Chemosphere 258 (2020) 127279

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review

Adsorption isotherm models: Classification, physical meaning,

application and solving method
Jianlong Wang a, b, *, Xuan Guo a
a
Laboratory of Environmental Technology, INET, Tsinghua University, Beijing, 100084, PR China
b
Beijing Key Laboratory of Radioactive Waste Treatment, Tsinghua University, Beijing, 100084, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The derivation and physical meaning

of 13 adsorption isotherms were
analyzed.

The application of adsorption
isotherm models were evaluated and
summarized.

The model validity evaluation equa-
tions were discussed based on
literature.

A user interface for solving isotherms
was developed based on Excel
software.

a r t i c l e i n f o a b s t r a c t

Article history: Adsorption is widely applied separation process, especially in environmental remediation, due to its low
Received 29 April 2020 cost and high efficiency. Adsorption isotherm models can provide mechanism information of the
Received in revised form adsorption process, which is important for the design of adsorption system. However, the classification,
28 May 2020
physical meaning, application and solving method of the isotherms have not been systematical analyzed
Accepted 30 May 2020
Available online 10 June 2020
and summarized. In this paper, the adsorption isotherms were classified into adsorption empirical iso-
therms, isotherms based on Polanyi’s theory, chemical adsorption isotherms, physical adsorption iso-
Handling Editor: Y Yeomin Yoon therms, and the ion exchange model. The derivation and physical meaning of the isotherm models were
discussed in detail. In addition, the application of the isotherm models were analyzed and summarized
Keywords: based on over 200 adsorption equilibrium data in literature. The statistical parameters for evaluating the
Adsorption fitness of the models were also discussed. Finally, a user interface (UI) was developed based on Excel
Isotherm models software for solving the isotherm models, which was provided in supplemental material and can be
Physical meaning easily used to model the adsorption equilibrium data. This paper will provide theoretical basis and
Solving method
guiding methodology for the selection and use of the adsorption isotherms.
User interface
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Classification and physical meanings of the isotherm models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

* Corresponding author. Full post address: Energy Science Building, INET, Tsing-
hua University, Beijing, 100084, PR China.
E-mail address: wangjl@tsinghua.edu.cn (J. Wang).

https://doi.org/10.1016/j.chemosphere.2020.127279
0045-6535/© 2020 Elsevier Ltd. All rights reserved.
2 J. Wang, X. Guo / Chemosphere 258 (2020) 127279

2.1. Adsorption empirical isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2.1.1. Linear model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2. Freundlich isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.3. Redlichepeterson (ReP) isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.4. Sips isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.5. Toth isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.6. Temkin isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2. Adsorption models based on Polanyi’s potential theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2.1. Dubinin-Radushkevich (D-R) model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2.2. Dubinin-Astakhov (D-A) model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. Chemical adsorption models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.1. Langmuir model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3.2. Volmer isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.4. Physical adsorption models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.4.1. BET model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.4.2. Aranovich model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.5. Ion exchange isotherm model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3. Applications of the isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Statistical parameters for the evaluation of the isotherm models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5. Solving methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
6. Concluding remarks and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

1. Introduction adsorption capacity, which is significant in the evaluation of the

performance of the adsorbents.
Adsorption process is a surface phenomenon in which adsor- A variety of isotherms have been applied in adsorption systems,
bates transfer onto adsorbents. Over the past decades, adsorption such as the Langmuir model (Langmuir, 1916, 1918), linear model,
technology has been widely applied for the water and wastewater the Freundlich model (Freundlich, 1906), the Sips model (Sips,
treatment because it is low-cost, efficient, simple, and environ- 1948), the Temkin model (Temkin and Pyzhev, 1940), and the
mentally friendly. The adsorption mechanisms mainly include Brunauer, Emmett, and Teller (BET) model (Brunauer et al., 1938).
chemical adsorption corresponding to the formation of chemical Among these models, the linear, Freundlich, Sips, Temkin, and some
bonds, physical adsorption related to the van der Waals force, and other models are empirical models, which lack of effective theo-
the ion exchange (Fig. 1). The knowledge of adsorption mechanisms retical support. The adsorption mechanisms cannot be obtained
is of great importance to design the adsorbents and the adsorption through these models. Thus, the derivations and physical meanings
systems. The adsorption mechanisms have been investigated by the of these models should be investigated. In addition, the isotherms
modeling of the adsorption equilibrium data, the characterization have been classified according to the number of model parameters
of adsorbent before and after adsorption, the molecular dynamics (Foo and Hameed, 2010; Song and Shen, 2005; Ayawei et al., 2017;
study, and the density functional theory (DFT) calculation (Zhuang Al-Ghouti and Da’ana, 2020) or the shapes of the isotherms (S-, L-,
et al., 2020a; Ahmad et al., 2019; Ghazi et al., 2018). Among these H-, and C-shaped) (Limousin et al., 2007). However, the classifica-
methods, modeling of adsorption data by isotherm models is the tion based on the number of parameters lacks of theoretical basis.
most convenient and widely used one. In addition, the adsorption For example, the Langmuir and BET isotherms are two parameters
isotherm models can provide information of the maximum models, they represent the chemical adsorption and physical

Fig. 1. The possible adsorption mechanisms.

 J. Wang, X. Guo / Chemosphere 258 (2020) 127279
adsorption, respectively. The mechanism information cannot be
provided by the number of model parameters. The classification
based on the shapes of the models has also the limitation, because
the majority of adsorption equilibrium data of liquid-solid systems
are L-shaped. Therefore, the isotherms should be classified more
reasonable based on their physical meanings.
To the best of our knowledge, the physical meaning and the
classification of these isotherms are not thoroughly studied.
Moreover, several isotherms are used in incorrect or unsuitable
forms sometimes. For example, the adsorption potential ε of the
Dubinin-Radushkevich (D-R) model has been estimated in wrong
form of ε ¼ RT ln (1 þ 1/Ce), Where: Ce (mg∙L1) is the equilibrium
concentration; R (8.314 J mol1∙K1) is the universal gas constant; T
(K) is the temperature) (Tang et al., 2018; Hu and Zhang, 2019;
Bezzina et al., 2020). The most frequently used form of the BET
model, which was reported by Foo and Hameed (2010), Staudt et al.
(2013), Petkovska (2014), Saadi et al., and so on, was proved to have
poor estimations in the model parameters in liquid-solid system
(Ebadi et al., 2009).
The majority of published papers used linear regression method
to estimate the model parameters (Foo and Hameed, 2010). The
linear regression method is simple and convenient. However, the
linearization of the adsorption models can change the independent
and dependent variables, and introduce the propagated errors. In
this sense, the estimation of the model parameters is inaccurate
and biased (Ho, 2006; Kumar and Sivanesan, 2006; Bolster and
Hornberger, 2007). The accurate calculations of model parameters
can be given by the nonlinear regression, but it is more complicated
than the linear regression method. Therefore, convenient methods
for solving the nonlinear isotherms should be developed.
The objectives of this review paper were to classify the
adsorption isotherms according to their physical meaning and to
thoroughly analyze the isotherm models. Firstly, the classification,
derivation, and physical meaning of the isotherms were analyzed;
secondly, the application of the isotherm models was summarized
based on literature; thirdly, the statistical parameters which can
evaluate the fitness were analyzed; and finally, a software was
compiled in Excel to solve the nonlinear isotherms.
2. Classification and physical meanings of the isotherm
models
Isotherm refers to the relationship between the equilibrium
adsorbate concentrations in the liquid-phase and the equilibrium
adsorption amount on the solid-phase at a certain temperature. We
can model the equilibrium adsorption data by the isotherms, and
investigate the adsorption information, such as the adsorption
mechanisms, the maximum adsorption capacity, as well as the
properties of adsorbents by the isotherms.
In this section, thirteen isotherms were classified based on their
theoretical derivation and physical meaning as empirical models,
isotherm models based on the Polanyi’s potential theory, chemical
adsorption models, physical adsorption models, and ion exchange
models, according to their physical meanings. The adsorption
empirical isotherms (such as the linear, Freundlich, Sips and Toth
models) are characterized with lacking specific physical meaning.
The isotherm models based on the Polanyi’s potential theory (the
D-R and Dubinin-Astakhov (D-A) models) are semi-empirical
models, which can be used in the modeling of the adsorption of
porous materials. The chemical, physical, and ion exchange models
are theoretical models with rigorous deduction and specific phys-
ical meanings. The chemical isotherms describe the monolayer
adsorption process, the physical isotherms represent the multi-
layer adsorption, while the ion exchange isotherms can model
the ion exchange adsorption process. The derivations and meanings
3
of the isotherm models will be analyzed in this section.
2.1. Adsorption empirical isotherms
2.1.1. Linear model
The linear model (Henry’s law) has the following form:
qe ¼ KCe (1)
where qe (mg$g1) and Ce (mg$L1) are adsorbed amount and
adsorbate concentrations at equilibrium, K (L$g1) is the partition
coefficient.
The linear isotherm model has been used to represent the
partition of adsorbates between solid and liquid phases. The
mechanisms of partition processes are the electrostatic in-
teractions, the van der Waals interactions, as well as the hydro-
phobic interactions (Guo et al., 2019a; 2019b).
The deduction of the linear model is explained as follows.
Based on Langmuir theory (Langmuir, 1916, 1918), the adsorp-
tion and desorption rate are described by Eqs. (2) and (3):
ra ¼ ka ð1  qÞCt (2)
rd ¼ kd q (3)
where ra (mg$g1$h1) and rd (mg$g1$h1) are adsorption and
desorption rate, respectively, ka (L$g1$h1) and kd (mg$g1$h1)
are adsorption and desorption rate constants, respectively, q is the
coverage rate of the adsorption sites (at adsorption equilibrium
q ¼ qe), Ct (mg$L1) is the adsorbate concentration at time t.
If the coverage rate q ≪ 1, Eq. (2) is simplified to Eq. (4):
ra ¼ ka Ct (4)
At adsorption Equilibrium:
ka
qe ¼ Ce (5)
kd
qe equals to qe/qm. Let K equals to qmka/kd, Eq. (5) is transformed
to Eq. (1).
The adsorption mechanisms revealed by the linear model is
shown in Fig. 2. Based on the deduction of the linear model, the
linear model represents the condition that the coverage ratio of the
adsorption sites is low. Therefore, the linear model can represent
the monolayer adsorption at low initial adsorbate concentrations
C0. Khan et al. (2019) suggested that the Langmuir model approx-
imated to Henry’s law when the pressure is low in the adsorption of
gas on solid, which was similar with our results.
Fig. 2. The adsorption mechanisms revealed by the linear model.
4 J. Wang, X. Guo / Chemosphere 258 (2020) 127279

2.1.2. Freundlich isotherm 2.1.3. Redlichepeterson (ReP) isotherm

The Freundlich model is used to represent nonlinear adsorption
phenomenon (Freundlich, 1906). It is one of the most widely used
isotherm in adsorption. The linear and nonlinear forms of the
Freundlich model is given by the following equations:
1=n
qe ¼ KF Ce
1 1 þ aRP Ce
logqe ¼ logKF þ logCe
n
where KF (L $mg 1/n 11/n 1
$g ) and n are constants, the Freundlich
model will reduce to the linear model when n ¼ 1.
The nonlinear Freundlich model (Eq. (6)) can be solved by
nonlinear regression analysis. Eq. (7) is easily to be solved by
plotting log qe versus log Ce. However, the propagated errors are
generated in the linearization process, which lead to the inaccurate
estimations of parameters (Guo and Wang, 2019a). In this paper,
the nonlinear method is recommended in the calculation of the
parameters, which is given in following section.
The Freundlich model has been regarded as an empirical
equation without physical meaning. In many published papers, the
Freundlich isotherm was applied to represent the multi-layer
adsorption on heterogamous surfaces (Zaheer et al., 2019; Wang
et al., 2017). In 1947, Halsey and Taylor derived the Freundlich
model from the Langmuir isotherm:
The adsorption and desorption rate are described by Eqs. (2) and
(3). At adsorption equilibrium, ra ¼ rd:
The ReP model is an empirical hybrid model of the Langmuir
and Freundlich models, which has been frequently applied in the
homogeneous or heterogeneous adsorption processes. The ReP
isotherm model can be described by Eq. (13) (Redlich and
Peterson, 1959):
(6)
KRP Ce
qe ¼ g (13)
(7)
where KRP (L$g1) and aRP (Lg$mg-g) are constants, g is the exponent
(0 ¼ g  1). We can see from Eq. (13) that when g equals to 1, the
ReP model reduces to the Langmuir model (Eq. (26)), and when g
equals to 0 or Ce approaches to 0, it will reduce to the linear model
(Eq. (1)). In addition, if Ce approaches to infinite, qe z (KRP/aRP)
C(1g)
e , which reduces to the Freundlich model (Eq. (6)).
2.1.4. Sips isotherm model
The Sips model is another hybrid model combining the Lang-
muir and Freundlich models (Sips, 1948). According to Ebadi et al.
(2015), Sips model is the most applicable 3-parameter isotherm
model for monolayer adsorption. Sips model can describe the ho-
mogeneous or heterogeneous systems. The non-linear Sips
isotherm model is presented by Eq. (14).
qms KS Cens
qe ¼ (14)
1 þ KS Cens

qe ka where qms (mg$g1) is the maximum adsorbed amount, Ks (Lns$mg-

¼ Ce ¼ bðqÞCe (8)
1  qe
ns
kd ) and ns are the Sips constants.
The Sips model becomes the Langmuir model when ns ¼ 1, and
In which q (mg$g1) is the adsorbed amount given by Eq. (10), becomes the Freundlich model at low C0. However, the Sips model
b(q) is described by the following Equation (Halsey and Taylor, doesn’t satisfy the Henry’s law at low C0. The Sips model can be
1947): derived as following:
q If one adsorbate molecule can be adsorbed on 1/ns adsorption
bðqÞ ¼ A0 eRT (9) sites, the adsorption and desorption rate can be described by Eqs.
(15) and (16) (Ho et al., 2002):
q ¼  qmL lnq (10)
ra ¼ ka ð1  qÞ1=ns Ct (15)
1
where, qmL (mg$g ) is the maximum adsorption capacity, A0 is the
constant.
Substitution of Eqs. (9) and (10) into Eq. (8) yields: rd ¼ kd q1=ns (16)
At adsorption equilibrium, ra ¼ rd:
qe q
¼ A0 eRT Ce (11a)
1  qe 1=ns
ka ð1  qe Þ1=ns Ce ¼ kd qe (17)

qe qmL Rearrangement of Eq. (17) yields:

ln ¼ lnA0 Ce  lnqe (11b)
1  qe RT

When qe z 0.5, Eq. (11b) is simplified to Eq. (12): Cens
ka
kd
qe ¼
 (18)
RT RT
1 þ kka Cens
qe ¼ A0 Ceqml qmL
(12) d

