Journal of Hazardous Materials 390 (2020) 122156

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Journal of Hazardous Materials

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Review

Adsorption kinetic models: Physical meanings, applications, and solving T

methods
Jianlong Wanga,b,*, Xuan Guoa
a
Collaborative Innovation Center for Advanced Nuclear Energy Technology, INET, Tsinghua University, Beijing 100084, PR China
b
Beijing Key Laboratory of Radioactive Waste Treatment, Tsinghua University, Beijing 100084, PR China

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Editor: Daniel C.W. Tsang Adsorption technology has been widely applied in water and wastewater treatment, due to its low cost and high
Keywords: efficiency. The adsorption kinetic models have been used to evaluate the performance of the adsorbent and to
Adsorption investigate the adsorption mass transfer mechanisms. However, the physical meanings and the solving methods
Kinetic model of the kinetic models have not been well established. The proper interpretation of the physical meanings and the
Physical meaning standard solving methods for the adsorption kinetic models are very important for the applications of the kinetic
Solving method models. This paper mainly focused on the physical meanings, applications, as well as the solving methods of 16
adsorption kinetic models. Firstly, the mathematical derivations, physical meanings and applications of the
adsorption reaction models, the empirical models, the diffusion models, and the models for adsorption onto
active sites were analyzed and discussed in detail. Secondly, the model validity evaluation equations were
summarized based on literature. Thirdly, a convenient user interface (UI) for solving the kinetic models was
developed based on Excel software and provided in supplementary information, which is helpful for readers to
simulate the adsorption kinetic process.

1. Introduction technologies in water and waste water treatment, because it has many
advantages, such as simple design, low price, easy maintenance, and
Adsorption is a mass transfer process that pollutants from the liquid high efficiency (Wang and Chen, 2009, 2014; Wang and Zhuang, 2017,
phase to the solid adsorbent. Adsorption is one of the most widely used 2019; Wang et al., 2018a,b,c). The adsorption kinetic study provides

⁎
Corresponding author at: Energy Science Building, INET, Tsinghua University, Beijing 100084, PR China.
E-mail addresses: wangjl@mail.tsinghua.edu.cn, wangjl@tsinghua.edu.cn (J. Wang).

https://doi.org/10.1016/j.jhazmat.2020.122156
Received 20 November 2019; Received in revised form 20 January 2020; Accepted 20 January 2020
Available online 25 January 2020
0304-3894/ © 2020 Elsevier B.V. All rights reserved.
J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

Nomenclature KW&M Intraparticle diffusion coefficient (mg·g·h−1/2)

m Adsorbent mass (g)
(M) PCL Modified pineapple crown leaf MB Methylene blue
4-CP 4-chlorophenol MB1 Methyl blue
a Initial adsorption rate constant of the Elovich model (mg MG Malachite green
g−1 h−1) MO1 Methyl orange
A Constant of the Boyd’s equation MOFs UiO-66-type metal-organic frameworks
AB113 Acid Blue 113 ms Mass of adsorbent per unit volume of solution (g·L−1)
AB25 Acid blue 25 MSE Mean sum of squares error
AB434 Acid Blue 324 MWB Modified wheat bran
AdjR2 Adjust correlation coefficient n Number of active sites occupied by an adsorbate ion/
AR1 Acid red 1 molecule.
AR337 Acid Red 337 Nexp Number of the data points
b Desorption rate constant of the Elovich model (g mg−1) Npara Number of the model parameters
B Boy’s coefficient (h−1) PA Polyamide
BB69 Basic blue 69 P-CSs H3PO4– modified corn stalks
BBLS-CA Sludge-based carbonaceous adsorbent PE Polyethylene
BDE-99 Polybrominated diphenyl ethers-99 PMMA Poly(methyl methacrylate)
BY2 Basic Yellow 2 PR Phenol red
C0 Initial adsorbate concentration (mg·L−1) PS Polystyrene
Ce Equilibrium adsorbate concentration (mg·L−1) PVC Polyvinyl chloride
Cet Equilibrium adsorbate concentration at the surface of the q∞ Equilibrium adsorption capacity at infinite time (mg·g−1)
adsorbent (mg·L−1) qcal Calculated adsorption capacity (mg·L−1)
Cf Adsorbate concentration in the liquid film (mg·L−1) qe Adsorption capacity at equilibrium (mg·L−1)
CIP Ciprofloxacin qet Equilibrium adsorption capacity in the pores of the ad-
CPNM Chitosan coated polyacrylonitrile nanofibrous mat sorbent (mg·g−1)
Ct Adsorbate concentration at time t (mg·L−1) qexp Experimental adsorption capacity (mg·L−1)
Ctr Adsorbate concentration at distant r, (mg·L−1) qm Maximum adsorption capacity (mg·g−1)
Ctr|r 0=Adsorbate concentration at the center of the adsorbent qmax Langmuir constant (mg·g−1)
(mg·L−1) qmean Average value of the experimental adsorption capacity
Ctr|r r0=Adsorbate concentration at the external surface of the (mg·L−1)
adsorbent (mg·L−1) qt Adsorbed amount of the adsorbate at time t (mg·L−1)
CV Crystal violet r Distant of the adsorbate and the surface of the particle
Def Intraparticle diffusion coefficient (mm2·h−1) (cm)
DFC Diclofenac R Rate coefficient (h−1)
Dl Diffusional constant R2 Correlation coefficient
Dp Effective pore volume diffusion coefficient (cm2·s−1) r0 Radius of the adsorbent particle (cm)
Ds Surface diffusion coefficient (cm2·s−1) RB5G Reactive blue dye 5G
DY12 Direct yellow 12 RhB Rhodamine B
E33 Bayoxide®E33 ri Radial position of the adsorbate (mm)
FTMA-MTSurfactant-modified montmorillonite RSP Raw Spirulina platensis
HYBRID Hybrid fractional error function SSE Residual sum of squares error
IC Indigo carmine S Outer surface of adsorbent per unit volume (cm−1)
K Partition coefficient of the linear model (L·g−1) SMSP Sulphuric acid modified SP
k1 Pseudo-first-order rate constant (h−1) SMT Sulfamethazine
k1’ First-order rate constant of the mixed-order model (h−1) SMX Sulfamethoxazole
k2 Pseudo-second-order rate constant (g·mg−1·h−1) Sp External surface area per mass of adsorbent (cm2·g−1)
k2’ Second-order rate constant of the mixed-order model t Adsorption time (h)
(g·mg−1·h−1) tm Modeling time
ka Adsorption rate constant (L·mg−1·h−1) te Adsorption equilibrium time
kd Desorption rate constant (h−1) TA Tannic acid
kext Universal external mass transfer coefficient (L·g−1·h−1) V Solution volume (L)
kF External mass transfer coefficient (cm·s−1) α nth order rate constant (h−1)
kF&S Mass transfer coefficient between the bulk liquid and the ε Particle porosity
surface of the adsorbent (cm·h−1) εp Void fraction of the adsorbent (g·cm−3)
kint Internal mass transfer rate constant (h−1) θ Occupied fraction of the active sites (0 ≤ θ ≤ 1)
KL Langmuir constant (L·mg−1) ρ Density of the adsorbent particle (g·cm−3)
kM&W Mass transfer coefficient (cm·h−1) ρp Apparent density of the adsorbent particle (g·mL−1)
kn nth order rate constant (gn−1∙mg1-n∙min-1) χ2 Chi-square
ks External mass transfer coefficient (h−1)

