2 shows a schematic representation of a fixed bed adsorption operation.
In fixed bed adsorption systems, a solution with initial adsorbate concentration C0
(normally named influent) is pumped at a flow rate Q, through a column with
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 23

Fig. 2.2 Schematic representation of a fixed adsorption operation

Z height, which is packed with a certain amount m of adsorbent. During the

operation, the adsorbate is transferred from the solution to the adsorbate surface.
As a consequence, the solution is clarified, achieving an output concentration of Ct.
The output solution is normally named effluent. The equilibrium is attained when
the bed saturation occurs, i.e., Ct ¼ C0 (Shafeeyan et al. 2014).
In the case of fixed bed operations, the data analysis is performed aiming to
obtain the breakthrough time (tb), exhaustion time (te), length of mass transfer zone
(Zm), effluent volume (Veff), maximum capacity of the column (qeq), and removal
percentage (R). The breakthrough time (tb) is considered when the outlet adsorbate
concentration attains low levels (in general less than 5%) in relation to the initial
concentration, and the exhaustion time (te) is considered when the outlet concen-
tration attains 95% of the initial concentration. The Zm reflects the shortest possible
adsorbent bed length needed to obtain the breakthrough time tb at t ¼ 0. The metric
length of this zone is calculated by Eq. (2.5) (Worch 2008):


tb
Zm ¼ Z 1  ð2:5Þ
te

The volume of the effluent, Veff, is given by Eq. (2.6):

V eff ¼ Qttotal ð2:6Þ

where ttotal is the total operation time.

24 J.S. Piccin et al.

The maximum capacity of the column (qeq) is given by Eq. (2.7):


Ð
ttotal Ct
QC0 1 dt
0 Co
qeq ¼ ð2:7Þ
m

The integral in Eq. (2.7) is the area above the breakthrough curve from Ct/C0 ¼ 0
to Ct/C0 ¼ 1.
The removal percentage (R) is given by Eq. (2.8) (Dotto et al. 2015b):


Ð
ttotal Ct
1 dt
0 Co
R¼ 100 ð2:8Þ
ttotal

The fixed bed systems are useful and fundamental in order to scale up the
adsorption operations. The real operational conditions, such as flow rate and bed
height, can be simulated, and parameters for scale-up can be obtained. For example,
from laboratory fixed bed experiments, it is possible to estimate the column height
necessary to obtain a good quality effluent in a determined time. This height can be
easily transferred for pilot or industrial scale (Vieira et al. 2014; Dotto et al. 2015b).
To develop an adsorption operation, in discontinuous batch or in fixed bed
systems, the first step is the adsorbent choice and the second is the obtainment of
the adsorption isotherms. Adsorption isotherms are a relation between the amount
of adsorbate adsorbed in the adsorbent (qe) and the amount of adsorbate remaining
in the liquid phase (Ce), when the two phases are in dynamic equilibrium at a
determined temperature. In liquid phase adsorption systems, the isotherm curves
are important due to the following aspects:
• From the isotherm parameters, it is possible to obtain the maximum adsorption
capacity of a determined adsorbent under different experimental conditions. The
maximum adsorption capacity is an indicative of the adsorbent quality.
• Also from the isotherm parameters, it is possible to obtain information about the
energetic, steric, and affinity viewpoints.
• The isotherm shape can provide information about the interaction mechanism
that occurs between the adsorbent and the adsorbate.
• In terms of the adsorption rate modeling, a local equilibrium is generally
considered, in order to solve the partial differential equations. This local equi-
librium is mathematically described by the adsorption isotherms.
• Thermodynamic adsorption parameters, such as standard Gibbs free energy
change (ΔG0), standard enthalpy change (ΔH0), and standard entropy change
(ΔS0), can be found from the isotherms. These parameters are fundamental to
verify the spontaneity and nature of the adsorption operation.
In the light of this knowledge, the equilibrium isotherms should be examined
carefully. Firstly, the equilibrium experiments should be performed with several
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 25

experimental points. After, the isotherm curves should be correctly classified.

Suitable models should be fitted to the curves, in order to find an adequate
representation and consistent parameters. For this, a correct statistic treatment is
necessary. Finally, the isotherms can be used to find information about the adsorp-
tion operation.

2.2 Experimental Procedures to Obtain Equilibrium

Curves

For the construction of adsorption isotherm, it is necessary that a series of equilib-

rium concentration data of the liquid phase with its respective adsorption capacity is
obtained. These data not only should be in temperature equilibrium but also in all
other system conditions, such as adsorbent characteristics, agitation, solution vol-
ume, and especially pH, in the case of adsorption in liquid phase. Then, in the batch
adsorption tests, an adsorbent dosage (m) is mixed with a certain volume (V0) of a
solution at an initial solute concentration (C0).
In this context, a number of methods have been standardized to obtain the
adsorption isotherms and this section will handle some of these methods. The
American Society for Testing and Materials (ASTM) reports two methodologies
for the determination of adsorption isotherms in liquid phase. The ASTM D-3860 is
the standard practice for the determination of adsorptive capacity of activated
carbon by aqueous phase isotherm technique. This practice covers the determina-
tion of the adsorptive capacity of activated carbon to remove undesirable constit-
uents from water and wastewater. The method suggested by the ASTM, in this case,
reports that different adsorbent dosages are placed into contact with a solution
containing known solute concentration. Thus, when equilibrium is reached, differ-
ent values of equilibrium concentrations (Ce) are obtained and the adsorption
capacities (qe) are calculated by Eq. (2.4). According to the method, for the
activated carbon, usually after few hours equilibrium is reached. However, the
time required for equilibrium to be reached will be treated later.
Already the ASTM D-4706 test method covers the determination of the relative
activation level of unused or reactivated carbons by adsorption of iodine from
aqueous solution. This test method is based upon a three-point adsorption isotherm,
and the standard iodine solution is treated with three different weights of activated
carbon under specified conditions, according to the ASTM D-3860. The equilib-
rium data are processed using the Langmuir model (which will be discussed later)
and the iodine number is the maximum adsorption capacity of the monolayer (qm).
Van Den Hul and Lyklema (1968) and Hang and Brindley (1970) proposed a
method for determining the available surface area for adsorption in an aqueous
medium based on adsorption isotherm Methylene Blue dye (CAS No. 61-73-4).
This method is based on the adsorption of a layer of Methylene Blue on the surface
(internal and external) material. Based on the maximum monolayer adsorption
26 J.S. Piccin et al.