By definition of KF ¼ qmART/qmL
0 and n ¼ qmL/RT, Eq. (12) becomes
Eq. (6).
Thus, the Freundlich model describes the adsorption condition
at which the equilibrium coverage fraction is about 50%.
Ezzati (2019) derived the pseudo-first-order (PFO) model from
the Freundlich isotherm. The PFO model can describe the diffu-
sional adsorption (Guo and Wang, 2019c). Therefore, the Freundlich
model can also describe the physical adsorption process.
Based on the above, both the chemical adsorption with about
50% coverage fraction and the physical adsorption can be repre-
sented by the Freundlich model.
By definition of KS ¼ ka/kd, and qe ¼ qe/qms, Eq. (18) becomes Eq.
(14), the general form of the Sips model.
Therefore, the Sips model represents the monolayer adsorption
of one adsorbate molecule onto 1/ns adsorption sites (Fig. 3).
2.1.5. Toth isotherm model
This model is developed to widen the application of the Lang-
muir model in heterogeneous systems (Eq. (19)) (Toth, 1971). It
assumes that the adsorption energies of most adsorption sites are
smaller than mean energy (Ho et al., 2002).
 J. Wang, X. Guo / Chemosphere 258 (2020) 127279
Fig. 3. The adsorption mechanisms revealed by the Sips isotherm model.
KT Ce
qe ¼  1=z (19)
aT þ Cez
where KT (mg$g1) is the constant, aT (mgz$L-z) is the Toth constant,
z is a component that describes the degree of heterogeneity of the
adsorption systems. z is temperature independent, while the value
of aT increases with the increase of temperature (Rudsinski and
Everetta, 1992). When z ¼ 1, Toth model becomes Langmuir
isotherm. Larger deviation of z from 1 indicates that the adsorption
system is more heterogeneous.
2.1.6. Temkin isotherm
The Temkin model presumes that adsorption is a multi-layer
process (Temkin and Pyzhev, 1940). Extremely high and low con-
centrations values of the adsorbate in liquid phase are ignored.
Yang (1993) derived the statistical mechanical expression for the
Temkin isotherm and substituted the derived equation into the
Clapeyron-Clausius equation, confirmed that the differential heat of
adsorption was linear decreased with increasing coverage.
The Temkin model is presented by Eq. (20) (Temkin and Pyzhev,
1940):
RT
qe ¼ lnðACe Þ (20)
b
where A (L∙g1) and b (J∙mol1) are the constants.
2.2. Adsorption models based on Polanyi’s potential theory
Polanyi’s potential theory assumes that the adsorption system
contains a “adsorption space”, where the molecules lose potential
energies. The potential energies are temperature independent, and
increase in the spaces closing to the adsorbent. The highest po-
tential energy is reached in the pores or cracks inside the adsorbent
(Schenz and Manes, 1975; Polanyi, 1932).
2.2.1. Dubinin-Radushkevich (D-R) model
The D-R model was proposed as an empirical isotherm to
represent the adsorption of vapors on solids (Dubinin and
Radushkevich, 1947). The D-R model is developed according to
Polanyi’s theory and the assumption that the distribution of pores
in adsorbent follows the Gaussian energy distribution (Polanyi,
1932; Gil and Grange, 1996; Da˛ browski, 2001). The nonlinear D-R
model is presented as following:
5
qe ¼ qmDR eKDR ε
2
(21)
Cs
ε ¼ RTln (22)
Ce
where qmD-R (mg$g1) is the maximum adsorbed amount, KDR
(mol2$kJ2) is the model constant, ε (kJ$mol1) is the adsorption
potential based on the Polanyi’s potential theory, Cs (mg$L1) is the
solubility of adsorbates.
It should be noticed that ε has been incorrectly calculated in
many published papers as shown in Eq. (23):


1
ε ¼ RTln 1 þ (23)
Ce
Hu and Zhang (2019) demonstrated that Eq. (23) is a distinct
misconception. The terms ε and RT have the same dimension, and
the term (1 þ 1/Ce) is meaningless because the dimensions of 1 and
1/Ce are inconsistent.
The mean free energy (E, kJ$mol1) can be calculated by Eq. (24):
1
E ¼ pffiffiffiffiffiffiffiffiffiffiffi (24)
2KDR
E is frequently applied to determine whether the adsorption is
dominated by physical process (E < 8 kJ mol1) or chemical process
(8 < E < 16 kJ mol1) (Chabani et al., 2006).
2.2.2. Dubinin-Astakhov (D-A) model
The D-A model (Eq. (25)) was developed as a more generalized
version of the D-R model (Dubinin and Astakhov, 1971).

nDA 
 ε
EDA
qe ¼ e (25a)

nDA 
ε
 EDA
qe ¼ qmDA e (25b)
where qmD-A (mg$g1) is the maximum adsorbed amount, ε
(kJ$mol1) is the adsorption potential, which can be computed by
Eq. (22), EDA (kJ$mol1) is the characteristics energy, nDA is a con-
stant related to the percent of pore filling (Chen and Yang, 1994).
The theoretical basis of the D-A model is the Polanyi’s potential
theory (Polanyi, 1932). The D-A model is a semi-empirical model,
which can be used to investigate the micropore structures of the
adsorbent. Chen and Yang (1994) have derived the D-A model
based on the statistical mechanical principles. According to Chen
and Yang (1994), for adsorption of adsorbate onto adsorbent with
micropores and mesopores, the general isotherm model was
deduced to the D-A model when the equilibrium coverage fraction
was much greater than Ce/Cs. Cheng and Hu (2016) demonstrated
that the D-A model could be applied as a general model for the
adsorption of acetylene on MOFs. The D-A model can represent the
adsorption in homogeneous microporous systems.
2.3. Chemical adsorption models
The chemical adsorption isotherm models consider the mono-
layer adsorption process that the adsorbate molecules are adsorbed
in the adsorption sites of the adsorbents. The following studied
chemical adsorption models (the Langmuir and the Volmer
isotherm models) are theoretical models with specific physical
meanings and reasonable derivations.
6 J. Wang, X. Guo / Chemosphere 258 (2020) 127279
2.3.1. Langmuir model
The most commonly applied Langmuir isotherm was raised to
represent the gas-solid adsorption (Langmuir, 1916, 1918). The
nonlinear and linear Langmuir models are presented as following:
qm KL Ce
qe ¼
1 þ KL Ce
Ce Ce 1 ka Ce þ kd
¼ þ
qe qm KL qm
1
where KL (L$mg ) is the ratio of the adsorption rate and desorption
rate, qm (mg$g1) is the maximum adsorption capacity estimated
by the Langmuir model.
Eq. (26) is solved by the nonlinear regression method. Plotting
Ce/qe versus Ce can solve the linearized Langmuir model (Eq. (27)).
The Langmuir model can be linearized by 4 forms. Other forms of
the linearized Langmuir model (1/qe ¼ (1/(qmKL)*1/Ce þ 1/qm,
qe ¼ qm - (1/KL)*(qe/Ce), and qe/Ce ¼ qmKL - qeKL)) as well as the
comparison of linearization methods were discussed by Guo and
Wang (2019a). Langmuir-1 (Eq. (27)) could provide the most ac-
curate estimations of the parameters among the linearization
methods, which were similar with the nonlinear method. However,
the estimations of the Langmuir constants by the linearization
methods were inaccurate and biased, the error (%) of the estimated
parameters could reach up to 40% (Guo and Wang, 2019a). Even
though Langmuir-1 (Eq. (27)) can give relatively accurate estima-
tions of the model parameters, the performance of Langmuir-1 is
still poorer than the nonlinear method. Foo and Hameed (2010)
also concluded that the nonlinear method represented a powerful
tool, which avoided the drawbacks of linearization process. The
nonlinear method for the Langmuir isotherm is provided in the
following section.
Webber and Chakkravorti (1974) suggested to calculate sepa-
ration factor (RL):
1
RL ¼
1 þ KL C0
The values of RL > 1, RL ¼ 1, and RL < 1 reflect that the adsorption
is unfavorable, linear, and favorable, respectively.
To better understand the mechanisms revealed by the Langmuir
model, the assumptions and deductions of the Langmuir model are
reviewed as follows.
The basic assumptions of the Langmuir isotherm are: (1)
monolayer adsorption; (2) the distribution of adsorption sites is
homogeneous; (3) the adsorption energy is constant; and (4) the
interaction between adsorbate molecules is negligible.
The adsorption and desorption rate are described by Eqs. (2) and
(3). At adsorption equilibrium, Ct and q is replaced by the
Fig. 4. The adsorption mechanisms revealed by the Langmuir isotherm model.
equilibrium adsorbate concentration Ce and the equilibrium
coverage rate qe, and the adsorption rate equals to the desorption
rate:
ra ¼ rd (29)
(26) Simultaneous Eqs. (2), (3) and (29) yield:
ka Ce
qe ¼ (30)
(27)
qe is the ratio of qe and qm. By definition of KL ¼ ka/kd, Eq. (30)
transforms to Eq. (26), which is the standard form of Langmuir
model.
Thus, Langmuir model describes equilibrium condition of
monolayer homogeneous adsorption (Fig. 4). ra is directly propor-
tional to (1 - q) and Ct. rb is only directly proportional to q. qe rep-
resents the coverage ratio of the whole adsorption system,
therefore, the term “homogeneous” means the macroscopic ho-
mogeneous adsorption. For most adsorption processes, the adsor-
bent materials are homogeneous in macroscopic view, and the
solution is homogeneous with agitation. Therefore, even though
the adsorbent materials (such as microplastics, activated carbons
from natural sources, modified mineral, and shale) have irregular
shapes and non-uniform surfaces in microscope, the adsorption can
also be represented by the Langmuir isotherm (Guo and Wang,
2019b; Mondal and Majumder, 2019; Liu et al., 2018). The mono-
layer adsorption on the surfaces and in the pores inside the
adsorbent can also be modeled by Langmuir model. This may help
to explain the results that the equilibrium data can be adequately
represented by Langmuir isotherm, while diffusion is the rate-
controlling-step. For example, Suzaki et al. (2017) concluded that
Langmuir model described the adsorption isotherm of metals in
fixed-bed columns, and the adsorption rate limiting step was in-
ternal diffusion. Marin et al. (2014) demonstrated that the rate
limiting step of dye onto SD-2 was internal diffusion, while the
Langmuir model was adopted to model the process.
(28)
2.3.2. Volmer isotherm model
The Volmer model is a distributed monolayer adsorption model,
which assumes that the adsorbate molecules can move on the
surfaces of adsorbents, and the interactions between adsorbates are
negligible. It is presented as following (Volmer, 1925):
qe qe
bV Ce ¼ e1qe (31)
1  qe
where bv (L$mg1) is the affinity constant, qe ¼ qe/qmV (qmV
(mg$L1) is the maximum adsorbed amount estimated by the
Volmer model).Rearrangement of Eq. (31) yields:
 J. Wang, X. Guo / Chemosphere 258 (2020) 127279 7

models were reviewed.