2
J. Wang and X. Guo
Fig. 1. Adsorption mass transfer steps.
information of the adsorption rate, the performance of the adsorbent
used, and the mass transfer mechanisms. Knowing the adsorption ki-
netic is essential for the design of the adsorption systems. The adsorp-
tion mass transfer kinetic includes three steps, as shown in Fig. 1. The
first step is the external diffusion. In this step, the adsorbate transfers
through the liquid film around the adsorbent. The concentrations dif-
ference between the bulk solution and the surface of the adsorbent are
the driving force of the external diffusion. The second step is the in-
ternal diffusion. The internal diffusion describes the diffusion of the
adsorbate in the pores of the adsorbent. The third step is the adsorption
of the adsorbate in the active sites of the adsorbent.
Various adsorption kinetic models, such as the pseudo-first-order
(PFO) model (Lagergren, 1898), the pseudo-second-order (PSO) model
(Ho et al., 1996), the mixed-order (MO) model (Guo and Wang, 2019a),
the Ritchie’s equation (Ritchie, 1977), the Elovich model (Elovich and
Larinov, 1962), and the phenomenological mass transfer models
(Blanco et al., 2017; Marin et al., 2014; Scheufele et al., 2016; Hu et al.,
2019; Suzaki et al., 2017) have been developed to describe the ad-
sorption kinetic process. However, some problems are existed in the
applications of these kinetic models. The first one is that the most ap-
plied PFO and PSO models are empirical models and lack of specific
physical meanings. We cannot investigate the mass transfer mechan-
isms by these empirical kinetic models. Therefore, the physical mean-
ings of the empirical kinetic models should be established. The second
one is that the differential kinetic models, such as the phenomen-
ological external/internal and adsorption in active sites models have
specific physical meanings, but the solving methods are complicated.
Few studies have investigated the mass transfer processes by these
models (Blanco et al., 2017; Marin et al., 2014; Scheufele et al., 2016;
Hu et al., 2019; Suzaki et al., 2017; Guo and Wang, 2019b). The
complex solving methods hinder the applications of these models. The
third one is that in some published papers, the kinetic models are ap-
plied or solved in inappropriate manner. For example, the Frusawa and
Smith (F&S) model can only be used for modeling the adsorption pro-
cess that the isotherm is linear (Frusawa and Smith, 1973). However, it
has been applied for the adsorption process that the isotherm is Lang-
muir-type (Özer et al., 2005; Wang et al., 2008).
In addition, the linear regression method is the most widely applied
method in the calculations of the model parameters, owing to its sim-
plicity (Ma et al., 2018; Ersan et al., 2019; Shang et al., 2019; Delgado
et al., 2019; Darwish et al., 2019; Sabarinathan et al., 2019). However,
the linearization process changed the independent/dependent vari-
ables. This process could introduce propagate errors to the in-
dependent/dependent variables, and could cause inaccurate estima-
tions of the parameters (El-Khaiary et al., 2010; Ho, 2006a,b; Kumar
and Sivanesan, 2006; Guo and Wang, 2019c). The nonlinear method
can provide consistent and accurate estimations for model parameters
3
Journal of Hazardous Materials 390 (2020) 122156
(El-Khaiary et al., 2010). It is of great significance to provide the
nonlinear solving method for the adsorption kinetic models.
Based on the above, the physical meanings, applications, and sol-
ving methods of 16 adsorption kinetic models were thoroughly studied
in this paper.
The objectives of this review paper were: (1) to describe the
mathematical derivations and to analyze the physical meanings of the
adsorption reaction kinetic models, the empirical models, the diffusion
models, and the models for adsorption onto active sites; (2) to sum-
marize the applications of the adsorption kinetic models based on lit-
erature; (3) to review the model validity evaluation equations; and (4)
to develop a convenient user interface (UI) for solving the kinetic
models based on Excel.
2. Adsorption reaction models and empirical models
2.1. Pseudo-first-order (PFO) model
The PFO model was firstly proposed by Lagergren (1898). The dif-
ferential form of the PFO model is described by Eq. (1) (Lagergren,
1898):
dqt
= k1 (qe qt )
dt (1)
Integrating Eq. (1) for the conditions of q0 = 0 yields:
qt = qe (1 e k1 t )
(2)
The linearized form of the PFO model is presented as follows.
ln(qe qt ) = lnqe k1 t (3)
Eq. (3) has been frequently used to fit the kinetics data and to cal-
culate the parameters qe and k1, by plotting ln(qe-qt) vs. t (Ma et al.,
2018; Ersan et al., 2019; Shang et al., 2019; Delgado et al., 2019;
Darwish et al., 2019; Sabarinathan et al., 2019; Khan et al., 2019;
Agarwal and Rani, 2017; Gamoudi and Srasra, 2019). However, the
linearization process may cause inaccurate estimations of the para-
meters (El-Khaiary et al., 2010; Ho, 2006a,b; Kumar and Sivanesan,
2006). The nonlinear method, which can provide accurate estimations
for model parameters, is provided in the following section.
The PFO parameter qe is the equilibrium adsorption amount esti-
mated by the PFO model. Rodrigues and Silva (2016) reported that the
PFO model was theoretically consistent and equaled to the linear
driving force (LDF) model, when the adsorption isotherm could be re-
presented by the linear model (Eq. (4)).
qe = KCe (4)
The PFO parameter k1 is frequently used to describe how fast the
adsorption equilibrium is achieved (Plazinski et al., 2009). However, as
J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