capacity (qm) obtained by Langmuir model (Eq. (2.18)) that is treated subsequently,
it is possible to obtain the number of molecules adsorbed per unit area (the
projected area of the Methylene Blue molecule is 1.08  1018 m2/molecule) and
the total area (ap, in m2/g) of the adsorbent according to Eq. (2.9):

ap ¼ 1:7388qm ð2:9Þ

Although the methods of ASTM suggest that the adsorption isotherms are
performed by different dosages of adsorbent, more recent works by adsorption,
especially those that use nonconventional adsorbents, have chosen to use fixed
adsorbent dosages, and different point isotherms are obtained varying the solute
initial concentration of the solution. By this method, variations in the adsorption
system conditions are less susceptible. In this case, for example, stock solutions
containing 300 or 400 mg/L (or more) are diluted in the ratio 1:1 (solution/solvent)
obtaining different initial conditions. Both methods (different dosages of adsorbent
and different initial concentrations of the solute solution) lead to the same result if
the technique is properly developed.
However, we want to draw attention to the considerations regarding the adsorp-
tion equilibrium. Several authors have presented data kinetic adsorption capacity
justifying that equilibrium is achieved within hours after consecutive measurements
performed in relatively short times (few minutes or a few hours) showing similar
results. However, we consider that for determining the correct balance, this should
be measured in longer periods of time, i.e., from 8 to 12 h, being performed until
there are no observed changes in the equilibrium concentration. The evaluation of
these changes can be detected by lower coefficients of variation of 5% in the
equilibrium concentration in three consecutive measurements, as suggested by
some authors.

2.3 Classification of the Equilibrium Isotherms

As described above, the equilibrium isotherms show the amount of adsorbate that
can be adsorbed by the adsorbent (qe) in relation to the equilibrium concentration of
the adsorbate in fluid phase (Ce). These are critical parameters in the adsorption
system design. Furthermore, the shape of the equilibrium curve helps to explain
certain phenomena associated with the interaction between the adsorbate and
adsorbent. Therefore, the isotherm shape not only provides information on the
affinity between the molecules but also reflects the possible mode of interaction
between adsorbate and adsorbent (Wong et al. 2004).
The classification of liquid–solid adsorption isotherms describes a system (Giles
et al. 1960) and suggests how their form can be used to diagnose the adsorption
mechanism, in order to obtain information regarding the physical nature of the
adsorbate and the adsorbent surface and also to measure the specific surface area of
the adsorbent. In this classification, the equilibrium curves are identified according
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 27

s L H C
1
Adsorption capacity qe (mg or mol)/g
2

σ σ
σ σ
3
4
mx

Equilibrium concentration Ce (mg or mol)/L

Fig. 2.3 Adsorption isotherm classification (Giles et al. 1960)

to the initial slope into four main classes, and subgroups are described for each
class, based on the shapes of the upper parts and slope changes. Figure 2.3 shows
the classification proposed by Giles et al. (1960).
The main classes are (i) S curves or vertical orientation isotherm, (ii) L curves or
normal or “Langmuir” isotherms, (iii) H curves or high affinity isotherms, and
(iv) C curves or constant partition isotherm.
S Curves As can be seen in Fig. 2.3, the S type isotherm has an inclined slope of the
curve followed by a vertical orientation. Initially, when the adsorbate concentration
increases, there is a chance of the adsorbate to find an available site so that it can
occupy, due to competition between solute molecules. Thus, the adsorption capac-
ity is “limited,” reaching a plateau. However, this behavior in type S isotherms is
opposed, causing the increase of curve slope. This is due to a vertical orientation
tendency of the solute molecules in a higher concentration, and then more sites are
28 J.S. Piccin et al.

Fig. 2.4 Schematic representation of the molecule orientation in S type isotherms: (a) at low
concentration; (b) at high concentration (Giles et al. 1960)

available for adsorption. In practice, the S curve usually appears when three
conditions are fulfilled: (a) the solute molecule is monofunctional; (b) there is a
moderate intermolecular attraction, leading to pack vertically in regular array in the
adsorbed layer; and (c) there is strong competition, for substrate sites, from
molecules of the solvent or another adsorbed species. Figure 2.4 shows a schematic
representation of the orientation of the molecules in S type isotherms.
L Curves The normal or Langmuir isotherms are most commonly found in solute
adsorption in aqueous solution. The initial shape of the equilibrium curve follows
the basic premise that the higher the solute concentration, the greater the adsorption
capacity until the number of adsorption site clearance is limited, occurring compe-
tition between solute molecules for the available sites. Usually, it is an indicative
that the molecules are adsorbed flat on the surface or, sometimes, of vertically
oriented adsorbed ions with particularly strong intermolecular attraction. Thus they
have one of the following characteristics: (i) the adsorbed molecules are more likely
to be adsorbed flat or (ii) are systems with high polar solute and substrate. This
isotherm type indicated that the adsorption occurs due to relatively weak forces,
such as van der Waals forces.
H Curves The basic difference between the normal isotherms or L type with the
high affinity isotherm relates to the beginning of the equilibrium curve. While L
type isotherm has its beginning in the origin, H type isotherm shows an initial
portion with a vertical orientation, and qe values are higher than zero, even when the
concentration of solute tends to values close to zero. The adsorbed species are often
large units, for example, ionic micelles or polymeric molecules However, some-
times, they can be simple ions, which exchange with others of much lower affinity
with adsorbent surface, for example, sulfonated dye. This isotherm type indicates
chemisorption and adsorption by electrostatic forces. Other classifications com-
monly used for H type isotherms are like an irreversible isotherm, because when an
adsorption occurs at a high concentration, a concentration reduction does not
change the adsorption capacity.
C Curves The isotherms with partition constant are characterized by a linear
behavior of the equilibrium data at low concentrations of solute. This behavior
follows Henry’s law for ideal gas equilibrium phases, which translated to adsorp-
tion processes, and suggests that the adsorption capacity is proportional to the
solute concentration, up until the maximum possible adsorption, where an abrupt
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 29

change to a horizontal plateau occurs. This is the type of curve obtained for the
partition of a solute between two practically immiscible solvents. In such cases, the
affinity of the solute by the solid is greater than the affinity for the solvent, or when
the adsorption sites are available in quantities sufficient for the adsorption of all
solute, but the bonding forces between the solute and the solvent are weak and
depend on the liquid phase concentration.