qe qe
bV C e ¼ eqmV qe (32)
qmV  qe
2.4.1. BET model
Afonso et al. (2016) derived the Volmer model according to BET model was proposed to represent adsorption of gas to
adsorption kinetics:The adsorption rate raV: multimolecular layers (Brunauer et al., 1938). It is a theoretical
multi-layer physical adsorption model (Fig. 5). It has been applied
Ct
raV ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi að1  qÞSV p (33) for calculation the specific areas and the pore size distribution of
2pMRT the porous materials (Duong, 1998). The basic presumptions of BET
isotherm are that the adsorption is multi-layer homogeneous
where raV (mol$kg1$s1) is the adsorption rate, M is the molar
adsorption, the adsorption energy in the first layer is different with
mass, Sv is the specific surface areas of adsorbents, a is the pro-
other layers, and for each layer, the adsorption rate equals to the
portion of the successful impacts and total impacts on the surface of
desorption rate. Ebadi et al. (2009) presented the application of the
the adsorbent, p is the probability that the intermolecular area is
BET model in liquid-solid systems (Eq. (36)). Detailed derivation of
sufficient for molecules to arrive the surfaces, p ¼ exp(-q/(1-q))).The
this model was provided in Ebadi et al. (2009).where KBET1
desorption rate rdV:
(L$mg1) and KBET2 (L$mg1) are adsorption equilibrium parame-
EA ters in first and upper layers, nBET is the number of adsorption
rdV ¼ k0 nV eRT (34) layers, qmBET (mg$g1) is the maximum monolayer adsorbed
amount.
where rdV (mol$kg1$s1) is the desorption rate, EA (J$mol1) is the
For n ¼ 1, BET isotherm reduces to Langmuir isotherm. For
desorption energy, k0 (s1) is the maximum desorption frequency
n ¼ ∞, Eq. (36) is simplified to Eq. (37) (Ebadi et al., 2009):
reached at infinite T, nV (mol$kg1) is the specific adsorbed
amount.At adsorption equilibrium, raV ¼ rdV: qmBET KBET1 Ce
qe ¼ (37)
Ce qe EA
ð1  KBET2 Ce Þ½1  KBET2 Ce þ KBET1 Ce 
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi að1  qe ÞSV e1qe ¼ k0 nV eRT (35)
2pMRT The BET model has another non-linear form (Eq. (38)), which is
1 the most familiar form adopted by literatures, such as Foo and
Considering that qe ¼ nV/nm (nm (mol$kg ) is the maximum
Hameed (2010), Staudt et al. (2013), and Petkovska (2014), and
  
specific adsorbed amount) and bV ¼ aSV = nm k0 exp  RT
EA
Saadi et al..
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qmBET CBET Ce
2pMRT ,Eq. (35) becomes Eq. (31). qe ¼   (38)
ðCs  Ce Þ 1 þ ðCBET  1Þ CCes
2.4. Physical adsorption models
where CBET is the constant, Cs (mg$L1) is the solubility of the
The theoretical physical adsorption isotherm models simulate adsorbate. Cs can be calculated as an adjustable parameter or be
the multi-layer adsorption process. The Van Der Waals force is the treated as a constant taken from solubility data.
main driving forces of the physical adsorption. In this section, the Ebadi et al. (2009) compared the three methods in the appli-
Brunauer, Emmett, and Teller (BET) and the Jovanovich isotherm cations of the BET model: (a) using Eq. (38) where Cs is a constant
taken from solubility data, (b) using Eq. (38) where Cs is an
adjustable parameter, and (c) using Eq. (37). The results indicated
that the application of Eq. (38) to liquid-solid adsorption system led
to poor estimations of the model parameters. The correct form of
the BET model should be Eqs. (36) and (37).

2.4.2. Aranovich model

The Aranovich isotherm is a theoretically corrected poly-
molecular adsorption isotherm, which contains two parameters
and can be used to model the adsorption with broader range of
adsorbate concentrations (Aranovich, 1992). This model is correctly
used in the determination the surface areas of porous adsorbents
(Aranovich, 1992). The basic assumptions of the Aranovich
isotherm are that the surfaces of the adsorbent are flat and ho-
mogeneous, only the “nearest neighbors” interact, and the
desorption energy depends on number of the layers. This model
can solve the problem caused by not taking lateral interactions into
account and the prohibition of vacancies in the adsorbate. The
Fig. 5. The adsorption mechanisms revealed by the BET model. Aranovich isotherm can be described by the following equation
h i (Aranovich, 1992; Duong, 1998):
qmBET KBET1 Ce 1ðnBET þ1ÞðKBET2 Ce ÞnBET þnBET ðKBET2 Ce ÞnBET þ1
qe ¼ 

  qmA CA CCsAe
nBET þ1 qe ¼ sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ð1KBET2 Ce Þ 1þ KKBET1 ffi

KBET1 (39)
BET2
1 KBET2 Ce  KBET2 ðKBET2 Ce Þ

Ce
1 CsA 1þ CA CCsAe
(36)

where qmA (mg$g1) is the maximum adsorbed amount, CA is the

8 J. Wang, X. Guo / Chemosphere 258 (2020) 127279

Aranovich constant, CsA (mg$L1) is the adsorbates monolayer adsorption isotherms (except for the linear isotherm model).
saturation concentration. This model will change to the Henry’s law The best-fit isotherms for adsorption of metals, dyes, pharma-
at low C0. Detailed derivation of the Aranovich isotherm could be ceuticals, and other types of organic pollutants onto biosorbents
seen in Aranovich (1992). and abiotic adsorbents are presented in Tables 2e5. The best-fit or
optimum isotherm refers to the isotherm which can best model the
2.5. Ion exchange isotherm model experimental data, with high value of the coefficient of determi-
nation (R2) or low values of other statistical parameters, such as
The exchange of adsorbate ion MeA with Zþ þ
A or ZA charge onto nonlinear chi-square (c2) and residual sum of squares error (SSE).
þ þ The numbers of the optimum isotherm models are summarized
adsorbent with MeB ion with ZB or ZB charge is described by the

nya and Nagy, 2009; Nagy et al., 2016):
following Equations (Ko in Fig. 6 based on more than 200 adsorption data sets (Abazari et al.,
2019; Ahmed et al., 2017; Ahsan et al., 2018; Akinpelu et al., 2019;
zB MeAZA þ þ zA MeBZB þ  S4zA MeBZB þ þ zB MeAZA þ  S (40) Arami et al., 2008; Asgaria et al., 2019; Barman et al., 2018; Basu
et al., 2019; Beekaroo and Mudhoo, 2011; Bhatti et al., 2016;
Bhosle et al., 2016; Bhowmik et al., 2018; Bouras et al., 2017; Cao
zB MeAZA  þ zA MeBZB   S4zA MeBZB  þ zB MeAZA   S (41) et al., 2019; Chaabane et al., 2020; Chaari et al., 2019;
Chakraborty et al., 2018; Chen and Wang, 2007a, 2007b; 2008a,
where S is the surface adsorption sites. 2008b; 2009, 2011; 2012a, 2012b; 2016a, 2016b; Chen et al., 2014,
The equilibrium constant KB,A of Eqs. (40) and (41) is calculated 2016; 2019, 2020a; 2020b; Cheng and Hu, 2016; Cheng et al., 2019;
by Eq. (42): Costa et al., 2015; da Silva and Pietrobelli, 2019; Dayanidhi et al.,
2020; Deniz and Kepekci, 2016; de Sousa et al., 2018; Dursun,
qZAB cZBA 2006; El-Zahhar et al., 2014; Guo and Wang, 2019b; Guo et al.,
KB; A ¼ (42)
qZBA cZAB 2019a; Hamza et al., 2018; Haque et al., 2010; Hodson et al., 2017;
Hossain et al., 2012; Hu et al., 2019; Igwe and Abia, 2007; Gamoudi
Where qA (mg$g1) and qB (mg$g1) are the adsorbate con- and Srasra, 2019; Karmakara et al., 2019; Lebron et al., 2019; Li et al.,
centrations of MeA and MeB in the solid adsorbent, respectively, cA 2019; Lim et al., 2020; Liu et al., 2020a, 2020b; Luo and Wang, 2018;
(mg$L1) and cB (mg$L1) are the adsorbate concentrations of MeA Maged et al., 2020; Mahmoodi et al., 2010; Mahmoud et al., 2017;
and MeB in solution. Mallek et al., 2018; Mirsoleimani-azizi et al., 2018; Mnasri-Ghnimi
For homovalent exchange process (ZA ¼ ZB) (Nagy et al., 2016): and Frini-Srasra, 2019; Nagy et al., 2016; Ngabura et al., 2018;
qA cB Nguyen et al., 2016; Oveisi et al., 2018; Pan et al., 2005, 2009a;
KB; A ¼ (43) 2009b, 2009c; Phasuphan et al., 2019; Pi et al., 2017; Ping et al.,
qB cA
2006; Reddad et al., 2002; Ringot et al., 2007; Saeidi et al., 2020;

 Sarma et al., 2018; Sebastian et al., 2019; Selvakumar and
cA 1 c
¼ cA þ B (44) Rangabhashiyam, 2019; Shahawy and Heikal, 2018; Shikuku et al.,
qA x KB; A 2018; Silva et al., 2020; Singh et al., 2018; Souza et al., 2018;
Subramanyam and Das, 2014; Sun et al., 2019; Tang et al., 2018;
cB 1   Thang et al., 2019; Tian et al., 2018, 2020; Torabian et al., 2014;
¼ c þ KB; A cA (45)
qB x B Tosun, 2012; Wan et al., 2019; Wang, 1999a, 1999b; 2002; Wang
and Chen, 2006, 2009; 2014; Wang and Guo, 2020; Wang and
where x (mg$L1) is the amount of concentrations of MeA and MeB Shih, 2011; Wang and Wang, 2016, 2019; Wang and Zhuang, 2017,
ions on solid phase. 2019a; 2019b, 2019c; 2020; Wang et al., 2000a, 2000b; 2001, 2016;
For monovalent and bivalent ions exchange process (ZA ¼ 1, 2018; Wu et al., 2013, 2018; 2019; Xing et al., 2016, 2019; 2020;
ZB ¼ 2) (Nagy et al., 2016): Xing and Wang, 2016; Xu et al., 2020; Xu and Wang, 2017; Xue et al.,
2019; Yin et al., 2017; Yu and Wang, 2016; Yu et al., 2016, 2017;
q2A cB Zango et al., 2020; Zazycki et al., 2017; Zhang et al., 2016a, 2016b;
KB; A ¼ (46)
qB c2A 2020a, 2020b; Zhao et al., 2012; Zhou et al., 2010; Zhu and Wang,
2017; Zhu et al., 2012, 2014; Zhuang and Wang, 2019a, 2019b;
2019c; Zhuang et al., 2018a, 2018b; 2018c, 2018d; 2019a, 2019b;
qB c2A
KA;B ¼ (47) 2020a, 2020b; Z_ o
łtowska-Aksamitowska et al., 2018). We mainly
q2A cB
focus on the literatures published in recent 5 years, but some

 models (such as the D-R, D-A, BET, ReP models) are not frequently
cA 1 2 qA cB used in recent years, therefore, some literatures published in earlier
¼ c þ (48)
qA xmono A KB; A cA years are also included.
As shown in Tables 2e5 and Fig. 6, the Langmuir model is the
! most commonly applied optimum isotherm to represent the data of
cB 1 1 c2A
¼ 2cB þ (49) metals ions, dyes, pharmaceuticals, as well as other types of organic
qB xmono KA; B ðxmono  2qB Þ
pollutants onto adsorbents, followed by the Freundlich model. One
reason is that these two models are most frequently adopted in the
where xmono (mg$L1) is the exchange sites, xmono ¼ qA þ 2qB. adsorption studies, owing to the simplicity of the method (linear
regression method). In addition, the Langmuir model represents
3. Applications of the isotherms homogeneous monolayer adsorption, and the adsorption systems
are homogeneous in macroscopic view for most adsorption pro-
The isotherms are shown in Table 1. The linearized isotherms are cesses, as concluded in previous sections. The third reason is that a
not suitable to be used to estimate the parameters because the large number of the adsorption processes is monolayer chemi-
estimations are biased and inaccurate, as reviewed in previous sorption which relate to the surface bonding (Zhuang et al., 2020b;
sections. Therefore, we only present the nonlinear forms of the
 J. Wang, X. Guo / Chemosphere 258 (2020) 127279 9

Table 1
Summary of the adsorption isotherm models.

Classification Model’s name Model equation References

Adsorption empirical isotherm models Linear isotherm model (Henry’s law) qe ¼ KCe e
Freundlich isotherm model qe ¼ KF Ce
1=n Freundlich (1906)
RedlichePeterson (ReP) isotherm model KRP Ce Redlich and Peterson (1959)
qe ¼ g
1 þ aRP Ce
Sips isotherm model qms KS Cens Sips (1948)
qe ¼
1 þ KS Cens
Toth isotherm model K T Ce Toth (1971)
qe ¼ 1=z
ðaT þ CeZ Þ
Temkin isotherm model RT Temkin and Pyzhev (1940)
qe ¼ lnðACe Þ
b
Adsorption models based on the Dubinin-Radushkevich (D-R) isotherm Cs Dubinin and Radushkevich (1947)
qe ¼ qmDR eKDR ε ; ε ¼ RTln
2

Polanyi’s model Ce

nDA 
potential theory Dubinin-Astakhov (D-A) isotherm model ε Dubinin and Astakhov (1971)
 Cs
qe ¼ qmDA e EDA ; ε ¼ RTln
Ce
Chemical adsorption models Langmuir isotherm model qm KL Ce Langmuir, (1916), 1918
qe ¼
1 þ K L Ce
Volmer isotherm model qe Volmer (1925)
qe
bV Ce ¼ eqmV  qe
qmV  qe
Physical adsorption models BET isotherm model (n ¼ ∞) qe ¼ Brunauer et al. (1938)
qmBET KBET1 Ce
ð1  KBET2 Ce Þ½1  KBET2 Ce þ KBET1 Ce 
Aranovich isotherm model Ce Aranovich (1992)
qmA CA
CsA
qe ¼
s ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

ffi 
Ce Ce
1 1 þ CA
CsA CsA


Ion exchange isotherm model Homovalent ion exchange model cA 1 c Ko
nya and Nagy, (2009); Nagy et al.,
¼ c þ B
qA x A KB; A (2016)
cB 1
¼ ðcB þ KB; A cA Þ
qB x


Monovalent and bivalent ions exchange cA 1 2 qA cB
¼ c þ
model qA xmono A KB; A cA
!
cB 1 1 c2A
¼ 2cB þ
qB xmono KA; B ðxmono  2qB Þ