shown in Eq. (1), the adsorption rate dqt/dt is related to both k1 and (qe- benzene onto activated carbon, MB onto BBLS-CA, resorcinol onto
qt). Small value of k1 and big value of (qe-qt) could be obtained when CTAB/NaOH/flyash composites, Cu (II) onto RSP and SMSP could be
the adsorption is slow. Therefore, it is more precise to calculate the PFO better fitted by the PFO model than the PSO model at high C0 (Darwish
rate by Eq. (5), instead of describing the adsorption rate by comparing et al., 2019; Khan et al., 2019; Ho and Mckay, 1998; Stähelin et al.,
the values of k1. 2018; Agarwal and Rani, 2017; Sari et al., 2017; Gunasundari and
Kumar, 2017). Siyal et al. (2019) investigated the adsorption of anionic
PFO rate = k1 (qe qt ) (5)
surfactant onto fly ash based geopolymer, concluded that when C0 in-
The PFO model used to be considered as empirical model for a long creased from 100 mg L−1 to 880 mg L−1, the values of the correlation
time. Azizian (2004) deduced the PFO model from the Langmuir ki- coefficient (R2) of the PFO model increased from 0.0035 to 0.937. Ma
netics model (Eq. (6)) (Langmuir, 1918), and analyzed the physical et al. (2018) reported that the values of R2 of the PFO model increased
meanings of this model. from 0.7556 to 0.9587, with the increase of C0 of Congo Red from 100
mg L−1 to 800 mg L−1. In the reported of MV onto granular activated
d
= ka Ct (1 ) kd carbon, it was concluded that by increasing C0 from 2.77 × 10−6
dt (6)
to7.49 × 10−6 mol·L−1, the values of R2 of the PFO model increased
Ct can be given by Eq. (7): from 0.9704 to 0.9886 (Azizian et al., 2009).
mqm The second one is that the adsorption process is in the initial stage.
Ct = C0 = C0
(7) Hu et al. (2018) found that when t approached to zero, the PSO model
V
approximated to the PFO model. Ho and Mckay (1999) studied the
Substitution of Eq. (7) into Eq. (6) yields: adsorption of Pb(II) onto peat, found that the PFO model adequately
d mqm represented the kinetics data for the first 20 min (Table 1).
= ka C0 (1 ) kd The third one is that the adsorbent material has a few active sites. In
dt V (8)
this sense, the external diffusion or the internal diffusion is the rate
Effort has been made to study the physical meanings and the ap- controlling step. The adsorption of metals ions and hydrophilic com-
plications of the PFO model. Azizian (2004) concluded that when pounds onto microplastics could be represented by the PFO model (Guo
C0 > > mqmθ/V, Eq. (8) was transformed to Eq. (9), which could be et al., 2019a; Turner and Holmes, 2015). One possible reason is that
simplified to the PFO model. microplastics are hydrophobic compounds, and the diffusion of hy-
d drophilic compounds to the surface of the hydrophobic microplastics is
= ka C0 (1 ) kd difficult. Therefore, the external/internal diffusion is the rate limiting
dt (9)
step. However, the adsorption of hydrophobic organic compounds
Liu and Shen (2008) also concluded that the simplification of the (such as lubrication oil and polybrominated diphenyl ethers) onto mi-
Langmuir kinetics model to the PFO and PSO models was C0-dependent. croplastics could be better described by the PSO model (Hu et al., 2017;
Zhang (2019) suggested that the conditions for the PFO model were: (1) Xu et al., 2019). The diffusion of hydrophobic compounds to the surface
C0/β approached to zero; (2) C0/β approached to infinite; and (3) kaβ/ of microplastics is easier than the hydrophilic compounds. The ad-
kd approached to zero. Our previous research (Guo and Wang, 2019a) sorption onto active sites may be the rate controlling step. Therefore,
concluded that mqm/V was approximately a constant for a given ad- the PFO model represents the condition that a few active sites exist in
sorption process, therefore when a few active sites were occupied the adsorbent material or a few adsorbate ions/molecules can interact
compared with C0, mqmθ/V could be neglect. Three conditions could with the active sites.
satisfy this hypothesis, as presented in Fig. 2. As summarized in Table 1, the majority of literature modeled the
The first one is that the value of C0 is high. Table 1 summarizes the whole adsorption process instead of modeling the initial stage of the
applications of the PFO model. The adsorption of BB69 and AB25 onto adsorption. Therefore, the conditions for the PFO model are at high
peat, MO1 onto NiO NPs and CuO NPs, Cr(VI) onto iron electrodes,

Fig. 2. Physical meanings of the PFO and PSO models.

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J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

Table 1
Applications of the PFO model.
Adsorbent Adsorbate tm/t te C0 (mg·L−1) Reference

a
Peat BB69 0–250 min/250 min 250 min 500 Ho and Mckay, 1998
Peat AB25 0–250 min/250 min – 200
NiO NPs MO1 0–1440 min/1440 min 540 min 200 Darwish et al., 2019
CuO NPs MO1 0–1440 min/1440 min 540 min 200
Iron electrodes Cr(VI) 0–120 min/120 min – 100 Khan et al., 2019
Activated carbon Benzene 0–120 min/120 min 70 min 110 Stähelin et al., 2018
BBLS-CA MB 0–360 min/360 min 90 min 500 Sari et al., 2017
CTAB/NaOH/flyash Resorcinol 0–24 h/24 h 3 ha 200 Agarwal and Rani, 2017
RSP Cu(II) 0–150 min/150 min 110 mina 300 Gunasundari and Kumar, 2017
SMSP Cu (II) 0–150 min/150 min 60 mina 500
Peat Pb(II) 0–20 min/90 min 90 mina 504 Ho and Mckay, 1999
Peat Pb(II) 0–20 min/90 min 30 mina 209
PA SMT 0–24 h/24 h 16 h 2 Guo et al., 2019a
PE SMT 0–24 h/24 h 16 h
PVC SMT 0–24 h/24 h 16 h
PE Ag(Ⅰ) 0–168 h/168 h 30 ha 5 × 10–3 Turner and Holmes, 2015
PE Cu(Ⅱ) 0–168 h/168 h 30 ha
PE Ni(Ⅱ) 0–168 h/168 h 30 ha

-:Not mentioned.
a
Obtained from the figures in references.

initial concentration of adsorbate and the adsorption is not controlled
by the adsorption in active sites. In some cases, the PFO model could
represent the external/internal diffusion.
2.2. Pseudo-second-order (PSO) model
The PSO model (Eq. (10)) was firstly applied to model the adsorp-
tion of lead onto peat (Ho et al., 1996). Then the PSO model was widely
adopted to describe the adsorption processes. Most published papers
used the PSO model to predict the adsorption experimental data and to
calculate the adsorption rate constants.
dqt
= k2 (qe qt ) 2
dt (10)
The integrated PSO model is described as following:
qe2 k2 t
qt =
1 + qe k2 t (11)
In order to calculate the model parameters, the nonlinear PSO
model is always transformed to the linear form (Eq. (12)).
t 1 t that the kinetics data closed to or at equilibrium produced bias and
= +
qt k2 qe2 qe (12)
The linearization of the PSO model changes the weight of qt, and
introduces propagated errors, which leads to the inaccurate calculations
of the model parameters (El-Khaiary et al., 2010; Ho, 2006a,b; Kumar
and Sivanesan, 2006; Guo and Wang, 2019c). The nonlinear method for
solving the PSO model is provided in the following section.
Similar with the PFO rate constant k1, the PSO rate constant k2 is
also used to describe the rate of adsorption equilibrium (Plazinski et al.,
2009). But the adsorption rate dqt/dt is related to both k2 and (qe-qt)2.
Thus, it is more precise to calculate the PSO rate by Eq. (13).
PSO rate = k2 (qe qt ) 2 (13)
The physical meanings of the PSO model have been investigated.
Azizian (2004) found that when C0 was low, the Langmuir kinetics
model (Eq. (8)) could be simplified to the PSO model. Liu (2008) sug-
gested that the PSO model was related to the vacant active sites. Zhang
(2019) reported that the conditions for the PFO model were C0/β ap-
proached to 1 and kaβ/kd approached to infinite. Marczewski (2010a)
found that the conditions for the PSO model were the equilibrium
surface coverage fraction θe approached to 1 and C0/β approached to 1.
Our previous study (Guo and Wang, 2019a) concluded that the PSO
model could represent three conditions (Fig. 2).
The first one is that the value of C0 is low. Sabarinathan et al. (2019)
studied the adsorption of MB onto molecular polyoxometalate, found
that the values of R2 of the PSO model decreased from 0.8979 to 0.5905
with the increase of C0 from 140 mg L−1 to 300 mg L−1. The appli-
cations of the PSO model in literature are summarized in Table 2. As
shown in Table 2, at low initial concentrations of adsorbate, the ad-
sorption kinetics of BB69 and AB25 onto peat, MO1 onto NiO NPs and
CuO NPs, Cr(VI) onto iron electrodes, benzene onto activated carbon,
MB onto BBLS-CA, resorcinol onto CTAB/NaOH/flyash composites, Cu
(II) onto RSP and SMSP are better modeled by the PSO model (Ho and
Mckay, 1998; Darwish et al., 2019; Khan et al., 2019; Stähelin et al.,
2018; Sari et al., 2017; Agarwal and Rani, 2017; Gunasundari and
Kumar, 2017).
The second one is at the final stage of the adsorption process. As
shown in Table 2, the PSO model could better represent the adsorption
of Pb(II) onto peat for 20–90 min than the PFO model (Ho and Mckay,
1999). However, this phenomenon may extend the applications of the
PSO model, because the adsorption kinetics data reported in most
published papers are from the initial to the final (equilibrium) stage of
the adsorption process (Tables 1 and 2). Simonin (2016) demonstrated
unfairly promoted the PSO model. Simonin (2016) suggested using
kinetics data for which the fractional uptake was lower than 85 %.
The third one is that the adsorbent material is abundant with active
sites. In the reported of Pb(Ⅱ) onto hydrochar and modified hydrochar,
it was observed that for modified hydrochar, the value of R2 of the PSO
model was 0.990, while for hydrochar, this value was 0.945 (Xia et al.,
2019). As listed in Table 2, the adsorption of pollutants on modified
materials, such as Al-modified biochar, modified clay, modified titanate
nanotubes, modified pineapple crown leaf, modified chitosan, surfac-
tant-modified montmorillonite, modified hydrochar, H3PO4 modified
corn stalks, modified mesoporous silica, modified bentonite, cobalt
ferrite silica magnetic nanocomposite, modified Algerian geomaterial,
modified wheat bran, modified hydrogel, modified bacterial cellulose
membrane, magnetic amidoxime functionalized chitosan and MOFs
could be better modeled by the PSO model (Yin et al., 2018; Gamoudi
and Srasra, 2019; Wang et al., 2018b; Gogoi et al., 2018; Lou et al.,
2018; Li et al., 2018, 2019; Xia et al., 2019; Islam et al., 2019; Tang
et al., 2019; Gao et al., 2019; Huang et al., 2017; Amiri et al., 2017;
Bentaleb et al., 2017; Zhang et al., 2017; Zhuang et al., 2017, 2018,
2019; Fan et al., 2017; Cheng et al., 2019). In general, the modified
materials are abundant with active sites. Therefore, the adsorption