2.3.1 Subclasses

The subclass 1 of S type isotherm indicates a complete vertical behavior of the

adsorption capacity, possibly caused by surface precipitation of solute on the
surface of the adsorbent. In the case of classes L, H, and C, they occur when the
adsorption sites were not fully occupied, or there was not a complete vertical
orientation of the molecules of the solvent. This isotherm type is usually described
by the Freundlich model (for the case of L and H type) or Henry’s law (for the
C type).
The subclass 2 indicates that there is no intermolecular interaction between the
solute, forming a long plateau, indicating a saturation of the adsorbent monolayer.
In this case, a high energy barrier should be overcome before the additional
adsorption can occur on new sites, after the surface has been saturated to the first
degree. Therefore, the solute has high affinity for the solvent, but low affinity for the
layer of solute molecules already adsorbed. In this case, equilibrium data can be
represented by Langmuir model and the plateau is represented by the maximum
adsorption capacity (qm) (for the case of L and H isotherm type).
In subclass 3, a short plateau must mean that the adsorbed solute molecules
expose a surface, which has nearly the same affinity for more solute as the original
surface possessed. This indicates that the solute in the solution has some
intermolecular interaction with the solute in the adsorbent surface, leading to the
formation of multilayers.
The subclasses 4 are attributed to the development of a fresh surface in which
adsorption can occur. The second plateau represents the complete saturation of the
new surface. This additional layer may occur when (i) a proportion of the original
surface may be uncovered by reorientation of the molecules already adsorbed, due
to intermolecular interactions, (ii) formation of new surfaces in crystalline solids,
generating new adsorption sites, or (iii) already exposed parts that allow the
formation of two layers, for example, due to formation of micelles.
Finally, the mx subclass occurs occasionally when a fall in slope occurs after the
first inflection. This is probably due to the association of the solutes in solution;
with increase in concentration, the solute–solute attraction begins to increase more
rapidly than the adsorbent–solute attraction.
30 J.S. Piccin et al.

2.4 Adsorption Isotherm Models

2.4.1 Henry’s Law

Henry’s law can be applied for the adsorption on a uniform surface at sufficiently
low concentrations, in which all molecules are isolated from their nearest neigh-
bors. The relationship between the fluid phase concentration and the adsorbed phase
equilibrium concentration is linear, with a constant of proportionality, which is
equal to the adsorption equilibrium constant, known as the Henry constant (KH).
This linear relationship is commonly referred to as Henry’s law by analogy with the
limiting behavior of dissolution of gases in liquids. The constant of proportionality,
which is simply the adsorption equilibrium constant, is referred to as the Henry
constant (KH) and may be expressed in terms of concentration:

qe ¼ K H Ce ð2:10Þ

For physical adsorption, there is no change in molecular state of adsorption, i.e.,

for adsorption on a uniform surface at sufficiently low concentration, all molecules
are isolated from their nearest neighbors. The equilibrium relationship between
fluid phase and adsorbed phase concentration will be linear, and the relation to the
surface concentration (ns) can be presented in Eq. (2.11):

KH
ns ¼ Ce ð2:11Þ
a

where a is the specific surface area per unit volume of the adsorbate (Ruthven
1984).

2.4.2 Monolayer Adsorption and the Langmuir Isotherm

The adsorbent and the adsorbate are in dynamic equilibrium, and the fractional
coverage of the surface depends on the concentration of the adsorbate. The extent of
surface coverage is normally expressed as the fractional coverage, θ (Langmuir
1918):

Number of adsorption sites occupied

θ¼ ð2:12Þ
Number of adsorption sites available

The physical simplicity of the isotherm is based on four assumptions (Atkins and
De Paula 2006):
• Adsorption cannot occur beyond monolayer coverage.
• Each site can hold only one adsorbate molecule.
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 31

• All sites are energetically equivalent and the surface is uniform.

• The ability of a molecule to adsorb in a given site is independent of the
occupation of neighboring.
In the dynamic adsorption equilibrium, the adsorption and desorption rates are
the same, so

AðaqÞ þ MðsurfaceÞ , AMðsurfaceÞ ð2:13Þ

The rate of surface coverage due to adsorption is proportional to the solution

concentration CA of A and the number of vacant sites N(1  θ), where N is the total
number of sites and can be expressed as

dθ
¼ ka CA N ð1  θÞ ð2:14Þ
dt

The change of θ due to desorption is proportional to the number of adsorbed

species Nθ, so

dθ
¼ kd Nθ ð2:15Þ
dt

where the kinetic constants are ka for adsorption and kd for desorption.
At equilibrium, there is no change in the composition in both phases (the sum of
these two rates is equal to zero), and solving for θ results in the Langmuir isotherm:

K L Ce
θ¼ ð2:16Þ
1 þ K L Ce

where the Langmuir constant (KL) is

ka
KL ¼ ð2:17Þ
kd

Considering the exchange of molecules between adsorbed and liquid phase, the
fraction covered can be considered the relation between the adsorption capacity at
equilibrium (qe) and the maximum adsorption capacity, which occur when all sites
of the monolayer are occupied (qm).
qe
θ¼ ð2:18Þ
qm

Replacing Eq. (2.18) in Eq. (2.16), the Langmuir equation becomes

qm k L C e
qe ¼ ð2:19Þ
1 þ k L Ce
32 J.S. Piccin et al.

2.4.3 Multilayer Adsorption and the BET Isotherm

When the initial adsorbed layer becomes a surface for further adsorption, instead of
the isotherm stabilized in a saturated monolayer, the formation of multilayers can
be expected. The most widely used isotherm for the multilayer adsorption was
derived by Brunauer et al. (1938) and is called the BET isotherm. In liquid systems,
the BET isotherm is (Ebadi et al. 2009)

qBET k1 Ce
qe ¼ ð2:20Þ
ð1  k 2 C e Þð1  k 2 C e þ k 1 C e Þ

where qBET is the monolayer adsorption capacity (mg/g), k1 and k2 are the BET
constants (L/mg).

2.4.4 Other Isotherm Models

In the Langmuir isotherm model, the independence and energetic equivalence of

the adsorption sites are attributed. Deviations of this supposition can be identified
using other models. Various attempts have been made to take these variations into
account.

2.4.4.1 Temkin Isotherm

The Temkin isotherm equation assumes that the heat of adsorption of all the
molecules in the layer decreases linearly with coverage due to adsorbent–adsorbate
interactions and that the adsorption is characterized by a uniform distribution of the
binding energies, up to some maximum binding energy. The Temkin model is given by

RT
θ¼ ln ðK T Ce Þ ð2:21Þ
ΔQ

where θ is the fractional coverage (defined in Eq. 2.17), R is the universal gas
constant (kJ/mol K), T is the temperature (K), ΔQ ¼ ΔH is the variation of
adsorption energy (kJ/mol), and KT is the Temkin equilibrium constant (L/mg).