Manaa et al., 2020). The Temkin, Sips, and ReP empirical models
are also applied in some adsorption processes (Tables 2e5 and
Fig. 6). Theoretically, the Sips and ReP models can provide better
predictions for the equilibrium data than the Langmuir model,
because they are 3-parameter models, which combine the Lang-
muir and Freundlich models and are more flexible in parameter
estimations. However, the complications of the nonlinear regres-
sion method make it difficult to solve the Sips and ReP models.
Therefore, the applications of the Sips and ReP models are less than
the Langmuir model. The linear model can successfully describe the
adsorption systems with low C0 (Tables 4 and 5). Guo et al. (2019a)
reported that the adsorption of SMT on microplastics with
C0 ¼ 0e12 mg L1 could be modeled by the linear isotherm. Zhou
et al. (2010) found that the isotherm of PFOA and PFOS on acti-
vated sludge was linear at low values of C0 (0.08e0.63 mm mol$L1
and 0.046e0.93 mm mol$L1, respectively). Zhang et al. also sug-
gested that the adsorption isotherm of 9-nitroanthracene onto
microplastics was linear when C0 ¼ 10e500 mg L1. These results
are coincidence with the theoretical analysis of the linear isotherm
studied in previous section. The D-R model was used to model the
adsorption of metals, dyes, and pharmaceuticals onto biosorbents
and abiotic adsorbents (Tables 2e4 and Fig. 6). However, it has been
used in incorrect form, as reviewed in the previous section. The
correct form of the D-R model is provided in Table 1. The ion ex-
change isotherm was applied in the adsorption of metals ions.
(Nagy et al., 2016). As shown in Tables 2e5 and Fig. 6, the appli-
cations of other types of isotherm models, such as the D-A, BET,
Toth, and Volmer models, are limited. The possible reason is that
the nonlinear solving methods of these models are complicated.
Therefore, we develop a convenient UI to solve these nonlinear
models based on Excel, which is introduced in the following
section.
Based on the theoretical analysis in above sections, it can be
seen that different isotherm models represent different adsorption
mechanisms. However, in most cases, we do not know the possible
adsorption mechanisms. Therefore, we should use isotherms as a
useful tool to investigate the adsorption mechanisms, instead of
understanding the mechanisms and then modeling the equilibrium
data with a certain isotherm. We recommend to fit the equilibrium
data by the chemical, physical and other theoretical isotherm
models, and obtain the optimum isotherm by judging the statistical
parameters.
4. Statistical parameters for the evaluation of the isotherm
models
The statistical parameters (error functions) used to evaluate the
fitness of the isotherms are depicted in Table 6 and Fig. 7, based on
(Sebastian et al., 2019; Basu et al., 2019; Ngabura et al., 2018; Souza
et al., 2018; Wang et al., 2016; Bhatti et al., 2016; Dursun, 2006;
Cheng et al., 2019; Hu et al., 2019; Zazycki et al., 2017; Dayanidhi
et al., 2020; Cao et al., 2019; Zhuang et al., 2018a; b; Mahmoud
et al., 2017; Reddad et al., 2002; Igwe and Abia, 2007; Hossain
et al., 2012; Guo and Wang, 2019b; X. Zheng et al., 2020; Tang
et al., 2018; Hodson et al., 2017; Xing et al., 2016; Chaabane et al.,
2020; Asgaria et al., 2019; Mnasri-Ghnimi and Frini-Srasra, 2019;
Lim et al., 2020; Liu et al., 2020b; Bhosle et al., 2016; Nagy et al.,
2016; Tosun, 2012; Singh et al., 2018; Selvakumar and
Table 2

10
Applications of the adsorption isotherms in the adsorption of metals.

Adsorbate Adsorbent type Adsorbent Adsorption conditions Optimum Model parameters Statistical parameters References
isotherm

Cd(II) Biosorbents Magnetite nanoparticles 200 rpm, C0 ¼ 10e20 ppm Langmuir qmax ¼ 37.03 (mg$g1); KL ¼ 0.23 R2 ¼ 0.98 Sebastian et al. (2019)
synthesi  zed from Hevea bark Freundlich (L$mg1) R2 ¼ 0.99
KF ¼ 6.9 (L1/n$mg11/n$g1); 1/n ¼ 0.90
Na(I) 200 rpm, C0 ¼ 10e20 ppm Langmuir qmax ¼ 3.95 (mg$g1); KL ¼ 0.44 R2 ¼ 0.97
(L$mg1)
Cr(III) Cymbopogon flexuosus 298 K, C0 ¼ 10e200 mg L1 Freundlich KF ¼ 13.4 (L1/n$mg11/n$g1); n ¼ 1 R2 ¼ 0.99 Basu et al. (2019)
immobilized
in sodium alginate beads
Zn(II) Durian peel 120 rpm, 303 K, C0 ¼ 10 Temkin b ¼ 0.5675 kJ mol1; A ¼ 0.0653 L mg1 R2 ¼ 1; Ngabura et al. (2018)
e200 mg L1 SSE ¼ 0.7816
Zn(II) 120 rpm, 313 K, C0 ¼ 10 Temkin b ¼ 0.4223 kJ mol1; A ¼ 0.0662 L mg1 R2 ¼ 1; SSE ¼ 2.5226
e200 mg L1
Zn(II) 120 rpm, 323 K, C0 ¼ 10 Temkin b ¼ 0.7369 kJ mol1; A ¼ 0.0715 L mg1 R2 ¼ 1; SSE ¼ 3.7837
e200 mg L1
Cd(II) Malpighia emarginata D.C. seed 300 rpm Langmuir qmax ¼ 0.124 (mg$g1); KL ¼ 0.095 R2 ¼ 0.9998 Souza et al. (2018)
fiber (L$mg1)
Cr 300 rpm Langmuir qmax ¼ 0.118 (mg$g1); KL ¼ 0.066 R2 ¼ 0.9993
(L$mg1)

J. Wang, X. Guo / Chemosphere 258 (2020) 127279

Cu(II) 300 rpm Langmuir qmax ¼ 0.095 (mg$g1); KL ¼ 0.078 R2 ¼ 0.9996
(L$mg1)
Ni(II) 300 rpm Langmuir qmax ¼ 0.081 (mg$g1); KL ¼ 0.063 R2 ¼ 0.9995
(L$mg1)
Pb(II) Gelation with alginate C0 ¼ 100e1000 mg L1 Langmuir qmax ¼ 435.3 (mg$g1); KL ¼ 0.046 R2 ¼ 0.977 Wang et al. (2016)
(L$mg1)
Cu(II) C0 ¼ 100e1000 mg L1 Langmuir qmax ¼ 167.1 (mg$g1); KL ¼ 0.011 R2 ¼ 0.882
(L$mg1)
Zr(IV) Citrus peel biomass C0 ¼ 10e100 mg L1 Langmuir qmax ¼ 68.4774 (mg$g1); RL ¼ 0.00544 R2 ¼ 0.997 Bhatti et al. (2016)
Pb(II) Pretreated Aspergillus niger 150 rpm Langmuir qmax ¼ 34.69 (mg$g1); KL ¼ 0.021 ε% ¼ 1.3 Dursun (2006)
(L$mg1)
Pb(II) 150 rpm ReP aRP ¼ 0.066 (dm3 mg1)g, KRP ¼ 1.65 ε% ¼ 3.3
(dm3 mg1); g ¼ 0.93
Sr(II) Modified mercerized bacterial 150 rpm, 303.15 K, C0 ¼ 5 Langmuir qmax ¼ 44.86 (mg$g1); KL ¼ 0.085 R2 ¼ 0.996 Cheng et al. (2019)
cellulose membrane e900 mg L1 (L$mg1)
Sr(II) Algal sorbent derived from 100 rpm, pH ¼ 5 Sips qms ¼ 1.72 (mmol$g1); KS ¼ 1.56 R2 ¼ 0.990; c2 ¼ 0.089; Hu et al. (2019)
Sargassum horneri (Lns$mmol-ns); ns ¼ 1.70 RMSE ¼ 0.051; AICc ¼ 81.6
Au Activated carbon (AC) 250 rpm Langmuir qmax ¼ 7.86 (mg$g1); KL ¼ 0.8987 R2 ¼ 0.9895 Zazycki et al. (2017)
(L$mg1); RL ¼ 0.059
V(Ⅳ) Eggshell powder (ES) C0 ¼ 100e500 mmol L1 Freundlich KF ¼ 1.09 (L1/n$mmol11/n$g1); 1/ R2 ¼ 0.9988 Dayanidhi et al. (2020)
n ¼ 0.6707
Fe(II) C0 ¼ 100e500 mmol L1 Freundlich KF ¼ 1.27 (L1/n$mmol11/n$g1); 1/ R2 ¼ 0.9947
n ¼ 0.8551
Fe(III) C0 ¼ 100e500 mmol L1 Freundlich KF ¼ 1.59 (L1/n$mmol11/n$g1); 1/ R2 ¼ 0.9974
n ¼ 0.8546
Pb(II) Multi-pore activated carbons 175 rpm Langmuir qmax ¼ 1.34 (mmol$g1); KL ¼ 37.05 R2 ¼ 0.993 Cao et al. (2019)
(MPAC) (L$mmol1)
Ni(II) 175 rpm Langmuir qmax ¼ 0.97 (mmol$g1); KL ¼ 22.53 R2 ¼ 0.983
(L$mmol1)
U(Ⅵ) Modified chitosan beads 150 rpm, pH ¼ 6, T, 298 K, Langmuir qmax ¼ 117.65 (mg$g1); KL ¼ 0.14 R2 ¼ 0.9995 Zhuang et al. (2018a)
C0 ¼ 10e600 mg L1 (L$mg1)
Cd(II) Heat-inactivated marine C0 ¼ 0.02e0.2 mol L1, pH 7.0 Langmuir qmax ¼ 3333.333 (mg$g1); RL ¼ 0.874 2
R ¼ 0.9992 Mahmoud et al. (2017)
Aspergillus flavus
Pb(II) Sugar beet pulp C0 ¼ 0.2  103e2.5  10-3 M Langmuir qmax ¼ 0.356 (mmol$g1); KL ¼ 16.9 R2 ¼ 0.987 Reddad et al. (2002)
(L$mmol1)
Cu(II) C0 ¼ 0.2  103e2.5  10-3 M Langmuir qmax ¼ 0.333 (mmol$g1); KL ¼ 3.73 R2 ¼ 0.984
(L$mmol1)
Cd(II) C0 ¼ 0.2  103e2.5  10-3 M Freundlich KF ¼ 0.185 (L1/n$mmol11/n$g1); 1/ R2 ¼ 0.975
n ¼ 0.26
Cd(II) Rice husk 850 mm pH ¼ 7.5 D-R e R2 ¼ 0.9988 Igwe and Abia (2007)
Pb(II) Rice husk 450 mm pH ¼ 7.5 D-R e R2 ¼ 0.9765
Zn(II) Rice husk 450 mm pH ¼ 7.5 D-R - R2 ¼ 0.9956
Cu(II) Palm oil fruit shells 120 rpm, C0 ¼ 1e35 mg L1 Sips qs ¼ 45.275; KS ¼ 1.328; ns ¼ 0.898 R2 ¼ 0.994; c2 ¼ 3.797; Hossain et al. (2012)
ReP aRP ¼ 2.054; KRP ¼ 59.502; g ¼ 0.938 R2 ¼ 0.994; c2 ¼ 4.4244;
Toth KT ¼ 34.902; aT ¼ 0.608; z ¼ 0.813 R2 ¼ 0.994; c2 ¼ 4.4043;
Sr(II) Abiotic Polyethylene (PE) 160 rpm, C0 ¼ 0e10 mg L1 Freundlich KF ¼ 0.225 (L1/n$mg11/n$g1); n ¼ 1.35 R2 ¼ 0.989; c2 ¼ 10.8; SSE ¼ 390; Guo and Wang (2019b)
adsorbents AICc ¼ 40.1
Cu(II) L-cysteine
(Cys) intercalated pH ¼ 5, C0 ¼ 5e500 mg L1 Langmuir qmax ¼ 58.07 (mg$g1); KL ¼ 0.1328 R2 ¼ 0.9735 X. Zheng et al., 2020
MgAl-layered double hydroxide (L$mg1)
1
Pb(II) (MgAl-Cys-LDH) pH ¼ 5.73, C0 ¼ 20e1400 mg L Langmuir qmax ¼ 186.2 (mg$g1); KL ¼ 0.0033 2
R ¼ 0.9557
(L$mg1)
Cd(II) pH ¼ 5.85, C0 ¼ 5e500 mg L1 Langmuir qmax ¼ 93.11 (mg$g1); KL ¼ 0.2190 R2 ¼ 0.9511
(L$mg1)
Pb(II) Porous inorganic polymer 250 shakes/min, C0 ¼ 50 Langmuir qmax ¼ 621.12 (mg$g1); KL ¼ 7.69 R2 ¼ 0.998 Tang et al. (2018)
microspheres e150 mg L1 D-R (L$mg1) R2 ¼ 0.995
qmD-R ¼ 620.76 (mg$g1);
KDR ¼ 2.36  108 (mol2$kJ2)
Zn(II) High density polyethylene 220 rpm, C0 ¼ 0.1e10 mg L1 Freundlich ln KF ¼ 5.49; 1/n ¼ 0.43 R2 ¼ 0.72 Hodson et al. (2017)
(HDPE)