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J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

Table 2
Applications of the PSO model.
Adsorbent Adsorbate tm/t te C0 (mg·L−1) Reference

a
Peat BB69 0–250 min/250 min 30 min 50 Ho and Mckay, 1998
Peat AB25 0–250 min/250 min – 20
NiO NPs MO1 0–1440 min/1440 min 540 min 50 Darwish et al., 2019
CuO NPs MO1 0–1440 min/1440 min 540 min 50
Iron electrodes Cr(VI) 0–120 min/120 min – 60 Khan et al., 2019
Activated carbon Benzene 0–120 min/120 min 70 min 69 Stähelin et al., 2018
BBLS-CA MB 0–360 min/360 min 90 min 100 Sari et al., 2017
CTAB/NaOH/flyash Resorcinol 0–24 h/24 h 3 ha 50 Agarwal and Rani, 2017
RSP Cu(II) 0–150 min/150 min 100 mina 50 Gunasundari and Kumar, 2017
SMSP Cu(II) 0–150 min/150 min 50 mina 50
Peat Pb(II) 20–90 min/90 min 90 mina 504 Ho and Mckay, 1999
Peat Pb(II) 20–90 min/90 min 30 mina 209
CPNM AB113 0–120 h/120 h 120 h 100 Lou et al., 2019
PE lubrication oil 0–48 h/48 h 12 ha – Hu et al., 2017
PS lubrication oil 0–48 h/48 h 12 ha –
PE BDE-99 0–24 h/24 h 30 min 0.5 Xu et al., 2019
Al-modified biochar Nitrate 0–24 h/24 h 24 h 50 Yin et al., 2018
Al-modified biochar Phosphate 0–24 h/24 h 24 h 50
Modified clay MO1 0–4 h/4 h 2h 200 Gamoudi and Srasra, 2019.
Modified clay IC 0–4 h/4 h 1h 200
Modified clay PR 0–4 h/4 h 1h 200
Modified titanate nanotubes Ag(Ⅰ) 0–150 min/150 min 20 min 122 Wang et al., 2018b
(M) PCL Cr(VI) 0–180 min/180 min 120 mina 20 and 30 Gogoi et al., 2018
Cr(III) 0–180 min/180 min 120 mina 20 and 30
Modified chitosan Re(VII) 0–24 h – 20 Lou et al., 2018
FTMA-MT Phenol 0–21 h 7h – Li et al., 2018
Modified hydrochar Pb(II) 0–360 min/360 min 240 mina 10 Xia et al., 2019
Modified-chitosan Cr(VI) 0–150 min/150 min 90 min 40–100 Islam et al., 2019
P-CSs MB 0–300 min/300 min 140 min 30–90 Tang et al., 2019
Modified mesoporous silica Steroid estrogens 0–90 min/90 min 30 min 2 Gao et al., 2019
Maleylated modified hydrochar MB 0–300 min/300 min 150 min 600–1000 Li et al., 2019
Cd(II) 0–300 min/300 min 30 min 40–90
Modified bentonite RhB 0–70 min/70 min 40 min 100 Huang et al., 2017
Modified bentonite AR1 0–70 min/70 min 90 min 100
Cobalt ferrite silica magnetic nanocomposite MG 0–70 min/70 min 40 min 100 Amiri et al., 2017
Modified Algerian geomaterial 2,4-dichlorophenol 0–200 min/200 min 60 min 81.5–244.5 Bentaleb et al., 2017
MWB Anionic azo dyes 0–12 h/12 h 11 h 50 Zhang et al., 2017
Modified hydrogel Tetracycline 0–24 h/24 h 24 h 300 Zhuang et al., 2017
Modified hydrogel CIP 0–24 h/24 h 24 h 300
Modified chitosan/CoFe2O4 Cu(II) 0–90 min/90 min 50 min 200 Fan et al., 2017
Pb(II) 0–90 min/90 min 50 min 200
Modified Bacterial cellulose membrane Sr(II) 0–10 h/10 h 10 h 100 Cheng et al., 2019
Magnetic amidoxime functionalized chitosan U(VI) 0–180 min/180 min 180 min 480 Zhuang et al., 2018
MOFs DFC 0–500 min/500 min 200 min 80 Zhuang et al., 2019
Cerium modified chitosan As(III) 0–540 min/540 min 300 min 10 and 30 Zhang et al., 2016
E33 Phosphate 0–294 h/294 h 294 ha 140 Lalley et al., 2016
E33/Mn Phosphate 0–294 h/294 h 294 ha 140
E33/Ag I Phosphate 0–294 h/294 h 294 ha 140
E33/Ag II Phosphate 0–294 h/294 h 294 ha 140
NiO NPs MO1 0–1440 min/1440 min 540 min 200 Darwish et al., 2019
BBLS-CA MB 0–360 min/360 min 90 min 500 Sari et al., 2017

-: Not mentioned.
a
Obtained from the figures in references.

kinetics is dominated by the adsorption onto active site. and the step of adsorption on active sites, respectively (Guo and Wang,
2019a). In addition, the MO model represents the overall adsorption
2.3. Mixed-order (MO) model process. The following conditions satisfy the assumption of the MO
model: (1) arbitrary stage of the adsorption; (2) the rate controlling step
The mixed-order (MO) model has the following form (Guo and is the diffusion or the adsorption; and (3) arbitrary initial adsorbate
Wang, 2019a): concentration in solution (Guo and Wang, 2019a).
Eq. (14) is similar in the form to the hybrid-order’ (HO) model (Eq.
dqt (17)) provided in Liu and Shen (2008), and the mixed 1, 2-order rate
= k1’ (qe qt ) + k 2’ (qe qt ) 2
dt (14) equation (MOE) (Eq. (18)) derived by Marczewski (2010b).
The PFO and PSO rate of the MO model can be calculated by Eqs. d t 2
(15) and (16). = kL1 ( t) + kL2 ( t)
dt
e e
(17)
PFO rate' = k1’ (qe qt ) (15) dF
= k1a (1 FL) + k2a aeq (1 FL ) 2
dt (18)
PSO rate' = k2’ (qe qt ) 2 (16)
Where kL1, kL2, k1a, aeq, and k2a are coefficients.
In most cases, the PFO rate and PSO rate describe the diffusion step As described in Eq. (17), the HO model is the relationship between