2.4.4.2 Freundlich Isotherm

The Freundlich isotherm assumes that the adsorption occurs on a heterogeneous

surface, and the amount that is adsorbed increases infinitely with an increase in
concentration (Freundlich 1906). In liquid phase, this isotherm is given by
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 33

qe ¼ kF C1=n
e
F
ð2:22Þ

where kF is the Freundlich constant (a common error is noted in kF unit, i.e., mg1c
Lc/g, where c ¼ 1/nF) and 1/nF is the heterogeneity factor. This isotherm attempts to
incorporate the role of adsorbate–adsorbate interactions on the surface.

2.4.4.3 Dubinin–Radushkevich (D-R) Isotherm

The Dubinin–Radushkevich (D-R) isotherm model considers that adsorbent size is

comparable to the micropore size, and the adsorption equilibrium relation for a
given adsorbate–adsorbent combination can be expressed independently of temper-
ature by using the adsorption potential (ε), according to Eq. (2.23):


1
ε ¼ RT ln 1 þ ð2:23Þ
Ce

The D-R isotherm assumes a Gaussian-type distribution for the characteristic

curve and the model can be described by Eq. (2.24):
 
qe ¼ qmax exp βε2 ð2:24Þ

where qmax is the D-R constant (mg/g) and β gives the mean sorption free energy
E (kJ/mol) at the moment of its transfer to the solid surface from the bulk solution
and can be computed using Eq. (2.25):

1
E¼ ð2:25Þ
ð2βÞ1=2

2.4.4.4 Redlich–Peterson (R-P) Model

The Redlich and Peterson (1959) developed an empirical isotherm model at three
parameters used to represent the adsorption equilibrium over a wide concentration
range and can be applied in either homogeneous or heterogeneous systems due to its
versatility. The R-P model combines elements of Langmuir and Freundlich models
and is shown in Eq. (2.26):

kR Ce
qe ¼ ð2:26Þ
1 þ aR Ce β

where kR and aR are the R-P constant (L/g and Lβ/mgβ, respectively) and β is the
exponent, which can vary between 1 and 0.
34 J.S. Piccin et al.

Besides the R-P model, a number of other isotherm models of three and four
parameters were developed empirically. However, most are simple modifications of
Langmuir and Freundlich models, without a significant relevance in adsorption
studies.

2.4.5 Statistical Physics Models

Some models based on statistical physics are used to fit and interpret the adsorption
isotherms in liquid phase. The hypotheses of the statistical physics models are more
complicated and are developed by using the canonical ensemble in statistical
physics. Consequently, the interpretations of the adsorption process using the
statistical physics models are more useful. The statistical physics models have
physicochemical parameters, which are able to explain the adsorption from the
macroscopic and microscopic viewpoints.
The statistical physics models suppose that a variable number of ions/molecules
are adsorbed on NM receptor sites per unit surface (identical receptor sites) and
independent receptor sites (NM1 and NM2) of the adsorbent surface. To establish the
statistical physics models, it is necessary to write the expression of the partition
function of one receptor site. The general expression is given by
X
Zgc ¼ eβðεi μÞNi ð2:27Þ
N i ¼0, 1...

where (εi) is the adsorption energy of receptor site, μ is the chemical potential of
receptor site, Ni is the occupation state of receptor site, and β is defined as 1/kBT
(where kB is the Boltzmann constant and T the absolute temperature).
If the receptor sites are identically related to NM receptor sites, the total grand
canonical partition function is written as
 N
Z gc ¼ zgc M ð2:28Þ

But, if the receptor sites are independent (two types of receptor sites), the total
grand canonical partition function is given by
 N  N
Zgc ¼ zgc1 M1 zgc2 M2 ð2:29Þ

According to the literature, the average site occupation number No can be written as

∂ ln Z gc
N o ¼ kB T ð2:30Þ
∂μ

When the thermodynamic equilibrium is reached, the equality between the

chemical potentials can be written as μm ¼ μ/n where μ is the chemical potential
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 35

of the adsorbed ions/molecules, n is the number or fraction of ions/molecules per

site, and μm is the chemical potential of dissolved ions/molecules as


N
μm ¼ kB T ln ð2:31Þ
ztr

where ztr is the translation partition function, according to


2πmkB T 3=2
ztr ¼ V ð2:32Þ
h2

where m is the adsorbed mass, h is the Planck constant, and V is the volume of
studied system. Finally, the adsorbed quantity as function of concentration describ-
ing the expression of the statistical physics model is given by

Q ¼ nN 0 ð2:33Þ

By the application of the general methodology describing the statistical physics

model development, the expressions of the discussed models are presented in
Table 2.1.

2.4.6 Typical Values of Isotherm Parameters for Different

Adsorbate–Adsorbent Systems

Table 2.2 presents typical values of the parameters of the isotherm models for
different adsorption systems in liquid phase. Henry’s law is applied to represent C1
isotherm type, according to Giles et al. (1960) classification, when the number of

Table 2.1 Statistical physics models based on the general partition function
Model Equation
Monolayer model with one energy Q (2.34)
Q¼ c0 n
1=2
1þ
c
Monolayer model with two energies n1 N 1M n2 N 2M (2.35)
Q¼ c n1 þ c n2
1 2
1þ 1þ
c c

n
2n
Double layer model with two energies c c (2.36)
þ2
c1 c2
Q ¼ nN M
n
2n
c c
1þ þ
c1 c2
Multilayer model with saturation ½F1 ðcÞ þ F2 ðcÞ þ F3 ðcÞ þ F4 ðcÞ (2.37)
Q ¼ nN M
½GðcÞ
Table 2.2 Isotherm parameters for several adsorbent–adsorbate systems
36