J. Wang, X. Guo / Chemosphere 258 (2020) 127279

Zn(II) Woodland soil 220 rpm, C0 ¼ 0.1e10 mg L1 Freundlich ln KF ¼ 5.76; 1/n ¼ 0.65 R2 ¼ 0.94
Co(II) Nanoscale zero valent iron pH ¼ 5.7 Langmuir qmax ¼ 131.58 (mg$g1) e Xing et al. (2016)
(ZVI)/graphene (GF) composite
1 2
Cu(II) Functionalized graphene oxide 293 K, pH ¼ 7 Langmuir qmax ¼ 3.891 (mmol$g ); KL ¼ 0.074 R ¼ 0.988 Chaabane et al. (2020)
sheets GO-EDA-CAC-BPED (L$mmol1)
Ni(II) 293 K, pH ¼ 7 Langmuir qmax ¼ 3.508 (mmol$g1); KL ¼ 3.392 2
R ¼ 0.990
(L$mmol1)
Co(II) 293 K, pH ¼ 7 Langmuir qmax ¼ 3.401 (mmol$g1); KL ¼ 0.086 R2 ¼ 0.992
(L$mmol1)
Cs(I) Metal organic framework 200 rpm Langmuir qmax ¼ 86.2 (mg$g1); KL ¼ 0.01 R2 ¼ 0.98 Asgaria et al., 2019
(MOF) (L$mg1)
Sr(II) 200 rpm Langmuir qmax ¼ 58.47 (mg$g1); KL ¼ 0.01 2
R ¼ 0.99
(L$mg1)
Cd(II) Pillared clays C0 ¼ 10e100 mg L1 Langmuir qmax ¼ 7e24 (mg$g1); KL ¼ 0.749 R2 ¼ 0.997e0.998 Mnasri-Ghnimi and Frini-
e3.346 (L$mg1) Srasra (2019)
Pt(IV) Metal-organic frameworks of 120 rpm, C0 ¼ 0e1600 mg L1 Langmuir qmax ¼ 277.6 (mg$g1); KL ¼ 0.018 R2 ¼ 0.9696 Lim et al. (2020)
MIL-101(Cr)eNH2 (L$mg1)
Pd(II) 120 rpm, C0 ¼ 0e1600 mg L1 Langmuir qmax ¼ 140.7 (mg$g1); KL ¼ 0.003 R2 ¼ 0.9703
(L$mg1)
As(III) Fe0/COFs 300 rpm, C0 ¼ 1.08e4.59 mg L1 Freundlich - R2 ¼ 0.990 Liu et al. (2020b)
Sr(II) Phosphonate-functionalized pH ¼ 3 Freundlich - R2 ¼ 0.969 Bhosle et al. (2016)
polymer
Co Bentonite clay 1440 rpm, pH ¼ 6.5 Ion KAB ¼ 0.64; xmono ¼ 9  104(mg$L1) e Nagy et al. (2016)
exchange
4 1
Mn 1440 rpm, pH ¼ 6.5 Ion KAB ¼ 0.85; xmono ¼ 6.2  10 (mg$L ) e
exchange
4 1
Hg 1440 rpm, pH ¼ 2.76 Ion KAB ¼ 1.02; xmono ¼ 4.2  10 (mg$L ) e
exchange
Ammonium Clinoptilolite 200 rpm, C0 ¼ 30e250 mg L1, ReP aRP ¼ 0.084; KRP ¼ 0.863; g ¼ 0.905 R2 ¼ 0.999 Tosun (2012)
pH ¼ 4.5 Temkin b ¼ 748.566; A ¼ 0.469 R2 ¼ 0.999
Ammonium 200 rpm, C0 ¼ 30e250 mg L1, ReP aRP ¼ 0.585; KRP ¼ 2.217; g ¼ 0.701 R2 ¼ 0.994
pH ¼ 4.5
Ammonium 200 rpm, C0 ¼ 30e250 mg L1, ReP aRP ¼ 0.610; KRP ¼ 2.387; g ¼ 0.709 R2 ¼ 0.993
pH ¼ 4.5

11
Table 3

12
Applications of the adsorption isotherms in the adsorption of dyes.

Adsorbate Adsorbent Adsorbent Adsorption conditions Optimum Model parameters Statistical References
type isotherm parameters

Rhodamine-B (RB) Biosorbents Banana peel powder e Langmuir qmax ¼ 1.6572e3.8804 (mg$g1); KL ¼ 0.0658e0.0913 (L$mg1) R2 ¼ 0.9459 Singh et al. (2018)
e0.9740
Rhodamine-B (RB) Modified biosorbent from Kappaphycu C0 ¼ 10e50 mg L1 Langmuir qmax ¼ 112.35 (mg$g1); KL ¼ 0.001 (L$mg1) R2 ¼ 0.9459 Selvakumar and
alvarezii (EKA) Rangabhashiyam (2019)
Modified biosorbent from Gracilaria C0 ¼ 10e50 mg L1 Langmuir qmax ¼ 105.26 (mg$g1); KL ¼ 0.1 (L$mg1) R2 ¼ 0.9459
Salicornia (EGS)
Modified biosorbent from Gracilaria C0 ¼ 10e50 mg L1 Langmuir qmax ¼ 97.08 (mg$g1); KL ¼ 0.01 (L$mg1) R2 ¼ 0.9459
edulis (ECG)
Congo red (CR) Magnetic mycelial pellets 120 rpm, C0 ¼ 25 Sips qmax ¼ 101.8 (mg$g1) e Q. Zhang et al., 2016a,
e5000 mg L1 2016b
Sunset yellow (SY) Modified skin of Iron stick yam pH ¼ 2, C0 ¼ 100 Langmuir qmax ¼ 476.20 (mg$g1); KL ¼ 10.21 (L$mg1) R2 ¼ 0.9840 Y. Zhang et al., 2016a,
(ISY@PEI) e500 mg L1 2016b
Lemon yellow (LY) pH ¼ 2, C0 ¼ 100 Langmuir qmax ¼ 138.92 (mg$g1); KL ¼ 6.24 (L$mg1) R2 ¼ 0.9821
e500 mg L1
Acid Red 14 Mesoporous egg shell membrane (ESM) 200 rpm ReP KRP ¼ 293714.7 (L$g1); aRP ¼ 349186.2 (Lg$mg-g); g ¼ 0.897703 R2 ¼ 0.992 Arami et al. (2008)
(AR14)
Acid Blue 92 200 rpm ReP KRP ¼ 758653.5 (L$g1); aRP ¼ 481025.2 (Lg$mg-g); g ¼ 0.633962 R2 ¼ 0.998

J. Wang, X. Guo / Chemosphere 258 (2020) 127279

(AB92)
Congo red (CR) Modified Glossogyne tenuifolia leaves C0 ¼ 100e500 mg L1 Freundlich KF ¼ 2.268 (L1/n$mg11/n$g1); n ¼ 3.457 R2 ¼ 0.994 Yang and Hong (2018)
malachite green C0 ¼ 100e500 mg L1 Freundlich KF ¼ 1.548 (L1/n$mg11/n$g1); n ¼ 22.23 R2 ¼ 0.997
(MG)
Congo red (CR) Penicillium janthinellum sp. strain (P1) 120 rpm, C0 ¼ 25 Langmuir qmax ¼ 344.83 (mg$g1); KL ¼ 0.1261 (L$mg1) R2 ¼ 0.9991 Wang et al. (2015a)
e500 mg L1
Basic Blue 41 Canola hull 200 rpm, C0 ¼ 25 Langmuir qmax ¼ 67.5676 (mg$g1); KL ¼ 1.4095 (L$mg1) R2 ¼ 0.9963 Mahmoodi et al., 2010
(BB41) e100 mg L1
Basic Red 46 200 rpm, C0 ¼ 25 Langmuir qmax ¼ 49.0196 (mg$g1); KL ¼ 0.0165 (L$mg1) R2 ¼ 0.9964
(BR46) e100 mg L1
Basic Violet 16 200 rpm, C0 ¼ 25 Langmuir qmax ¼ 25 (mg$g1); KL ¼ 0.1973 (L$mg1) R2 ¼ 0.9892
(BV16) e100 mg L1
Sulfur blue 15 Acidithiobacillus thiooxidans 200 rpm, pH ¼ 7.7, Langmuir qmax ¼ 1428.6 (mg$g1); KL ¼ 0.00464 (L$mg1) R2 ¼ 0.9982 Nguyen et al. (2016)
(SB15) C0 ¼ 200e2000 mg L1
Reactive-azo (RA) Pistachio by-product C0 ¼ 50e2000 mg L1 Sips qms ¼ 109.535 (mg$g1); KS ¼ 0.0111.409 (Lns$mg-ns); 1/ns ¼ 1.409 R2 ¼ 1 Deniz and Kepekci
(2016)
Congo red (CR) Aspergillus carbonarius M333 250 rpm, C0 ¼ 20 Langmuir qmax ¼ 99.01 (mg$g1); KL ¼ 0.036 (L$mg1) R2 ¼ 0.988 Bouras et al. (2017)
e125 mg L1
Penicillium glabrum Pg1 250 rpm, C0 ¼ 20 Langmuir qmax ¼ 101.01 (mg$g1); KL ¼ 0.079 (L$mg1) R2 ¼ 0.998
e125 mg L1
Methylene Blue Fucus vesiculosus ZnCl2 250 rpm, C0 ¼ 50 Sips qms ¼ 1380.465 (mg$g1); KS ¼ 0.0130.513 (Lns$mg-ns); ns ¼ 0.513 R2 ¼ 0.979 Lebron et al. (2019)
e700 mg L1
Spirulina maxima ZnCl2 250 rpm, C0 ¼ 50 Sips qms ¼ 316.393 (mg$g1); KS ¼ 0.0261.248 (Lns$mg-ns); ns ¼ 1.248 R2 ¼ 0.998
e700 mg L1
Chlorella pyrenoidosa ZnCl2 250 rpm, C0 ¼ 50 Sips qms ¼ 210.844 (mg$g1); KS ¼ 0.0411.019 (Lns$mg-ns); ns ¼ 1.019 R2 ¼ 0.997
e700 mg L1
Congo red (CR) Cashew nut shell (CNS) 120 rpm, C0 ¼ 20 ReP KRP ¼ 5.548 (L$g1); aRP ¼ 3.186 (Lg$mg-g); g ¼ 0.638 qms ¼ 14.29 R2 ¼ 0.999
e100 mg L1 Sips (mg$g1); KS ¼ 0.102 (Lns$mg-ns); ns ¼ 1.841 R2 ¼ 0.999
Toth KT ¼ 67.39 (L$g1), aT ¼ 1.013 (mgz$L-z), z ¼ 0.178 R2 ¼ 0.999
Reactive Red 158 Cocos nucifera L. Shell Powder 200 rpm, adsorbent D-R qmD-R ¼ 0.0035 (mg$g1); KDR ¼ 0.01 (mol2$kJ2) R2 ¼ 0.999 Beekaroo and Mudhoo
(RR158) dosage: 12.5 g/L (2011)
2
200 rpm, adsorbent Temkin b ¼ 194.931; A ¼ 0.010 R ¼1
dosage: 7.5 g L1
200 rpm, adsorbent Temkin b ¼ 1394.244; A ¼ 0.050 R2 ¼ 0.999
dosage: 10 g L1
Methyl orange Abiotic Magnetic zeolite imidazolate 150 rpm Freundlich KF ¼ 0.124 (L1/n$mg11/n$g1); 1/n ¼ 2.113 R2 ¼ 0.995 Xue et al. (2019)
(MO) adsorbents framework-67 composites (MZIF-67)
Direct blue 86 150 rpm Langmuir qmax ¼ 0.085 (mg$g1); KL ¼ 303.03 (L$mg1) R2 ¼ 0.996
(DB-86)
Methyl orange Porous metal-organic framework (MOF) C0 ¼ 5e200 ppm Langmuir qmax ¼ 57.9 (mg$g1) e Haque et al. (2010)
(MO) MIL-53
1
Porous metal-organic framework (MOF) C0 ¼ 5e200 ppm Langmuir qmax ¼ 114 (mg$g ) e
MIL-101
Basic Yellow 28 Smectite rich natural clay e Sips qms ¼ 76.12 (mg$g1); 1/ns ¼ 0.451 R2 ¼ 0.99 Chaari et al. (2019)
(BY28) Langmuir qmax ¼ 76.92 (mg$g1); KL ¼ 0.119 (L$mg1) R2 ¼ 0.996
Cristal Violet (CV) Tunisian Smectite Clay 300 rpm, C0 ¼ 12.5 Toth e R2 ¼ 0.999 Hamza et al. (2018)
e100 mg L1
2
Yellow B2R Chia seeds (Salvia hispanica) oil 150 rpm, 303 K, C0 ¼ 50 Toth e R ¼ 0.9927 da Silva and Pietrobelli
extraction e675 mg L1 (2019)
Bromophenol blue Polymer-clay composite P(AAm-AA)- Room temperature Freundlich 1/n ¼ 0.347 R2 ¼ 0.989 El-Zahhar et al. (2014)
(BPB) Kao
Methyl orange Fe2O3/Mn3O4 nanocomposite 200 rpm, Adsorbent dose Langmuir qmax ¼ 322.58 (mg$g1); KL ¼ 0.256 (L$mg1) R2 ¼ 0.9972; Bhowmik et al. (2018)
(MO) 0.25 g L1 c2 ¼ 1.634
1 1 2
200 rpm, Adsorbent dose Langmuir qmax ¼ 121.95 (mg$g ); KL ¼ 0.956 (L$mg ) R ¼ 0.999;
1 g L1 c2 ¼ 0.331
Acid Orange 7 Modified porous cellulose-based C0 ¼ 20e90 mg mL1 Langmuir qmax ¼ 257.67 (mg$g ) 1
R2 ¼ 0.9909 Wan et al. (2019)
(AO7) microsphere C0 ¼ 20e90 mg mL1 Langmuir qmax ¼ 178.99 (mg$g1) R2 ¼ 0.9605