6
J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

θt and t, which makes it difficult to directly apply the HO model to the
kinetics experimental data. The MOE was simplified according to some
assumptions, such as k2aaeq/(k1a+ k2aaeq) < 1 (Marczewski, 2010a),
leading to the lower precision in the estimations of the model para-
meters. Therefore, the MO model presented by Guo and Wang (2019a)
is recommended to model the kinetics processes.
The MO model has been successfully used to describe the adsorption
of SMT onto MOFs, and SMX, SMT, and CEP-C onto microplastics (Guo
and Wang, 2019b; Zhuang et al., 2020). The MO model is a differential
equation, which can be solved by the Runge-Kutta method. Although
the solving method of the MO model based on MATLAB is provided in
our previous study (Guo and Wang, 2019a), the application of the
program in MATLAB is still complicated. Therefore, we developed an UI
in Excel software, which is easily to be used for solving the MO model.
The details are shown in the following section.
Plotting qt versus ln(t) can solve Eq. (21) by the linear regression
method. In the past decade, the Elovich model has been used to re-
present the adsorption of liquid-solid systems. The applications of the
Elovich model are summarized in Table 3. Eq. (21) is the most fre-
quently applied form of the Elovich model, which has been successfully
used for modeling the adsorption of metals ions and organic pollutants
on adsorbents. Only a few published papers adopted Eq. (20) for the
estimations of the Elovich parameters (Lin et al., 2018; Brito et al.,
2018; Kalhor et al., 2018). However, the assumption for Eq. (21),
namely, abt > > 1, may reduce the accuracy of the Elovich model.
Thus, although the application of Eq. (21) is simple and convenient, it is
not recommend using Eq. (21) to model the kinetics data.
In the following section, we provided the nonlinear method for Eq.
(20) based on Excel UI. In addition, Eq. (22) is recommended to cal-
culate the Elovich rate:

Elovich rate = ae bqt (22)

2.4. Elovich model

The basic assumptions of the Elovich model were (1) the activation 2.5. Ritchie’s equation and pseudo-nth-order (PNO) model
energy increased with adsorption time and (2) the surface of the ad-
sorbent was heterogeneous. The Elovich model is an empirical model Ritchie’s equation was firstly proposed for modeling the adsorption
without definite physical meanings. It is commonly used to model the kinetic data of gases on solids (Ritchie, 1977). The physical meaning of
chemisorption of gas onto solid. The Elovich model has been described Ritchie’s equation is that the adsorption is dominated by the adsorption
by Eq. (19) (Elovich and Larinov, 1962): in active sites. And one adsorbate ion/molecule can occupy n active
dqt sites. The desorption process is not considered in this model. Ritchie’s
= ae bqt
equation is presented by Eq. (23) (Ritchie, 1977):
dt (19)
d
Integrating Eq. (19) for the condition of q0 = 0 yields: = (1 )n
dt (23)
1
qt = ln(1 + abt ) After integration with the initial condition of q0 = 0, Ritchie’s
b (20)
equation becomes:
Eq. (20) is a nonlinear equation, which can be solved by the non- For n = 1,
linear least square regression method (plot qt versus t) or by the linear
=1 e t (24)
method (plot qt versus ln(1+abt)). However, the nonlinear method is
more complex than the linear method. And the linear method needs to For n ≠ 1,
give the appropriate initial values of ab, which is difficult for the re-
1
searchers (Ho, 2006a,b). Chien and Clayton (1980) simplified Eq. (20) =1 [1 + (n 1) t ]1 n (25)
with the assumption of abt > > 1:
θ can be described by the ratio of qt and q∞ (q∞ can be obtained from
qt =
1 1 1
ln(abt ) = ln(ab) + ln(t ) the adsorption isotherm model (q∞ = f(Ce)), Eqs. (24) and (25) be-
b b b (21) comes:

Table 3
Applications of the Elovich model.
Adsorbent Adsorbate Elovich model Ref.

Alfisol Tetracycline Eq. (21) Bao et al., 2010

Ultisol Tetracycline Eq. (21)
Contaminant barrier minerals Pb(Ⅱ) Eq. (21) Inyang et al., 2016
Contaminant barrier minerals Cd(Ⅱ) Eq. (21)
β-cyclodextrin-based adsorbent Cu(Ⅱ) Eq. (21) Huang et al., 2012
Synthesized TiO2 nanoparticles Hg(II) Eq. (21) Dou et al., 2011
TiO2/montmorillonite Hg(II) Eq. (21)
Surfactant-Modified Natural Zeolites Benzene Eq. (21) Seifi et al., 2011
Surfactant-Modified Natural Zeolites Toluene Eq. (21)
Surfactant-Modified Natural Zeolites Ethylbenzene Eq. (21)
Surfactant-Modified Natural Zeolites Xylenes Eq. (21)
Desert soils Inositol hexaphosphate Eq. (21) Fuentes et al., 2014
Gl-PZSNTs-Fe3O4 MB Eq. (21) Wang et al., 2019
Honeycomb-like porous activated carbon Cu(II) Eq. (21) Mondal and Majumder, 2019
Modified eggshell membrane MO1 Eq. (21) Candido et al., 2019
Modified eggshell membrane MB1 Eq. (21)
Anodized iron oxide nanoflakes Phosphate Eq. (21) Afridi et al., 2019
Iron oxide-gelatin nanoadsorbent DY12 Eq. (21) Alinejad-Mir et al., 2018
Cement kiln dust BB69 Eq. (21) Magdy and Altaher, 2018
Modified rice straw Cr(VI) Eq. (20) Lin et al., 2018
Carbons Dianix® royal blue CC Eq. (20) Brito et al., 2018
Amino functionalized silica nano hollow sphere Imidacloprid pesticide Eq. (20) Kalhor et al., 2018
Raw pomegranate peel Cu(II) Eq. (21) Ben-Ali et al., 2017
Alfalfa white proteins concentrate Polyphenols Eq. (21) Frdaous et al., 2017

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J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