Adsorbent Adsorbate Parameters References

Henry law kH (L/g)
Fungal biomass Acid yellow 49 0.848 Russo et al. (2010)
Chromium tanned leather waste Acid yellow 194 1.909 Piccin et al. (2013)
Calcined diatomite Methylene Blue 0.26 Khraisheh et al. (2005)
Reactive black 0.36
Reactive yellow 0.17
Diatomaceous earth Reactive black 0.42 Al-Ghouti et al. (2003)
Reactive yellow 0.18
Langmuir model kL (L/mg) qm (mg/g)
Sugarcane bagasse Ni(II) 0.173 64.1 Dotto et al. (2016b)
Chitosan/bentonite composite Methylene Blue 2.055 496.5 Dotto et al. (2016c)
Chitosan FD&C red 40 0.395 372.9 Piccin et al. (2009)
Papaya seeds Tartrazine 0.373 51.0 Weber et al. (2014)
Fungal biomass Acid blue 62 0.024 300 Russo et al. (2010)
Natural palygorskite Methylene Blue 0.010 187.3 Zhang et al. (2015)
S. melongena leaf powder Pb(II) 0.274 71.4 Yuvaraja et al. (2014)
CoFe2O4 graphene oxide Pb(II) 0.095 299.4 Zhang et al. (2014)
Hg(II) 0.237 157.9
Activated carbon Lanaset gray G 0.208 108.7 Baccar et al. (2010)
Activated carbon Anthracene 0.260 8.35 Saad et al. (2014)
Activated carbon Fluoxetine 0.375 1112.0 Nabais et al. (2008)
Freundlich model kF (mg1  cLc/g) nF
Ca-bentonite Congo red 26.91 3.23 Lian et al. (2009)
Dried soya bean meal Reactive red 2 5.268 1.079 Sahadevan et al. (2009)
NKA-2 resin Flavones 23.11 1.789 Chen and Zhang (2014)
Fe3O4 nanospheres Neural red 10.62 2.17 Iram et al. (2010)
J.S. Piccin et al.
Activated carbon Polyphenols 6787.97 0.112 Marsal et al. (2009)
Acid-treated oil shale ash Deltamethrin 2.406 2.01 Al-Qodah et al. (2007)
Cationic polymer-loaded bentonite Acid scarlet GR 15.35 4.484 Li et al. (2010)
Acid dark blue 2G 20.58 5.319
Cashew nut shell Congo red 1.357 2.279 Kumar et al. (2010)
Cationic polymer/bentonite Acid dark blue 2G 12.834 4.47 Qian Li et al. (2010)
Fungal biomass Acid red 266 114 3.7 Russo et al. (2010)
Temkin model kT (L/g) ΔQ (J/mol)
Activated carbon from waste biomass Methylene Blue 33.8 1307 Nunes et al. (2009)
Zeolites Phenol 16.7 537.6 Yousef et al. (2011)
Surface modified tannery waste Rhodamine B 1.04 69.9 Anandkumar and Mandal (2011)
Cr (VI) 7.06 117.3
BET model k1 (L/mg) k2 (L/mg) qBET (mg/g)
Perfluorooctyl alumina MTBE 1.2251  102 4.6965  104 3.5 Ebadi et al. (2007)
Chitosan films Vanadium 1.3  102 2.97  103 90.13 Cadaval et al. (2016)
Formaldehyde-pretreated Pinus pinaster bark Phenol 37.84 6.19  102 0.086 Vázquez et al. (2007)
Chromium-tanned leather waste Acid black 210 0.522 1.7  103 108.8 Piccin et al. (2013)
Carbonized bark Pentachlorophenol 16.224 0.184 0.841 Ebadi et al. (2009)a
RP model kR (L/mg) αR (Lβ/mgβ) β
Cashew nut shell Congo red 5.548 3.186 0.638 Kumar et al. (2010)
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . .

Zeolites Phenol 51.5 6.28 0.72 Yousef et al. (2011)

a
Using data of Edgehill (1998)
37
38 J.S. Piccin et al.

adsorption sites is very superior to the number of adsorbate molecules, due to a

hydrophobic interaction between the adsorbent and adsorbate. The increase of kH
constant represents an increase of adsorption capacity at low concentrations.
The Langmuir model is satisfactory to represent H2 or L2 isotherm type,
according to Giles et al. (1960) classification. In practice, the constant kL is
associated with increased affinity of the adsorbate by adsorbent, since kL represents
the inverse of the equilibrium concentration in the liquid phase when the adsorption
capacity reaches 50% of the monolayer adsorption capacity (or f(1/kL) ¼ 0.5qm,
where f is the function of the Langmuir isotherm). Therefore, kL increase leads to a
higher initial slope of the adsorption isotherm. On the other hand, qm is associated
with the curve plateau formation and complete saturation of the monolayer adsor-
bate. qm is in the order from unity to tens of milligrams per gram in the case of
monatomic ion adsorption and in the order from hundreds to thousands of milli-
grams per gram for dyes and larger molecule adsorption. However, Table 2.2 shows
that the maximum monolayer adsorption capacity can vary due to many factors,
such as chemical structure of the adsorbate and adsorbent, molecular size, and
nature of the adsorbent.
The Freundlich model is satisfactory to describe the adsorption isotherm data of
types S, L, and C (subclass 1). The 0 < nF < 1 when the isotherm is of class S
(or unfavorable), nF > 1 when the isotherm is of class L (or favorable), and nF ¼ 1
when the isotherm is of class C. In the latter case, usually when the number of
adsorption sites is greater than the number of molecules to be adsorbed, the
Freundlich model is simplified to Henry model. Already, the kF values are associ-
ated with the initial slope of the isotherm curve.
The BET isotherm is an extension of the Langmuir theory for monolayer
adsorption to multilayer adsorption, and it is satisfactory to represent the H3 or
L3 isotherm type, according to the Giles et al. (1960) classification. qBET and k1
have the same physical significance as to that of qm and kL Langmuir constant,
respectively.
Then, an increase in the equilibrium concentration leads to an increase of
adsorption capacity. This behavior is due to secondary adsorption at a given site,
forming a multilayer and providing a suitable adjustment to the BET model. The
multilayer formation may occur due to a change in organizational form of dye
molecules arranged on the surface of the adsorbent, in horizontal to vertical
alignment, or due to solubility reduction caused by superficial hydrophobic inter-
actions between the adsorbate and the adsorbent (Piccin et al. 2013). The k2
constant represents the inverse of the concentration value when the isotherm
becomes a vertical line and is associated with superficial solubility of adsorbate
(Cs ¼ 1/k2). The k2 value increment is due to a vertical orientation of the isotherm at
lower equilibrium concentration in the liquid phase. In this case, Ebadi et al. (2009)
demonstrated that the use of adsorbent solubility concentration leads to serious
errors in the interpretation of the adsorption data. According to the authors, k2 or Cs
must be obtained by adjusting the model to experimental data. When k2 tend to
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 39

600
333 K
313 K
500
293 K

400
qe (mg/g)