J. Wang, X. Guo / Chemosphere 258 (2020) 127279

Reactive dyes MIL-101-Cr metal organic framework 293 K, 150 rpm Langmuir qmax ¼ 450 (mg$g1); KL ¼ 0.05 (L$mg1) R2 ¼ 0.93 Karmakara et al., 2019
black 5 (RDBK
5)
Reactive dyes blue 293 K, 150 rpm Langmuir qmax ¼ 435 (mg$g1); KL ¼ 0.08 (L$mg1) R2 ¼ 0.96
2 (RDB 2)
Basic Red 46 Metal-organic framework NH2-MIL- In the presence of Langmuir qmax ¼ 1250 (mg$g1); KL ¼ 1.431 (L$mg1) R2 ¼ 0.995 Oveisi et al. (2018)
(BR46) 125(Ti) ultrasonic irradiation
Basic Blue 41 In the presence of Langmuir qmax ¼ 1429 (mg$g1); KL ¼ 1.290 (L$mg1 R2 ¼ 0.993
(BB41) ultrasonic irradiation
Methylene Blue In the presence of Langmuir qmax ¼ 833 (mg$g1); KL ¼ 1.09 (L$mg1) R2 ¼ 0.953
(MB) ultrasonic irradiation
Methyl orange HDPyþ modified clay 2700 rpm, C0 ¼ 10 Langmuir qmax ¼ 277.27 (mg$g1); KL ¼ 0.29 (L$mg1) R2 ¼ 0.99 Gamoudi and Srasra
(MO) e1000 mg mL1 (2019)
Indigo carmine 2700 rpm, C0 ¼ 10 Langmuir qmax ¼ 326.31 (mg$g1); KL ¼ 0.01 (L$mg1) R2 ¼ 0.98
(IC) e1000 mg mL1
Procion Red MX5B Montmorillonite Mt 303 K, C0 ¼ 20 Temkin b ¼ 2.48 kJ mol1; A ¼ 0.21 L mg1 R ¼ 0.99 Sarma et al. (2018)
(MX5B) e150 mg mL1 Freundlich KF ¼ 0.31 (L1/n$mg11/n$g1); 1/n ¼ 0.62 R ¼ 0.99
Montmorillonite Mt 1 303 K, C0 ¼ 20 Temkin b ¼ 2.75 kJ mol1; A ¼ 0.19 L mg1 R ¼ 0.99
e150 mg mL1 Freundlich KF ¼ 0.37 (L1/n$mg11/n$g1); 1/n ¼ 0.6 R ¼ 0.99
Montmorillonite Mt 2 303 K, C0 ¼ 20 Temkin b ¼ 2.94 kJ mol1; A ¼ 0.18 L mg1 R ¼ 0.99
e150 mg mL1 Freundlich KF ¼ 0.4 (L1/n$mg11/n$g1); 1/n ¼ 0.6 R ¼ 0.99

13
Table 4

14
Applications of the adsorption isotherms in the adsorption of pharmaceuticals.

Adsorbate Adsorbent Adsorbent Adsorption conditions Optimum Model parameters Statistical parameters References
type isotherm

Ciprofloxacin (CIP) Biosorbents Magnetic biosorbents 298.15 K, 220 rpm Langmuir qmax ¼ 527.93 (mg$g1); KL ¼ 0.053 R2 ¼ 0.9911 Zheng et al. (2020)
(L$mg1)
318.15 K, 220 rpm Langmuir qmax ¼ 485.17 (mg$g1); KL ¼ 0.02 R2 ¼ 0.9894
(L$mg1)
Tetracyclines (TC) Sulfonated spent coffee waste e Langmuir qmax ¼ 473.93 (mg$g1); KL ¼ 0.05 R2 ¼ 0.988 Ahsan et al. (2018)
(SCWeSO3H) (L$mg1)
1
Diclofenac (DCF) Biochar C0 ¼ 100e20,000 mg L , pH ¼ 7 Langmuir qmax ¼ 7.25  103 (mg$g1); 2
R ¼ 0.998 Li et al. (2019)
KL ¼ 5.37  103 (L$mg1)
1
Trimethoprim (TMP) Biochar C0 ¼ 100e400,000 mg L , pH ¼ 7 Langmuir qmax ¼ 2.08  103 (mg$g1); 2
R ¼ 0.987
KL ¼ 1.17  103 (L$mg1)
Ibuprofen (IBP) Wood apple biochar (WAB) C0 ¼ 1e45 mg mL1 Freundlich KF ¼ 1.353 (L1/n$mg11/n$g1); 1/ R2 ¼ 0.957 Chakraborty et al. (2018)
n ¼ 1.603
Steam activated wood apple C0 ¼ 1e45 mg mL1 Langmuir qmax ¼ 12.658 (mg$g1); KL ¼ 0.08587 R2 ¼ 0.966
biochar (WASAB) (L$mg1)
Fluoxetine Spent coffee ground (SCG) 170 rpm, pH ¼ 9 Sips qms ¼ 14.31 (mg$g1); KS ¼ 1.78 R2 ¼ 0.996 Silva et al. (2020)
(Lns$mg-ns); 1/ns ¼ 2.54
Pine bark 170 rpm, pH ¼ 9 Sips qms ¼ 6.53 (mg$g1); KS ¼ 15.8 (Lns$mg- R2 ¼ 0.991

J. Wang, X. Guo / Chemosphere 258 (2020) 127279

ns
); 1/ns ¼ 6.74
Cork waste 170 rpm, pH ¼ 9 Sips qms ¼ 4.74 (mg$g1); KS ¼ 1.92 (Lns$mg- R2 ¼ 0.990
ns
); 1/ns ¼ 3.87
Tetracycline (TC) Magnetic nano-scale biosorbent C0 ¼ 40e120 mg mL1, pH ¼ 6 Langmuir qmax ¼ 1.47 (mg$g1); KL ¼ 4.78 R2 ¼ 0.986 Pi et al. (2017)
(Fe3O4/MFX) (L$mg1)
Ochratoxin A (OA) Beta-glucanes 400 rpm BET qmBET ¼ 0.24 (mg$g1); CBET ¼ 9.549 HYBRID ¼ 5.2701  10 3
Ringot et al. (2007)
(L$mg1)
Yeast cell wall fraction (LEC) 400 rpm BET qmBET ¼ 0.040 (mg$g1); CBET ¼ 19.924 HYBRID ¼ 5.5069  103
(L$mg1)
Ibuprofen (IBP) Modified chitin pH ¼ 6, C0 ¼ 250e2000 mg L1 Langmuir qmax ¼ 400.39 (mg$g1); KL ¼ 0.0017 R2 ¼ 0.962 Z_ o

łtowska-
(L$mg1) Aksamitowska et al.,
Acetaminophen (ACT) pH ¼ 6, C0 ¼ 250e2000 mg L1 Freundlich KF ¼ 5.173 (L1/n$mg11/n$g1); n ¼ 2.23 R2 ¼ 0.972 2018
Ibuprofen (IBP) Chitosan-modified waste tire e Freundlich KF ¼ 5.21  109 (L1/n$mg11/n$g1); 1/ R2 ¼ 0.9949 Phasuphan et al. (2019)
crumb rubber n ¼ 6.349
Diclofenac (DFC) e Freundlich KF ¼ 0.056 (L1/n$mg11/n$g1); 1/ R2 ¼ 0.9878
n ¼ 2.78
Naproxen e Freundlich KF ¼ 0.165 (L1/n$mg11/n$g1); 1/ R2 ¼ 0.9863
n ¼ 3.647
Tetracycline (TC) Human hair-derived high surface 120 rpm, C0 ¼ 25e355 mg mL1 Langmuir qmax ¼ 128.52 (mg$g1); KL ¼ 0.0168 R2 ¼ 0.9899 Ahmed et al. (2017)
area material (HHC) (L$mg1)
120 rpm, C0 ¼ 25e355 mg mL1 Langmuir qmax ¼ 210.18 (mg$g1); KL ¼ 0.00458 R2 ¼ 0.9948
(L$mg1)
Chlortetracycline Calcium-rich biochar C0 ¼ 40e2000 mg mL1, pH ¼ 6 ± 1 Freundlich KF ¼ 22.98 (L1/n$mg11/n$g1); n ¼ 1.91 R2 ¼ 0.982 Xu et al. (2020)
(CTC)
1 1 2
Dimetridazole (DMZ) Biomass carbon foam pellets C0 ¼ 40e600 mg mL D-R qmD-R ¼ 0.0012 (mol$g ); KDR ¼ 0.0028 R ¼ 0.9954 Sun et al. (2019)
(BCFPs) (mol2$kJ2)
1
Sulfamethazine (SMT) Polyamide (PA) 160 rpm, C0 ¼ 0e12 mg L Linear K ¼ 38.7 (L$kg1) R ¼ 0.982; c ¼ 0.0186 Guo et al. (2019a)
2 2
 Abiotic Polypropylene (PP) 160 rpm, C0 ¼ 0e12 mg L1 Linear K ¼ 15.1 (L$kg1) R2 ¼ 0.918; c2 ¼ 0.132
adsorbents Polystyrene (PS) 160 rpm, C0 ¼ 0e12 mg L1 Linear K ¼ 21.0 (L$kg1) R2 ¼ 0.996; c2 ¼ 0.073
Cephalosporin C (CEP- Aged Polystyrene (PS) 160 rpm, Freshwater, C0 ¼ 0 Linear K ¼ 21.0 (L$kg1) Adj R2 ¼ 0.989 Guo and Wang (2019b)
C) e10 mg L1
1 2
160 rpm, simulated seawater, Langmuir qmax ¼ 473.93 (mg$g ); KL ¼ 0.05 Adj R ¼ 0.988
C0 ¼ 0e10 mg L1 (L$mg1)
Diclofenac (DFC) Covalent organic frameworks (COFs) 160 rpm at room temperature, Sips qms ¼ 109 (mg$g1); KS ¼ 0.0140.56 R2 ¼ 0.997 Zhuang et al., 2020a,
C0 ¼ 10e200 mg L1 (Lns$mg-ns); ns ¼ 0.56 2020b
Sulfamethazine (SMT) 160 rpm at room temperature, Sips qms ¼ 113.2 (mg$g1); KS ¼ 0.0270.91 R2 ¼ 0.995
C0 ¼ 10e200 mg L1 (Lns$mg-ns); ns ¼ 0.91
Amoxicillin (AMX) Metal-organic framework (MOF; pH ¼ 7, C0 ¼ 10e90 mg L1 Langmuir qmax ¼ 486.4 (mg$g1); KL ¼ 0.126 R2 ¼ 0.9845 Abazari et al. (2019)
[Zn6(IDC)4(OH)2(Hprz)2]n) (L$mg1)
Tetracycline (TC) Metal-organic framework (MOF-5) e Langmuir qmax ¼ 232.558 (mg$g1); KL ¼ 0.377 2
R ¼ 0.9979
(L$mg1) Mirsoleimani-azizi et al.,
2018
Modification of natural bentonite clay C0 ¼ 5e200 mg L1 Freundlich KF ¼ 10.76 (L1/n$mg11/n$g1); n ¼ 2.079 R2 ¼ 0.989; SSE ¼ 164.1 Maged et al. (2020)
(BC)
Thermally activated bentonite (TB) C0 ¼ 5e200 mg L1 Freundlich KF ¼ 21.13 (L1/n$mg11/n$g1); n ¼ 1.944 R2 ¼ 0.997; SSE ¼ 163.5
Nalidixic acid (NA) Montmorillonite pH ¼ 4 Linear K ¼ 1.68 (L$g1) R2 ¼ 0.996 Wu et al. (2013)
Kaolinite pH ¼ 4 Freundlich KF ¼ 0.45 (L1/n$mg11/n$g1); 1/n ¼ 0.28 R2 ¼ 0.98
Tetracycline Hierarchical porous ZIF-8 e Freundlich KF ¼ 46.2 (L1/n$mg11/n$g1) R2 ¼ 0.965 Chen et al. (2019)
Hydrochloride (TH)