For n = 1, 1
qt = qe 1
qt = q (1 e t)
(26) (1 + (n 1)q n 1kn t1/(n
e
1) )
(31)
For n ≠ 1,
The PNO model mainly represents the adsorption processes that the
1 order factor is between 1 and 2 or larger than 2. Unfortunately, the PNO
qt = q q [1 + (n 1) t ]1 n (27)
model is an empirical equation without specific physical meanings. The
When n = 2, rearrangement of Eq. (27) yields: applications of the PNO model are summarized in Table 4. Caroni et al.
q t (2009) indicated that values of n of tetracycline adsorption on chitosan
qt = particles increased with the increase of the initial concentrations of
1+ t (28)
tetracycline. Liu et al. (2019) reported that the value of n was 2.276 at
Eq. (28) is the Ritchie’s second-order (RSO) equation. Note that the RSO low initial concentration of 17β-Estradiol (0.2 mg L−1), while it de-
equation is different with the nonlinear form of the PSO model (Eq. creased to 0.979 at high C0 (6 mg L−1). Leyva-Ramos et al. (2010)
(11)). The applications of Ritchie’s equation are summarized in Table 4. suggested that the values of n were not correlated with the experi-
The RSO model is frequently used in the adsorption of gas or liquid onto mental conditions, such as pH, C0, impeller speeds, and so on.
solid. Cheung et al. (2001) studied the adsorption kinetics of cadmium The nonlinear form of the PNO model cannot be written as the
onto bone char by using the RSO model. Fashi et al. (2018) applied the linear form. Therefore, the solution of the PNO model is more complex
RSO model to the adsorption data of CO2 onto piperazine-modified than the PFO and PSO models. Özer (2007) solved the PNO model using
activated alumina. Wang et al. (2018) demonstrated that Ritchie’s the nonlinear regression method by Statistica 6.0 software. Tseng et al.
equation could best fit the kinetics data of MB onto calcium alginate, (2014) used commercial SigmaPlot 11 software to solve the PNO
ball-milled biochar, and their composites. model. In the following section, a convenient method for solving the
Özer (2007) developed the pseudo-nth-order (PNO) model (Eq. Ritchie’s equation and the PNO model was provided. Eq. (32) is pro-
(29)) for modeling the adsorption kinetics data of Pb(II) on sulphuric posed for the calculation of the PNO rate:
acid-treated wheat bran.
PNOrate = kn (qe qt )n (32)
dqt
= kn (qe qt )n
dt (29)
For n = 1, the PNO model equals to the PFO model. After in- 3. Diffusional models
tegration with the initial condition of q0 = 0 and n ≠ 1, the PNO model
becomes: 3.1. External diffusion models
(qe qt )1-n =(n 1) kn t + qe 1 n
(30)
The external diffusion models assume that the diffusion of adsorbate
Rearrangement of Eq. (30) yields: in a bounding liquid film around the adsorbent is the slowest step.

Table 4
Applications of the Ritchie’s equation and the PNO model.
Adsorbent Adsorbate C0 (mg L−1) Model n Ref.

Bone char Cd(Ⅱ) 224–560 RSO 2 Cheung et al., 2001

Piperazine-modified activated Alumina CO2 – RSO 2 Fashi et al., 2018
Calcium alginate MB 50 Ritchie’s equation – Wang et al., 2018a
Ball-milled biochar MB 50 Ritchie’s equation –
Ball-milled biochar encapsulated in calcium-alginate beads MB 50 Ritchie’s equation –
Phthalonitrile compound Alkanes – RSO 2 Günay et al., 2018
Phthalonitrile compound Alcohols – RSO 2
Phthalonitrile compound Chlorinated – RSO 2
Macroporous ion-exchange resins Al(Ⅲ) 77.5 PNO 1.17–1.47 Nekouei et al., 2019
Macroporous ion-exchange resins Cu(Ⅱ) 7653 PNO 0.94–1.37
Macroporous ion-exchange resins Zn(Ⅱ) 425.5 PNO 0.38–1.38
Macroporous ion-exchange resins Ni(Ⅱ) 85.5 PNO 1.25–1.73
Macroporous ion-exchange resins Pb(Ⅱ) 183 PNO 0.998–1.36
Pure açaí biochar MB 50 PNO 1.65 Pessôa et al., 2019
NaOH-açaí biochar MB 50 PNO 2.26
Sulphuric acid-treated wheat bran Pb(II) 100 PNO 1.717–1.929 Özer, 2007
Molecularly imprinted polymers Quinoline 20 PNO 0.98–2.85 Saavedra et al., 2018
Chitosan spheres MO1 – PNO 2–2.5 Morais et al., 2008
Chitosan particles Tetracycline 15a PNO 4.5a Caroni et al., 2009
Chitosan particles Tetracycline 55a PNO 16a
Montmorillonite-carbon hybrids 17β-Estradiol 6 PNO 0.979 Liu et al., 2019
Montmorillonite-carbon hybrids 17β-Estradiol 0.2 PNO 2.276
Bone char fluoride 5.44 PNO 1.3 Leyva-Ramos et al., 2010
Bone char fluoride 8.35 PNO 2.0
Carbons prepared from betel trunk Phenol – PNO 1.50 Tseng et al., 2014
Carbons prepared from betel trunk MB – PNO 3.51
Carbons prepared from betel trunk Basic brown 1 – PNO 3.06
Carbons prepared from betel trunk Acid blue 74 (AB74) – PNO 1.77
Carbons prepared from betel trunk 2,4-dichloropenol – PNO 1.63
Carbons prepared from betel trunk 4-chloropenol – PNO 1.28
Carbons prepared from betel trunk 4-Cresol – PNO 1.40
Resin Iron ions 3000 PNO 1.92 Izadi et al., 2017

-: Not mentioned.
a
Obtained from the figures in references.

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J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

Table 5
Applications of the diffusional models.
Diffusional models Models name Adsorbent Adsorbate Reference

External diffusion models Boyd’s external diffusion equation Microporous activated carbon Metronidazole Ahmed and Theydan, 2013
F&S model Inactive CMC immobilized Aspergillus fumigatus beads Azo dye Wang et al., 2008
F&S model Enteromorpha prolifera AR337 Özer et al., 2005
F&S model Enteromorpha prolifera AB324
F&S model Natural untreated clay BY2 Öztürk and Malkoc, 2014
F&S model Bamboo Charcoal Organic materials Fu et al., 2012
F&S model Bamboo Charcoal Organic matter Fu et al., 2015
F&S model Wollastonite Cu(Ⅱ) Panday et al., 1986
M&W model Inactive CMC immobilized Aspergillus fumigatus beads Azo dye Wang et al., 2008
M&W model Enteromorpha prolifera AR337 Özer et al., 2005
M&W model Enteromorpha prolifera AB324
M&W model Bone char Cu (Ⅱ) Choy et al., 2004
M&W model Bone char Cd(Ⅱ)
M&W model Bone char Zn(Ⅱ)
M&W model Clinoptilolite rich mineral Cr(VI) Erdoğan and Ulku, 2012
M&W model Bacteria loaded clinoptilolite rich mineral Cr(VI)
M&W model Spent coffee ground Cu (Ⅱ) Dávila-Guzmán et al., 2013
M&W model Zeolite Cu (Ⅱ) Šljivić et al., 2011
M&W model Clay Cu (Ⅱ)
M&W model Diatomite Cu (Ⅱ)
EMT model Dowex Optipore SD-2 RB5G Blanco et al., 2017
EMT model Dowex Optipore SD-2 RB5G Marin et al., 2014
EMT model SB biomass RB5G Scheufele et al., 2016
EMT model Sargassum horneri Cs(Ⅰ) Hu et al., 2019
EMT model Sargassum horneri Sr(II)
EMT model Fixed-bed columns Cu(II) Suzaki et al., 2017
EMT model Fixed-bed columns Ni(II)
EMT model Fixed-bed columns Zn(II)
EMT model Microplastics SMX Guo et al., 2019b
EMT model Fixed-bed CIP Sausen et al., 2018
Internal diffusion models Boyd’s intraparticle diffusion model Mansonia wood sawdust Pb(II) Ofomaja, 2010
Boyd’s intraparticle diffusion model Dolomite Cr(VI) Albadarin et al., 2012
Boyd’s intraparticle diffusion model PMMA Phenol Al-Muhtaseb et al., 2011
Boyd’s intraparticle diffusion model Starchy adsorbents Water Okewale et al., 2013
Boyd’s intraparticle diffusion model Wood apple shell MG Sartape et al., 2017
Boyd’s intraparticle diffusion model Pre-treated bentonite clay Ag(Ⅰ) Cantuaria et al., 2016
Boyd’s intraparticle diffusion model Mesoporous activated carbon Cd(Ⅱ) Tan et al., 2016
Boyd’s intraparticle diffusion model Verde-lodo bentonite Ag(Ⅰ) Freitas et al., 2017
Boyd’s intraparticle diffusion model Verde-lodo bentonite Cu(II)
Boyd’s intraparticle diffusion model Amine-functionalized ordered mesoporous alumina MB Gan et al., 2015
Boyd’s intraparticle diffusion model Sand Neutral Red Rauf et al., 2007
W&M model PMMA Phenol Al-Muhtaseb et al., 2011
W&M model Activated carbons MB Wu et al., 2009
W&M model Activated carbons TA
W&M model Activated carbons Phenol
W&M model Activated carbons 4-CP
W&M model Caulerpa lentillifera Cu(II) Apiratikul and Pavasant, 2008
W&M model Caulerpa lentillifera Cd(II)
W&M model Caulerpa lentillifera Pb(II)
W&M model Activated carbon Dibenzothiophene Danmaliki and Saleh, 2016
W&M model Activated carbon MB Archin et al., 2019
W&M model Activated carbon AB 25
IMT model Dowex Optipore SD-2 RB5G Blanco et al., 2017
IMT model Dowex Optipore SD-2 RB5G Marin et al., 2014
IMT model SB biomass RB5G Scheufele et al., 2016
IMT model Sargassum horneri Cs(Ⅰ) Hu et al., 2019
IMT model Sargassum horneri Sr(II)
IMT model Fixed-bed columns Cu(II) Suzaki et al., 2017
IMT model Fixed-bed columns Ni(II)
IMT model Fixed-bed columns Zn(II)
IMT model Microplastics SMX Guo et al., 2019b
PVSD model PVSD model Bentonite clay MG Souza et al., 2017a
PVSD model Bentonite clay MG Souza et al., 2017b
PVSD model Bentonite clay CV Souza et al., 2019
PVSD model Granular activated carbon Pyridine Ocampo-Perez et al., 2010
PVSD model Granular activated carbon Metronidazole Díaz-Blancas et al., 2018
PVSD model Activated carbon pellets Acetaminophen Ocampo-Perez et al., 2017
PVSD model Biochar Ibuprofen Ocampo-Perez et al., 2019