300

200

100

0
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280
Ce (mg/L)
Fig. 2.5 Equilibrium isotherms following the BET multilayer model for vanadium adsorption
onto chitosan films (Cadaval et al. 2016)

zero, the BET model can be mathematically simplified to the Langmuir model,
releasing degrees of freedom for the model and simplifying the use of the data
(Piccin et al. 2013).
Figure 2.5 shows the equilibrium curves of vanadium adsorption onto chitosan
films at different temperatures (Cadaval et al. 2016). In this example, the temper-
ature increase led to an increase in the qBET value from 90.9 to 102.3 mg/g. This
behavior suggests an endothermic phenomenon. The k1 and k2 values increased
with increasing temperature. The k1 increase indicates that lower equilibrium
concentrations are necessary to saturate the monolayer, and the k2 increase indicates
that smaller equilibrium concentrations are necessary to the isotherm that becomes
a vertical line. However, Piccin et al. (2013) observed contrary behavior toward the
concentration of surface saturation (Cs). In this case, a temperature reduction led to
a reduction of Cs values, indicating that the highest adsorption capacities by
multilayer formation were obtained with lower equilibrium concentrations. This
reduction is associated with the solubility of the dye in water, generally lower at
high temperatures, and the increased adsorbate–absorbent forces at low
temperatures.
Regarding the Redlich–Peterson model, and other models of three and four
parameters reported in the literature (Wong et al. 2004; Piccin et al. 2009; Kumar
et al. 2010; Yousef et al. 2011), in most cases these do not provide suitable
adjustments to the experimental data to the point of its use to be justified. In this
case, simpler models such as Langmuir or Freundlich are satisfactory to represent
the experimental data.
40 J.S. Piccin et al.

2.5 Regression Methods and Error Analysis

Several models are able to describe the experimental results of adsorption and are
used in equilibrium, kinetics, and mechanisms studies. In the process of statistically
analyzing empiric data, errors that lead to the unreliable results can occur. The
misuse of linearization is a common error in data analysis. When the data are
transformed in order to achieve a linear equation, it is required to know how the
error-structure of the data is affected by this tranformation. When the errors are
additive on the dependent variable and the usual assumptions of normality and
equal variance throughout the range of the data are checked, then the transformation
of the dependent variable with a nonlinear function can eliminate the distributional
properties. This can occur in the linearization of adsorption isotherms; for example,
the Langmuir model (Eq. 2.19) is nonlinear; thus the dependent variable does not
depend linearly on the independent variable (El-Khaiary and Malash 2011).
These nonlinear forms can be mathematically manipulated and linearized at
different linear forms. Moreover, the statistical tests used to check the fit will often
not detect that the parameters are biased. Table 2.3 presents the different lineari-
zations to the Langmuir and Freundlich models.
The statistical regression methods consist in minimizing objective functions
through the variation of the model parameters. Table 2.4 summarizes some of
these functions and its main characteristics.
From Eqs. (2.42), (2.43), and (2.44), SSE, R2, and ABS provide a better fit for
higher yexp values, because errors are proportional to their magnitudes. SSE is the
most common error function in use. In the R2 function, the objective is to maximize
the results, and the ABS is similar to the SSE to some extent. In relation to
Eqs. (2.45), (2.46), (2.47), and (2.48), the values of (χ 2), ARE, HYBRID, and
MPSD improve the fit at low concentrations by dividing by the experimental
value HYBRID, and MPSD also includes the number of degrees of freedom of the
system, which is important in the analysis of models with different parameter
numbers.
The main objective function used for both linear and nonlinear regressions is the
sum of the squares of the errors (SSE). In the case of linearized forms of the
Langmuir model, the function y ¼ β0 + β1x represents the experimental data.

Table 2.3 Linearized form of adsorption isotherm models

Model Linearized form Plot
Langmuir I Ce 1 1 Ce (2.38)
¼ þ Ce vs:Ce
qe kL qm qm qe
Langmuir II 1 1 1 1 1 (2.39)
¼ þ vs:
qe qm kL qm Ce qe C e
Langmuir III qe qe (2.40)
¼ kL qm þ kL qe vs:qe
Ce Ce
Freundlich 1 log (qe) vs . log (Ce) (2.41)
logðqe Þ ¼ logðkF Þ þ logðCe Þ
nF
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 41

Table 2.4 Error function used for isotherm model regression

Function name Error function
Sum of square error (SSE) n 
P 2
(2.42)
SSE ¼ yi, exp  yi, mod
i¼1
Coefficient of determination (R2) n 
P 2
(2.43)
yi, exp  yi, mod
i¼1 SSE
R2 ¼ 1  n 
P 2 ¼ 1 
SST
yi, exp  yi, exp
i¼1
Sum of the absolute errors (ABS) n 
P  (2.44)
ABS ¼ y 
i, exp  yi, mod
i¼1
 2
Chi-square (χ 2) (2.45)
Pn yi, exp  yi, mod
χ2 ¼
i¼1 yi, mod
X n  
Average relative error (ARE) 100 y  yi, mod  (2.46)
ARE ¼  i, exp 
n i¼1  yi, mod 
 2
Hybrid fractional error function (2.47)
100 X n yi, exp  yi, mod
(HYBRID) HYBRID ¼
n  np i¼1 yi, mod
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Marquardt’s percent standard devi- u 2  32 (2.48)
u yi, exp  yi, mod
ation (MPSD) u 1 X n
MPSD ¼ 100t 4 5
n  np i¼1 yi, mod

Where yi, exp. is the experimental value of independent variable, yi, mod is the modeled value, yexp is
the mean of observed values, SST is the sum of squares of total deviations, n is the number total of
informations, and np is the number of parameters of the model

Thus, β0 and β1 values can be obtained from the minimization of the objective
function (SSE) using the method of linear least squares estimation. However, for
nonlinear form of the isotherm models, there is no closed method for obtaining
parameters. Instead, in this case, numerical algorithms are used to minimize the
objective function and obtain the values of the model parameters. Most algorithms
involve choosing initial values for the parameters. Then, the parameters are refined
iteratively, that is, the values are obtained by successive approximation. The most
commonly used algorithms, in this case, are the Gauss–Newton, Levenberg–
Marquardt and the Generalized Reduced Gradient.