J. Wang, X. Guo / Chemosphere 258 (2020) 127279

Chloramphenicol (CP) Hierarchical porous ZIF-8 e Freundlich KF ¼ 1.78 (L1/n$mg11/n$g1) R2 ¼ 0.992
Azithromycin (AZM) Faujasite-type zeolites 1 (FAU1) C0 ¼ 0e400 mg L1, pH ¼ 6.5 Langmuir qmax ¼ 8.5 (mg$g1); KL ¼ 29.93 R2 ¼ 0.847 de Sousa et al. (2018)
(L$mg1)
1
Faujasite-type zeolites 1 (FAU2) C0 ¼ 0e400 mg L , pH ¼ 6.5 Freundlich KF ¼ 9.4 (L1/n$mg11/n$g1); 1/n ¼ 0.106 2
R ¼ 0.831
Sulfamethoxazole Faujasite-type zeolites 1 (FAU1) C0 ¼ 0e400 mg L1, pH ¼ 6.5 Freundlich KF ¼ 26.10 (L1/n$mg11/n$g1); 1/ R2 ¼ 0.998
(SMX) n ¼ 1.571
Faujasite-type zeolites 1 (FAU2) C0 ¼ 0e400 mg L1, pH ¼ 6.5 Freundlich KF ¼ 105.46 (L1/n$mg11/n$g1); 1/ R2 ¼ 0.994
n ¼ 1.847
Tetracycline (TC) Montmorillonite 180 rpm, C0 ¼ 0.1e8 mmol L1 Langmuir qmax ¼ 1.06 (mmol$g1); KL ¼ 5.74 R2 ¼ 0.99 Wu et al. (2019)
(L$mmol1)
1
Ciprofloxacin (CIP) 180 rpm, C0 ¼ 0.1e8 mmol L Langmuir qmax ¼ 0.51 (mmol$g1); KL ¼ 11.1 2
R ¼ 0.99
(L$mmol1)
1
Sulfachloropyridazine Iron-modified clay 303 ± 1 K, C0 ¼ 1e2 mg L Temkin b ¼ 9.029 kJ mol1; A ¼ 2.924 L mg1 R2 ¼ 0.998 Shikuku et al. (2018)
(SCP)
Sulfadimethoxine 303 ± 1 K, C0 ¼ 1e2 mg L1 Temkin b ¼ 9.878 kJ mol1; A ¼ 3.175 L mg1 R2 ¼ 0.794
(SDM)
Sulfamethazine (SMT) Graphene 150 rpm, 298 K, C0 ¼ 2e100 mg L1 Langmuir qmax ¼ 91.08 (mg$g1); KL ¼ 0.201 R2 ¼ 0.969 Zhuang et al. (2018b)
(L$mg1)
1
150 rpm, 308 K, C0 ¼ 2e100 mg L Langmuir qmax ¼ 87.79 (mg$g1); KL ¼ 0.238 2
R ¼ 0.996
(L$mg1)
150 rpm, 318 K, C0 ¼ 2e100 mg L1 Langmuir qmax ¼ 104.93 (mg$g1); KL ¼ 0.234 R2 ¼ 0.991
(L$mg1)

15
Table 5

16
Applications of the adsorption isotherms in the adsorption of other types of organic pollutants.

Adsorbate Adsorbent Adsorbent Adsorption conditions Optimum Model parameters Statistical parameters References
type isotherm

Oil & Grease Biosorbents Phragmites australis e Freundlich KF ¼ 10.84 (L1/n$mg11/n$g1); 1/n ¼ 0.62 R2 ¼ 0.990 Shahawy and
BOD C0 ¼ 3500e20900 mg L1 Langmuir qmax ¼ 2036.66 (mg$g1); KL ¼ 0.00124 (L$mg1) R2 ¼ 0.99 Heikal (2018)
COD C0 ¼ 7300e43600 mg L1 Langmuir qmax ¼ 4385.96 (mg$g1); KL ¼ 0.000455 (L$mg1) R2 ¼ 0.995
Perfluorooctanoate Activated carbon felts (ACFs) VS 120 rpm, pH ¼ 7 Langmuir qmax ¼ 0.0649 (mmol$m2); KL ¼ 0.0198 (L$mmol 1) R2 ¼ 0.998 Saeidi et al. (2020)
(PFOA)
Perfluorooctanesulfonate 120 rpm, pH ¼ 7 Langmuir qmax ¼ 0.154 (mg$g1); KL ¼ 0.187 (L$mg1) R2 ¼ 0.999
(PFOS)
Perfluorooctanoate Activated sludge 150 rpm, C0 ¼ 0.08 Linear K ¼ 150e350 (L$kg1) - Zhou et al. (2010)
(PFOA). e0.63 mmol L1
Perfluorooctanesulfonate 150 rpm, C0 ¼ 0.046 Linear K ¼ 200e4050 (L$kg1) -
(PFOS) e0.93 mmol L1
Phenol (Ph) Granulated cork 40 rpm Freundlich KF ¼ 0.02 (L1/n$mg11/n$g1); 1/n ¼ 0.86 qmax ¼ 0.92 R2 ¼ 0.98 Mallek et al.
Langmuir (mg$g1); KL ¼ 0.016 (L$mg1) R2 ¼ 0.98 (2018)
2-chlorophenol (2-CP) Freundlich KF ¼ 0.05 (L1/n$mg11/n$g1); 1/n ¼ 0.81 qmax ¼ 1.54 R2 ¼ 0.99
Langmuir (mg$g1); KL ¼ 0.029 (L$mg1) R2 ¼ 0.99
2-nitrophenol (2-NP) Langmuir qmax ¼ 5.09 (mg$g1); KL ¼ 0.011 (L$mg1) R2 ¼ 0.99
2,4-dichlorophenol (2,4- Freundlich KF ¼ 0.20 (L1/n$mg11/n$g1); 1/n ¼ 0.80 R2 ¼ 0.99

J. Wang, X. Guo / Chemosphere 258 (2020) 127279

DCP)
Phenol (Ph) Chicken manure biochar 250 rpm, C0 ¼ 10 Langmuir qmax ¼ 106.2 (mg$g1); KL ¼ 7.53 (L$mg1) R2 ¼ 0.98 Thang et al. (2019)
2,4-dinitrophenol (DNP) e200 mg L1, pH ¼ 7.0 Langmuir qmax ¼ 148.1 (mg$g1); KL ¼ 6.45 (L$mg1) R2 ¼ 0.99
1
Acenapthene Urban wood waste activated carbon 308 K, C0 ¼ 2e10 mg L Temkin b ¼ 6.99 kJ mol1; A ¼ 14.43 L mg1 R2 ¼ 0.93 Barman et al.
Naphthalene Temkin b ¼ 0.25 kJ mol1; A ¼ 2.64  1010 L mg1 R2 ¼ 1 (2018)
Methanol Activated carbon 207C e D-A qmD-A ¼ 0.15; nDA ¼ 1.72 R2 ¼ 0.9901 Zhao et al. (2012)
Activated carbon 207 E A e D-A qmD-A ¼ 0.28; nDA ¼ 2.08 R2 ¼ 0.9865
Activated carbon WS-480 e D-A qmD-A ¼ 0.27; nDA ¼ 1.78 R2 ¼ 0.9942
9-Nitroanthracene Abiotic Polyethylene (PE) 60 rpm, C0 ¼ 10 Linear K ¼ 34.00 (L$g1) R2 ¼ 0.9818 J. Zheng et al.,
adsorbents e500 mg L1 2020
1 1
Polypropylene (PP) 60 rpm, C0 ¼ 10 Langmuir qmax ¼ 1.16  10 (mg$g3
); KL ¼ 0.04 (L$g ) 2
R ¼ 0.8802
e500 mg L1
1
Polystyrene (PS) 60 rpm, C0 ¼ 10 Linear K ¼ 24.81 (L$g ) R2 ¼ 0.9617
e500 mg L1
Naphthalene Functionalized multiwall carbon C0 ¼ 5e30 mg L1 Langmuir KL ¼ 277.78 (L$mg1) R2 ¼ 0.9703 Akinpelu et al.
Fluorene nanotubes (MWCNT-OH) C0 ¼ 5e30 mg L1 Langmuir KL ¼ 1428.6 (L$mg1) R2 ¼ 0.9517 (2019)
Benzo[b]fluoranthene SieMCMe41 mesoporous 150 rpm, C0 ¼ 150 Langmuir qmax ¼ 149.44 (mg$g1); KL ¼ 0.012 (L$g1) R2 ¼ 0.918 Costa et al., 2015
1
molecular sieve e1000 mg L
Benzo[k]fluoranthene 150 rpm, C0 ¼ 150 Langmuir qmax ¼ 147.09 (mg$g1); KL ¼ 0.011 (L$g1) R2 ¼ 0.942
e1000 mg L1
Benzo[a]pyrene 150 rpm, C0 ¼ 150 Langmuir qmax ¼ 164.69 (mg$g1); KL ¼ 0.014 (L$g1) R2 ¼ 0.946
e1000 mg L1
PCB-28 Coreeshell superparamagnetic Room temperature Langmuir qmax ¼ 40.01 (mmol$kg1); KL ¼ 12232.31 e Wang et al.
Fe3O4@b-CD composites (L$mmol1) (2015b)
1 1
PCB-52 Room temperature Langmuir qmax ¼ 30.32 (mmol$kg ); KL ¼ 380.96 (L$mmol ) e
Perfluorooctanesulfonate Alumina 150 rpm, C0 ¼ 40 Langmuir qmax ¼ 0.252 (mg$m2); KL ¼ 0.0587 (L$mg 1) R2 ¼ 0.938 Wang and Shih
1
(PFOS) e400 mg L (2011)
1
Perfluorooctanoate 150 rpm, C0 ¼ 40 Langmuir qmax ¼ 0.157 (mg$m2); KL ¼ 0.00908 (L$mg ) R2 ¼ 0.977
(PFOA) e400 mg L1
Perfluorooctanoate Polyaniline nanotubes (PASNTs) 308 K Langmuir qmax ¼ 1651 (mg$g1); KL ¼ 0.0716 (L$mg1) R2 ¼ 0.9884
(PFOA)
Perfluorooctanesulfonate 308 K Langmuir qmax ¼ 1100 (mg$g1); KL ¼ 0.06745 (L$mg1) R2 ¼ 0.9928
(PFOS)
Bisphenol A (BPA) Fe3O4@b-CD-CDI 298 K Langmuir qmax ¼ 52.68 (mg$g1); KL ¼ 0.153 (L$mg1) R2 ¼ 0.9910 Liu et al. (2020a)
318 K Langmuir qmax ¼ 47.03 (mg$g1); KL ¼ 0.115 (L$mg1) R2 ¼ 0.9753
Chrysene MIL-88(Fe) 200 rpm Langmuir qmax ¼ 42.378 (mg$g1); KL ¼ 3.746 (L$mg1) R2 ¼ 0.8665; RMSE ¼ 0.006; Zango et al. (2020)
NH2-MIL-88(Fe) 200 rpm Langmuir qmax ¼ 44.050 (mg$g1); KL ¼ 0.820 (L$mg1) R2 ¼ 0.988; RMSE ¼ 0.002;
 J. Wang, X. Guo / Chemosphere 258 (2020) 127279 17

Rangabhashiyam, 2019; Q. Zhang et al., 2016a, 2016b; Arami et al.,

Subramanyam and

2008; Yang and Hong, 2018; Wang et al., 2015a; b; Mahmoodi

Ping et al. (2006)

Torabian et al.

Cheng and Hu
et al., 2010; Nguyen et al., 2016; Deniz and Kepekci, 2016;
Das (2014)

Bouras et al., 2017; Lebron et al., 2019; Beekaroo and Mudhoo,

2011; Xue et al., 2019; Haque et al., 2010; Chaari et al., 2019;
(2014)

(2016)

Hamza et al., 2018; da Silva and Pietrobelli, 2019; El-Zahhar et al.,

2014; Bhowmik et al., 2018; Wan et al., 2019; Karmakara et al.,
R2 ¼ 0.9953; SSE ¼ 24.15513;

2019; Oveisi et al., 2018; Gamoudi and Srasra, 2019; Sarma

R2 ¼ 0.9953; SSE ¼ 4.70022;

et al., 2018; Zheng et al., 2020; Ahsan et al., 2018; Li et al., 2019;
Chakraborty et al., 2018; Silva et al., 2020; Pi et al., 2017; Ringot
HYBRID ¼ 3.777602

HYBRID ¼ 7.189632

et al., 2007; Z_ o

łtowska-Aksamitowska et al., 2018; Phasuphan
et al., 2019; Ahmed et al., 2017; Xu et al., 2020; Sun et al., 2019;
R2 ¼ 0.9556
R2 ¼ 0.9807

Guo et al., 2019a; Zhuang et al., 2020a, 2020b; Abazari et al., 2019;
R2 ¼ 0.994

R2 ¼ 0.967

Mirsoleimani-azizi et al., 2018; Maged et al., 2020; Wu et al.,

2013; Chen et al., 2019; de Sousa et al., 2018; Wu et al., 2019;
-

Shikuku et al., 2018; Shahawy and Heikal, 2018; Saeidi et al.,

2020; Zhou et al., 2010; Mallek et al., 2018; Thang et al., 2019;
Barman et al., 2018; Zhao et al., 2012; J. Zheng et al., 2020;
KRP ¼ 2.351 (L$g1); aRP ¼ 0.05369 (Lg$mg-g);

KF ¼ 220.59 (L1/n$mg11/n$g1); 1/n ¼ 1.227

KF ¼ 181.85 (L1/n$mg11/n$g1); n ¼ 1.3223
KF ¼ 175.55 (L1/n$mg11/n$g1); n ¼ 1.4123

Akinpelu et al., 2019; Costa et al., 2015; Wang and Shih, 2011; Liu
KF ¼ 5.635 (L1/n$mg11/n$g1); n ¼ 2.175

et al., 2020a; Zango et al., 2020; Subramanyam and Das, 2014;

b ¼ 0.235 J mol1; A ¼ 225.879 L g1

Torabian et al., 2014; Cheng and Hu, 2016; Ping et al., 2006). We
can see from Fig. 7 that the widely used statistical parameters are
the R2, adjust coefficient of determination (AdjR2), c2, SSE, root
mean square error (RMSE), and hybrid fractional error function
(HYBRID). The R2 values are most frequently calculated statistical
parameter. 81% of the reviewed references have adopted R2 to
evaluate the fitting results, because the R2 values can be simply
calculated by the Origin, SPSS, Excel software and so on. However,
g ¼ 0.9634

the differences in the R2 values are small in statistics. For example,

the R2 values of the Sips and Langmuir models were 0.99 and
0.996 in the adsorption of BY28 onto Smectite rich natural clay
e

(Chaari et al., 2019). This result makes it difficult to determine the

Freundlich

Freundlich
Freundlich
Freundlich

optimum isotherms. Therefore, other statistical parameters also

Temkin

should be calculated to evaluate the fitness. The calculation

ReP

D-A

equations of the statistical parameter are summarized in Table 6.