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J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

Several equations have been developed to model the external mass The value of kM&WS is calculated to describe the external diffusion.
transfer process. Eq. (41) is the most frequently used form of the M&W model. As
summarized in Table 5, the M&W model has been used to describe the
3.1.1. Boyd’s external diffusion equation adsorption kinetics data of dyes and metals onto biosorbent and mineral
Boyd et al. (1947) deduced a kinetic model to describe the diffusion (Wang et al., 2008; Choy et al., 2004; Erdoğan and Ulku, 2012; Dávila-
of adsorbate through a bounding liquid film: Guzmán et al., 2013; Šljivić et al., 2011).
Combining Eqs. (38) and (41) yields:
dqt
= 4 r0 2Dl ( Cf / r )r = r 0
dt (33) qt =
C0
(1 e k M&W St )
ms (42)
Assuming that the concentration gradient is linear, Eq. (33) is
simplified to Eq. (34) (Boyd et al., 1947): Eq. (42) can be solved by the nonlinear regression method.
dqt
= R (q qt ) 3.1.4. Phenomenological external mass transfer (EMT) model
dt (34)
The EMT model (Eq. (43)) assumes that the film diffusion is the
Where q∞ = 4πr03Clk/3 (k is the distribution coefficient). q∞ can also slowest step, and the equilibrium is obtained on the surface of the ad-
be obtained by the adsorption isotherm model (q∞ = f(Ce)). sorbent (Ruthven, 1984; Hines and Maddox, 1985). The driving force of
Integration of Eq. (34) at initial condition of q0 = 0 yields (Boyd the external diffusion is the concentration gradient of adsorbent in the
et al., 1947): liquid film.
qt = q (1 e Rt )
(35) dqt k
= s (Ct Cet ) = k ext (Ct Cet )
dt (43)
This equation is similar with the PFO model. Ahmed and Theydan
(2013) studied the adsorption kinetics of metronidazole onto micro- Then the equilibrium phenomenon is described by the adsorption
porous activated carbon using the linear form of Boyd’s equation (Eq. isotherm model. The isotherm model is presented as qet = f(Cet). Then
(36)), the results showed that the values of R2 of Boyd’s equation Cet = f−1(qet). For example, if the Langmuir model can adequately
ranged from 0.9471 to 0.9885. represent the adsorption isotherm, the equilibrium phenomenon is de-
scribed as following:
ln(1 qt / q ) = Rt + A (36)
qmax KL Cet
qt =
1 + KL Cet (44)
3.1.2. Frusawa and Smith (F&S) model
Frusawa and Smith (1973) developed an adsorption rate equation: Substitution of Eqs. (38) and (44) into Eq. (43) yields:
Ct 1 ms K 1 + ms K
k St dqt mqt qt
= + e ms K F&S = kext (C0 )
C0 1 + ms K 1 + ms K (37) dt V qmax KL qt KL (45)
The value of kF&SS is frequently used to describe the external dif- The initial conditions of the EMT model are q0 = 0 and Cet(0) = 0.
fusional process (Özer et al., 2005; Panday et al., 1986) The EMT model can be solved by the Runge-Kutta method. The solving
The F&S model assumes that the external diffusion is the slowest method is provided in the following section.
step, the intraparticle diffusion is negligible, and the isotherm is linear As shown in Table 5, the adsorption processes of dyes onto Dowex
(Eq. (4)) (Frusawa and Smith, 1973). Note that Eq. (37) cannot be used Optipore SD-2 and SB biomass, as well as metals ions onto argassum
for modeling the adsorption condition that the isotherm is not linear. horneri and fixed-bed columns have been modeled by the EMT model.
The applications of the F&S model are summarized in Table 5. The equilibrium phenomenon was described by the Langmuir (Blanco
Unfortunately, most studies applied Eq. (37) to their adsorption kinetics et al., 2017; Marin et al., 2014; Suzaki et al., 2017; Sausen et al., 2018),
data when the isotherm is described by the Langmuir isotherm model BET (Scheufele et al., 2016), Linear (Guo et al., 2019b), and Freundlich
(Özer et al., 2005; Wang et al., 2008; Öztürk and Malkoc, 2014; Fu (Hu et al., 2019; Guo et al., 2019b) isotherms.
et al., 2012, 2015).
In order to establish the relationship between qt and t, Eq. (38) is 3.2. Internal diffusion models
brought into Eq. (37), and the result is presented in Eq. (39):
V (C0 Ct ) The internal diffusion models assume that the diffusion of adsorbate
qt = (C0 Ct ) = within adsorbent is the slowest step. The diffusion of adsorbate in the
m ms (38)
liquid film around the adsorbent and the adsorption onto the active
C0 1 ms K 1 + ms K
k St sites are instantaneous. Here we reviewed three most used internal
qt = 1 e ms K F&S
ms 1 + ms K 1 + ms K (39) diffusion models, i.e., the Boyd’s intraparticle diffusion model, the
Weber and Morris (W&M) model, and the phenomenological internal
Eq. (39) can be solved by the nonlinear regression method, which is mass transfer (IMT) model.
provided in the following section.
3.2.1. Boyd’s intraparticle diffusion model
3.1.3. Mathews and Weber (M&W) model Boyd et al. (1947) reported an intraparticle diffusion model:
The Mathews and Weber (M&W) model is presented as follows
6 1 n2Bt
(Mathews and Weber, 1977). F =1 e
2 n=1 n2 (46)
r (1 ) ln (C0/ Ct ) −1
kM & W = 0 Where F = qt/q∞, q∞ (mg·g ) is obtained by the adsorption isotherm
3ms t (40)
model (q∞ = f(Ce)) (Yao and Chen, 2017).
The coefficient item 3ms/(r0ρ(1-ε)) can be replaced by the outer As the value of F up to 0.05, Eq. (46) is simplified to Eq. (47) (Boyd
surface coefficient S (cm−1). Rearrangement of Eq. (40) yields: et al., 1947):
Ct k M&W St F = 1.08 Bt (47)
=e
C0 (41)
Reichenberg (1953) suggested that for the values of F ranged from 0