2.5.1 Model Accuracy

The coefficient of determination (R2), defined above, to obtain the more suitable
model to represent equilibrium and kinetic and thermodynamic parameters is
another common practice in adsorption experiments.
The R2 value is very sensitive to extreme data points, resulting in misleading
indication of the fit. The R2 is also influenced by the range of the independent
42 J.S. Piccin et al.

variable and increases as the range of independent variable increases and decreases
as the range decreases. These issues can be avoided by fitting the data to the model
without any transformations and by examination of extreme points.
Another relevant fact is that the R2 can be made manipulated using more
parameters in the model, since the increase in the number of regression parameters
leads to decreases in SSE value. Therefore, the good fit cannot be based only on SSE
(and R2). This is especially common in adsorption studies when it comes to
estimating equilibrium parameters. For this fact, the analysis of the adjusted
determination coefficient (Radj2), which takes into account the experimental degrees
of freedom (n1) and the model degrees of freedom (n(np + 1)), can be a good
tool in selecting models. Radj2 is described in Eq. (2.49):
!
n1  
Radj 2 ¼ 1    1 þ R2 ð2:49Þ
1  np þ 1

where n is the number of information and np is the number of model parameters.

Moreover, Akaike’s information criterion (AIC) (Anderson and Burnham 2002)
is a well-established statistical method that can be used to compare the models with
different numbers or parameters. For a small sample size, AIC is calculated for each
model from Eq. (2.50):

  
SSE 2np np þ 1
AIC ¼ n ln þ 2np þ   ð2:50Þ
n n  np þ 1

A smaller AIC value suggests that the model has more likely to show a better fit.
The AIC values can be compared using the evidence ratio (Er), which is defined by

1
Er ¼ ð2:51Þ
e0:5Δ

where Δ is the absolute value of the difference in AIC between the two models. The
evidence ratio means how many times one model is more likely than the other one
in relation to the experimental data.

2.5.2 Comparison Between Linear and Nonlinear Regression

Methods

In this section, we want to show the effect of the regression method used on the
parameters of the model and the adjustment to the experimental data. To exemplify
this, we use common adsorption data of a FD&C Red No. 40 dye onto chitosan with
deacetylation degree of 84%, particle size of 99 μm, and pH 7.0 at 25  C (Piccin
et al. 2009). The model parameters were obtained by the different linearized forms
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 43

of models (Table 2.5), using the linear least squares estimation method, and by the
nonlinear models (Eqs. (2.19), (2.20), (2.21), and (2.22)), using GRG nonlinear
algorithm of add-in solver function of MS Excel (Microsoft, USA). Figure 2.6
shows the experimental data. Figure 2.7 shows the linearized data according to
Langmuir I, II, and III and Freundlich forms, respectively.
According to Fig. 2.7d, the linearized form of Freundlich model shows a best fit
(R2 ¼ 0.9797). However, the forms I and III of Langmuir model have poor
adjustment (R2 < 0.900) to the experimental data. However, in Table 2.5, it can
be observed that the R2 and SSE values for Langmuir, independent of the way of
obtaining the model parameters, provide a better fit to the experimental data. These
data make it clear that the different forms of linearization can lead to serious errors

Table 2.5 Model parameters and respective determination coefficient (R2) and sum of square
error (SSE) from adsorption of acid red No. 40 onto chitosan obtained by different regression
methods
Model Parameters
Langmuir kL  103 (L/mg) qm (mg/g) R2 SSE
Nonlinearized 4.656 181.6 0.9918 174.41
Langmuir I 4.121 193.6 0.9911 188.63
Langmuir II 2.659 269.4 0.9684 675.36
Langmuir III 3.739 207.4 0.9899 218.65
Freundlich kF (mg1c Lc/g) nF R2 SSE
Nonlinearized 2.896 1.559 0.9821 383.44
Linearized 1.659 1.328 0.9690 662.51

Fig. 2.6 Adsorption equilibrium data of acid red No. 40 dye by chitosan (Piccin et al. 2009)
44 J.S. Piccin et al.

Fig. 2.7 Adjustment of the linearized forms of models to equilibrium experimental data of FD&C
red No. 40 dye onto chitosan: (a) Langmuir I; (b) Langmuir II; (c) Langmuir III; and (d)
Freundlich

in the conclusion of which model is most suitable to represent the experimental

data. The use of one variable both as dependent and independent variable, as in the
case of Langmuir I (Ce) and Langmuir III (qe), leads to an inadequate correlation.
The error distribution of the dependent variable (Ce/qe or qe/Ce) is different from
both the error distributions of Ce and qe. In the case of Langmuir II, the reversal of
relative weights of data points because of 1/qe and 1/Ce in dependent and indepen-
dent variables, respectively, leads to distortion of error distribution. This distortion
can be observed in Fig. 2.7b, where most of the data are grouped together in a small
space of the Cartesian plane, near to the origin. For the Freundlich linearized model,
an alteration of relative weights of the data because of log(qe) in the dependent
variable and a distortion of relative weights of data because of log(qe) and log(Ce)
in the dependent and independent variables, leading to distortion of error distribu-
tion, occur.
Furthermore, it is observed that Langmuir II form, which has best linearized fit,
overestimates the qm values, when compared to the other forms of the model. In this
case, the model fit curve introduces distortions of the experimental data for high
adsorption capacity, as shown in Fig. 2.7 (solid lines), which can lead to errors in
the analysis and design of the equipment. For this reason, the correct form of the
analysis and modeling equilibrium curves is through normalized form (or not
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 45

linearized) of the equilibrium data. The linearization can be used as a method of

visual analysis of the data range to which a model will fit properly to the experi-
mental data (e.g., equilibrium curves with multilayer adsorption), but not as the
conclusion about the adjustment of or obtaining the model parameters.

2.6 Adsorption Thermodynamics

In solid–liquid adsorption systems, the estimation of the thermodynamic parame-

ters is essential. In general, the adsorption thermodynamics is studied by the
estimation of standard Gibbs free energy change (ΔG0), standard enthalpy change
(ΔH0), and standard entropy change (ΔS0) (Crini and Badot 2008). From these
parameters, it is possible to verify if the adsorption is favorable, spontaneous,
endothermic, or exothermic. It is possible to obtain information regarding the
disorder in the solid–liquid interface during the adsorption. Also, it is possible to
infer about the adsorption nature, i.e., physisorption or chemisorption, and verify if
the operation is controlled by enthalpy or entropy (Ruthven 1984; Dotto et al.
2016a). Indeed, the correct calculation of the adsorption thermodynamic parame-
ters is fundamental.
In the thermodynamic sense, the majority of the studies has considered the
adsorption as a reaction (Liu 2009):

A þ B !AB ð2:52Þ

The adsorbent (A) interacts with the adsorbate (B), forming AB. When this
reaction attains the thermodynamic equilibrium, the chemical potentials in the
liquid phase (μl) and in the solid–liquid interface (μsl) are equal, and the Gibbs
free energy change (ΔG) tends to zero, leading to Eq. (2.53) (Chen and Zhang
2014):