In following section, the above statistical parameters can be
C0 ¼ 0.025e1 mg L1
C0 ¼ 0.025e1 mg L1
C0 ¼ 0.025e1 mg L1

calculated by a convenient UI.

1
C0 ¼ 20e50 mg L

5. Solving methods

We developed a convenient UI based on Excel to provide a

e

useful tool for solving the nonlinear adsorption isotherm models

Metal-organic frameworks (MOFs)

and calculating the model parameters and statistical parameters.

Modified magnetic nanoparticles

The flow chart of the UI is provided in Fig. 8 (a). This Excel is

Soils treated with HA (HA)

attached in the supplemental material. Prior to use, please

Soils treated with HA (CK)
Soils treated with FA (FA)

download the Excel and open it in editable view. Solver Add-in

should be activated. The way to activate Solver Add-in is
explained as following: select file, then go to options, select Add
ins, select Solver Add-in, and press OK. In addition, please ensure
(CGMMNPs)
Natural soil

that the references in Fig. 8 (b) are all added.

The instructions for this UI are depicted in detail in Fig. 9.
Three points should be noticed: (a) when use the Temkin, D-R and
D-A models, (0, 0) should not be input; (b) the independent and
dependent variables of the Volmer model are qe and Ce, respec-
tively; and (c) the ion exchange model is not provided in the UI,
because the values of ZA and ZB are different in different
adsorption processes, and the model equations are distinct for
different values of ZA and ZB.
To test the accuracy of the estimations of the parameters, two
Anthracen (ANT)

Phenanthrene

sets of adsorption equilibrium data in Guo and Wang (2019d) are

tested by UI developed in this paper and by Origin (2018) soft-
Acetylene

ware. The results fitted by this UI are presented in Fig. 10, the
Phenol

model parameters estimated by the UI and the Origin software

are summarized in Table 7. The UI successfully solved the
18 J. Wang, X. Guo / Chemosphere 258 (2020) 127279

Fig. 6. Applications of isotherms (Nmodel is the number of optimum isotherms in literatures, L - Langmuir model, F - Freundlich model, T - Temkin model, S - Sips model, IE - ion
exchange model): (a): all types of adsorbate; (b): metals ions; (c) dyes; (d) pharmaceuticals; and (e) other types of organic pollutants. The left figures are the total amount of
adsorbate on all types of adsorbents. The right figures show the amount of adsorbate on biosorbents and abiotic adsorbents, respectively.
 J. Wang, X. Guo / Chemosphere 258 (2020) 127279 19

Table 6
Statistical parameters.

Error function Abbreviation Equation Description

Coefficient of determination R2 P 2 qexp (mg$L1): experimental adsorption capacity;

ðqmean  qcal Þ
R2 ¼ P P qmean (mg$L1): average value of experimental adsorption capacity,
ðqcal  qmean Þ2 þ
ðqcal  qexp Þ2
qcal (mg$L1): calculated adsorption capacity;
Adjust coefficient of determination Adj R2 2 2 ðNexp  1Þ
AdjR ¼ 1  ð1  R Þ Nexp: number of data points;
ðNexp  Npara  1Þ
Npara: number of parameters.
Nonlinear chi-square c2 P ðqexp  qcal Þ2 Þ
c2 ¼
q2cal
Residual sum of squares error SSE P
SSE ¼ ðqexp  qcal Þ2
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Root Mean Square Error RMSE 1 X
MSE ¼ ðqexp  qcal Þ2
Nexp
Hybrid fractional error function HYBRID 100 X qexp  qcal
HYBRID ¼
Nexp  Npara qexp

isotherms and provided the estimations of the parameters. The

estimated parameters by the UI and the Origin software are almost
the same, which indicate that the UI can give accurate and reliable
calculations of the models. In addition, the Origin software fails to
fit the adsorption data of cephalosporin C (CEP-C) on aged poly-
styrene (PS) using the Toth model and CEP-C onto aged poly-
ethylene (PE) using the Aranovich model. While the UI successful
fits the experimental data to these two models. This result dem-
onstrates that the applications of this UI are wider and more flex-
ible than the Origin software in the calculations of the parameters.

6. Concluding remarks and perspectives

This paper focused on the classification, physical meanings

Fig. 7. Applications of the statistical parameters.
application, and solution of the adsorption isotherms. We classified
the adsorption isotherms according to their physical meaning and
deduction. According to the classification, six empirical models,
two isotherm models based on Polanyi’s theory, two chemical
models, two physical models, and an ion exchange model were
thoroughly analyzed. The main conclusions were explained as
follows:

Fig. 8. Flow char (a) and references (b) for the UI.
20 J. Wang, X. Guo / Chemosphere 258 (2020) 127279

Fig. 9. Using steps for the UI.

lowed by the Freundlich model. The empirical models, such as
organic pollutants onto biosorbents and abiotic adsorbents, fol-
adsorption of metals ions, dyes, pharmaceuticals, and other types of
isotherm is the most frequently adopted optimum isotherm for the

recommended in the physical adsorption systems.

These two models have specific physical meanings, which are
Aranovich models are theoretical multi-layer adsorption models.
the macroscopic homogeneous adsorption systems. The BET and
chemical adsorption models. The Langmuir model can represent

adsorbent.
theory, which can be used to study the micropore structures of the
isotherms are semi-empirical models on the basis of Polanyi’s
adsorbate molecule can be adsorbed to 1/ns sites. The D-R and D-A
The Sips model describes the monolayer adsorption at which one
layer adsorption at which about 50% adsorption sites are occupied.
Freundlich model describes the physical adsorption or the mono-
tion at which the initial concentration of the adsorbate is low. The
from the Langmuir theory. The linear model represents the condi-

(b) aged polyethylene (PE).

onto microplastics in Guo and Wang (2019d) by the UI: (a) aged polystyrene (PS), and
Fig. 10. Fitting results of the models for the adsorption data of cephalosporin C (CEP-C)
For the application of the isotherms in literatures, the Langmuir

The Langmuir and Volmer models are theoretical monolayer

The linear, Freundlich, and Sips empirical models can be derived

J. Wang, X. Guo / Chemosphere 258 (2020) 127279

Table 7
Comparison of the model parameters estimated by the UI developed in this paper and by the Origin software for the adsorption data of cephalosporin C (CEP-C) onto microplastics in Guo and Wang (2019d).

Adsorbent Model Model parameters estimated by UI Model parameters estimated by Origin

Aged polystyrene (PS)
Aged polyethylene (PE)
1 1
Langmuir qmax ¼ 0.709 (mg$g ); KL ¼ 0.366 (L$mg ) qmax ¼ 0.709 (mg$g1); KL ¼ 0.366 (L$mg1)
Freundlich KF ¼ 0.1884 (L1/n$mg11/n$g1); n ¼ 1.975 KF ¼ 0.1884 (L1/n$mg11/n$g1); n ¼ 1.974
Sips qms ¼ 0.4998 (mg$g1); KS ¼ 0.3528 (Lns$mg-ns); ns ¼ 3.08 qms ¼ 0.4998 (mg$g1); KS ¼ 0.3528 (Lns$mg-ns); ns ¼ 3.18
Temkin b ¼ 13328 (kJ∙mol1); A ¼ 2.843 (L$mg1) b ¼ 13147 (kJ∙mol1); A ¼ 2.831 (L$mg1)
D-A EDA ¼ 10191(kJ$mol1); qmD-A ¼ 0.5008 (mg$L1); nDA ¼ 9.54 EDA ¼ 10414 (kJ$mol1); qmD-A ¼ 0.502 (mg$L1); nDA ¼ 9.59
D-R qmD-R ¼ 0.85 (mg$g1); KDR ¼ 1.4  108 (mol2$kJ2) qmD-R ¼ 0.861 (mg$g1); KDR ¼ 1.424  108 (mol2$kJ2)
Linear K ¼ 0.0720 (L$g1) K ¼ 0.0722 (L$g1)
ReP KRP ¼ 0.183 (L$g1); aRP ¼ 0.0448 (Lg$mg-g); g ¼ 1.806 KRP ¼ 0.183 (L$g1); aRP ¼ 0.0447 (Lg$mg-g); g ¼ 1.806
BET KBET1 ¼ 0.366 (L$mg1); KBET2 ¼ 0; qmBET ¼ 0.709 (mg$g1) KBET1 ¼ 0.310 (L$mg1); KBET2 ¼ 0; qmBET ¼ 0.820 (mg$g1)
Volmer bv ¼ 0.757 (L$mg1); qmV ¼ 1.862 (mg$g1) bv ¼ 0.757 (L$mg1); qmV ¼ 1.861 (mg$g1)
Toth KT ¼ 0.494 (L$g1); aT ¼ 15731 (mgz$L-z); z ¼ 9.273 Fit did not converge
Aranovich qmA ¼ 0.708 (mg$g1); CA ¼ 8406; CsA ¼ 22918 (mg$L1) qmA ¼ 0.709 (mg$g1); CA ¼ 8221; CsA ¼ 22448 (mg$L1)
Langmuir qmax ¼ 0.717 (mg$g1); KL ¼ 0.186 (L$mg1) qmax ¼ 0.717 (mg$g1); KL ¼ 0.186 (L$mg1)
Freundlich KF ¼ 0.113 (L1/n$mg11/n$g1); n ¼ 1.542 KF ¼ 0.113 (L1/n$mg11/n$g1); n ¼ 1.542
Sips qms ¼ 0.398 (mg$g1); KS ¼ 0.196 (Lns$mg-ns); ns ¼ 3.39 qms ¼ 0.398 (mg$g1); KS ¼ 0.196 (Lns$mg-ns); ns ¼ 3.39
Temkin b ¼ 15078 (kJ∙mol1); A ¼ 2.098 (L$mg1) b ¼ 15078 (kJ∙mol1); A ¼ 2.098 (L$mg1)
D-A EDA ¼ 9763 (kJ$mol1); qmD-A ¼ 0.407 (mg$L1); nDA ¼ 8.25 EDA ¼ 9761 (kJ$mol1); qmD-A ¼ 0.407 (mg$L1); nDA ¼ 8.25
D-R qmD-R ¼ 0.78 (mg$g1); KDR ¼ 2.0  108 (mol2$kJ2) qmD-R ¼ 0.790 (mg$g1); KDR ¼ 1.83  108 (mol2$kJ2)
Linear K ¼ 0.0568 (L$g1) K ¼ 0.0567 (L$g1)
ReP KRP ¼ 0.123 (L$g1); aRP ¼ 0.104 (Lg$mg-g); g ¼ 1.206 KRP ¼ 0.122 (L$g1); aRP ¼ 0.104 (Lg$mg-g); g ¼ 1.206
BET KBET1 ¼ 0.247 (L$mg1); KBET2 ¼ 0.012 (L$mg1); qmBET ¼ 0.562 (mg$g1) KBET1 ¼ 0.186 (L$mg1); KBET2 ¼ 0 (L$mg1); qmBET ¼ 0.717 (mg$g1)
Volmer bv ¼ 0.1003 (L$mg1); qmV ¼ 1.30 (mg$g1) bv ¼ 0.076 (L$mg1); qmV ¼ 1.535 (mg$g1)
Toth KT ¼ 0.5036 (L$g1); aT ¼ 13.27 (mgz$L-z); z ¼ 1.742 KT ¼ 0.5026 (L$g1); aT ¼ 13.45 (mgz$L-z); z ¼ 1.751
Aranovich qmA ¼ 0.715 (mg$g1); CA ¼ 406; CsA ¼ 2174 (mg$L1) Fit did not converge

21
22 J. Wang, X. Guo / Chemosphere 258 (2020) 127279
Temkin, Sips, and ReP models are also applied in some adsorption
processes. The linear model can be used as the optimum isotherm
for the adsorption systems with low C0. The D-R model is
frequently used in incorrect form ε ¼ RT ln(1 þ 1/Ce) in literature,
and the correct form should be ε ¼ RT ln Cs/Ce. Other types of
adsorption isotherms are seldom used in literature. The frequency
of the optimum models used in literature was in following order:
Langmuir > Freundlich > Temkin, Sips, linear, ReP > Others.
The statistical parameters R2, c2, SSE, RMSE and HYBRID are
commonly calculated for evaluating fitting results. The R2 is the
most frequently used statistical parameter. Over 81% of the
reviewed references have adopted R2 to assess the fitness. In some
cases, only calculating R2 is insufficient in comparison of the
models, because the differences in R2 are small. Other statistical
parameters also need to be calculated to determine the optimum
isotherm.
The nonlinear regression method is more accurate and powerful
for estimating the isotherm models parameters than the linear
regression method. But it is more complicated than the linear
method, which hinders the application of the nonlinear regression
method. In addition, some isotherm models, such as the Volmer
and Aranovich models, cannot be linearized. In order to widen the
application of the nonlinear regression method and the nonlinear
models, we developed an UI for solving the nonlinear adsorption
isotherms in Excel, which is provided in the Supplemental
Materials.
For using this UI, the readers only need to input the initial values
of the parameters and the experimental data. This UI can provide
accurate and reliable estimation of the isotherm models. The esti-
mated model parameters are almost the same with the calculation
results of the Origin software. It can also calculate the statistical
parameters (R2, c2, SSE, RMSE and HYBRID) for the evaluation of the
fitness of the isotherm models.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
The research was supported by the National Key Research and
Development Program (2016YFC1402507) and the Program for
Changjiang Scholars and Innovative Research Team in University
(IRT-13026).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2020.127279.
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