ΔG ¼ μsl  μl ¼ ΔG0 þ RT ln ðK e Þ ¼ 0 ð2:53Þ

then,

ΔG0 ¼ RT ln ðK e Þ ð2:54Þ

where R is the universal gas constant, T is the temperature, and Ke is the equilibrium
thermodynamic constant.
The relationship of ΔG0 with ΔH0 and ΔS0 can be expressed as (Liu 2009)

ΔG0 ¼ ΔH 0  TΔS0 ð2:55Þ

46 J.S. Piccin et al.

Substituting Eq. (2.54) in Eq. (2.55), the following relation is obtained:

ΔH 0 ΔS0
ln ðK e Þ ¼  þ ð2:56Þ
RT R

Then, by the plot of ln (Ke) versus (1/T), the values of ΔH0 and ΔS0 can be found.
The graph is known as the Van’t Hoff plot. This methodology is used in several
works in order to estimate the adsorption thermodynamic parameters (Crini and
Badot 2008; Dotto et al. 2015a).
The use of Van’t Hoff plot is relatively simple but is dependent of the correct
calculation of the equilibrium thermodynamic constant Ke. Indeed, the Ke values
are calculated by different manners in the literature, and some of these manners are
unreasonable (Milonjic 2007). For example, in most cases, Ke is used with units.
However, from the mathematical viewpoint, a parameter that has a dimension
cannot be computed logarithmically. The parameter in transcendental functions
must be dimensionless; otherwise, the computation for this parameter does not
make sense (Zhou et al. 2012). In other cases, Ke is obtained from the distribution
constant (Ke ¼ Cad/Ce) (being Ce and Cad, the adsorbate concentrations in solution
and in solid phase at equilibrium, respectively). This is valid only at very low
adsorbate concentrations. Another way is the use of the isotherm parameters (e.g.,
Langmuir, Ke ¼ ρqmKL). This is not completely correct but is reasonable, since the
initial slope of the isotherm can be compared with the Henry constant KH (Dotto
et al. 2013).
As presented above, the correct calculation of Ke is a discussed topic, without
common sense. Here, a reasonable mean to find Ke is presented. In a solid–liquid
adsorption system, the equilibrium thermodynamic constant is given by Eq. (2.57)
(Liu 2009):

activity of occupied sites

Ke ¼ ð2:57Þ
ðactivity of vacant sitesÞðactivity of adsorbate in solutionÞ

Assuming that the activity of the occupied and unoccupied sites is the same,
Eq. (2.57) becomes (Zhou et al. 2012)

θ
Ke ¼ ð2:58Þ
ð1  θÞαe

where αe is the activity of the adsorbate in solution at equilibrium and θ is the

fraction of the surface covered at equilibrium. For the Langmuir model, θ is given
by Eq. (2.18) (for other isotherms, qm can be replaced by the parameter relative to
the maximum adsorption capacity in mol/g). The activity of a substance can be
related to its molar concentration (Ce) according to Eq. (2.59) (Smith et al. 2005):

γ e Ce
αe ¼ ð2:59Þ
γ 0 C0
2 Adsorption Isotherms in Liquid Phase: Experimental, Modeling. . . 47

where γ e is the activity coefficient at the adsorption equilibrium, γ 0 is the activity

coefficient at the standard state, and C0 is the molar concentration of the standard
reference solution (1 mol/L).
Substituting Eqs. (2.18) and (2.59) in Eq. (2.58), for very dilute solutions (γ e ¼ γ 0),
Eq. (2.60) is obtained (Zhou et al. 2012):
qe
qm
Ke ¼
 ð2:60Þ
qe Ce
1
qm C 0

or


Ce
qm K e 0
qe ¼
C  ð2:61Þ
Ce
1 þ Ke 0
C

In this way, the dimensionless Ke can be found by fitting of the Eq. (2.61) with
the experimental data of qe (mol/g) versus Ce (mol/L), considering C0 ¼ 1 mol/L.
The regression and the parameter estimation should have good statistical indicators,
as presented in Sect. 2.5.
After the correct estimation of the thermodynamic parameters, some important
information about the adsorption can be obtained. For example, the negative values
of ΔG0 show a spontaneous and favorable process. The higher the ΔG0 magnitude,
the more favorable and spontaneous the adsorption. Negative values of ΔH0
indicate an exothermic process, while positive values of ΔH0 show an endothermic
process. The magnitude of ΔH0 can give an idea about the interactions that occur
between the adsorbent and adsorbate. Physisorption, such as van der Waals inter-
actions, is usually lower than 20 kJ/mol, and electrostatic interaction ranges from
20 to 80 kJ/mol. Chemisorption bond strengths can be from 80 to 450 kJ/mol. In
relation to the ΔS0, negative values show that the randomness decreases at the solid
solution interface during the adsorption, and positive values suggest the possibility
of some structural changes or readjustments in the adsorbate–adsorbent complex.
Finally, if ΔH0 contributes more than the TΔS0 to find negative values of ΔG0, the
adsorption is an enthalpy controlled process; otherwise, if TΔS0 contributes more
than ΔH0, the adsorption is an entropy controlled process (Crini and Badot 2008;
Bergmann and Machado 2015).

2.7 Concluding Remarks

This chapter presented some fundamental aspects about the equilibrium isotherms
in liquid phase adsorption, taking into account the academic and industrial view-
points. In order to obtain accurate and correct interpretations about the adsorption
48 J.S. Piccin et al.

operation from the equilibrium isotherms, some paramount aspects should be

remarked:
• The correct determination of the adsorption equilibrium requires at least 8 h of
experiment. The experiments should be performed until the liquid phase con-
centration remains constant (coefficients of variation lower than 5%) after three
consecutive measurements.
• The choice of the equilibrium models to be fitted with the experimental data
cannot be performed indiscriminately. The experimental equilibrium curves
should be classified according to the shape, and then only the adequate models
should be used to fit the experimental data.
• For a correct parameter estimation from the isotherm models, the use of
nonlinear estimation method is strongly suggested. To ensure the fit quality,
the coefficient of determination (R2) and at least one error analysis should be
used. In some cases, the adjusted determination coefficient (Radj2) and AIC are
also necessary.
• The Van’t Hoff plot (ln (Ke) versus (1/T)) is a simple and reasonable way to find
ΔH0 and ΔS0 values. However the equilibrium thermodynamic constant (Ke)
should be used without units. Otherwise, the thermodynamic parameters have no
sense.

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