10
J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

to 0.85, Eq. (46) could be rearranged to: qmax KL Ct

qet =
1 + KL Ct (53)
6 3
F= Bt (Bt )
3/2 2 (48a) Substitution of Eqs. (38) and (53) into Eq. (52) yields:
Or qt qmax KL Ct
= kint qt
2F F 1/2 t 1 + KL (C0 mqt / V ) (54)
Bt = 2 2 1
3 3 ((48)b) Eq. (54) can be solved by the Runge-Kutta method with the initial
When the values of F range from 0.86 to 1, Eq. (46) is transformed condition of q0 = 0. The applications of the IMT model are shown in
to Eq. (49) (Reichenberg, 1953): Table 5. The equilibrium phenomenon in the liquid-solid interface was
described by the BET (Scheufele et al., 2016), Freundlich (Hu et al.,
2
F=1 e Bt 2019), and Langmuir isotherms (Blanco et al., 2017; Marin et al., 2014;
6 (49a) Suzaki et al., 2017).
Or
3.3. Pore volume and surface diffusion (PVSD) model
2
Bt = ln (1 F)
6 ((49)b) The basic assumptions of the PVSD model are that (1) the adsorbent
If the experimental data obey the Boyd’s intraparticle diffusion particle is spherical, (2) the convective mass transport in the pores is
model, B is a constant. In other words, if the plot of Bt vs t is a straight negligible, (3) the solution is homogeneous, and (4) the adsorption on
line and passes through (0, 0), the adsorption process is controlled by active sites is simultaneous. The PVSD model is described by Eqs.
the intraparticle diffusion. Please note that in the applications of Boyd’s (55)–(60) (Leyva-Ramos and Geankoplis, 1985):
intraparticle diffusion model, the term Bt is the product of B and t. dCt
V = mSp kF (Ct Ctr |r=r0 )
In the past decades, Boyd’s intraparticle diffusion equation has been dt (55)
used to represent the internal mass transfer processes (Table 5). For
example, Ofomaja (2010) studied the adsorption of Pb(II) onto man- t = 0, Ct = C0 (56)
sonia wood sawdust using the Boyd’s model. Albadarin et al. (2012) qt qt
Ctr 1 C
demonstrated that the values of R2 of Boyd’s model for the adsorption of p + p = 2 r 2 Dp tr + p Ds
Cr(Ⅵ) (C0 = 10−50 mg L−1) onto dolomite ranged from 0.899 to
t t r r r r (57)
0.951. Al-Muhtaseb et al. (2011) concluded that the plot of Bt vs t didn’t t = 0,0 r r0, Ctr = 0 (58)
pass through (0, 0), which indicated that the adsorption of phenol onto
PMMA was not controlled by the intraparticle diffusion. Ctr
|r = 0 = 0
r (59)
3.2.2. Weber and Morris (W&M) model Ctr qt
Weber and Morris (1963) deduced a model to describe the in- Dp |r = r0 + p Ds |r = r 0 = kF (Ct Ctr )|r = r 0
r r (60)
traparticle diffusion process. The W&M model is presented as following:
The equilibrium phenomenon is described by the adsorption iso-
qt = kW&M t 1/2 (50) therm: qet = f(Cet). The PVSD model is simplified to the pore volume
diffusion (PVD) model when Ds = 0 and Dp ≠ 0 or to the surface dif-
By plotting qt vs. t, the parameter kW&M can be estimated. The plot of qt
fusion (SD) model when Dp = 0 and Ds ≠ 0.
vs t1/2 is a straight line and passes through (0, 0) when the intraparticle
Detailed numerical solution of the PVSD model is given by Souza
diffusion is the controlling process. Otherwise, the adsorption is con-
et al. (2017a). In recent years, the PVSD model has been used to de-
trolled by multiple processes.
scribe the diffusional adsorption of CV and MG onto bentonite clay
Because W&M model is simple and convenient, it has been widely
(Souza et al., 2017a, 2019), pyridine and metronidazole onto granular
applied to find out the rate controlling step, such as phenol onto PMMA
activated carbon (Ocampo-Perez et al., 2010; Díaz-Blancas et al., 2018),
(Al-Muhtaseb et al., 2011), TA, MB, phenol, and 4-CP on activated
acetaminophen onto activated carbon pellets (Ocampo-Perez et al.,
carbons (Wu et al., 2009), Cu(II), Cd(II), and Pb(II) onto Caulerpa
2017), and ibuprofen onto biochar (Ocampo-Perez et al., 2019)
lentillifera (Apiratikul and Pavasant, 2008), Dibenzothiophene, MB and
(Table 5).
AB 25 onto activated carbons (Danmaliki and Saleh, 2016; Archin et al.,
2019) (Table 5).
4. Models for adsorption onto active sites (AAS)

3.2.3. Phenomenological internal mass transfer (IMT) model The models for AAS assume that the adsorption onto active site is
The internal mass transfer phenomenon can be described by the the slowest step, and the diffusion process is negligible. Langmuir ki-
Fick’s law (Crank, 1979): netics model and Phenomenological AAS model, as well as the Ritchie’s
qt (ri, t ) D q (ri, t ) equation reviewed in the previous section can describe the AAS phe-
= ef (ri 2 t ) nomenon.
t ri 2 ri ri (51)

Eq. (51) can be simplified to the LDF model (Glueckauf and Coates, 4.1. Langmuir kinetics model
1947; Yang, 1987):
qt The Langmuir kinetics model can be described by Eq. (6) (Langmuir,
= kint (qet qt )
(52) 1918), as shown in the previous section. θ can be calculated by qt/qe,
t
and then Eq. (6) is transformed to Eq. (61):
The IMT model assumes that the internal diffusion is the slowest
dqt
process, and the equilibrium is obtained at the liquid-solid interface. = ka Ct (qe qt ) kd qt
dt (61)
The adsorption isotherm is used to describe the equilibrium phenom-
enon. For example, if the Langmuir model can describe the adsorption At adsorption equilibrium, Eq. (61) is reduced to the Langmuir
equilibrium data, qet is calculated as following: isotherm model (Langmuir, 1918). Eq. (61) need to be solved by the

11
J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

kL1 = ka2 (C0 qe ms ) 2+2ka kd (C0 + qe ms ) + kd (62)

kL2 = ka qe ms (63)

Shen et al. (2009) developed a simplified Langmuir kinetics model

using a simple geometric approach. Tien and Ramarao (2014) reported
a transformed Langmuir rate equation related to the PFO and PSO
models. For the applications of the Langmuir kinetics model, Al-Jabari
(2016) studied the adsorption kinetics of Cr(III) onto mineral particles
using the Langmuir kinetics. Marczewski et al. (2013) investigated the
adsorption and desorption kinetics of benzene on carbons using the
integrated Langmuir kinetics model. Marczewski (2011) extended the
application of Langmuir kinetics in dilute solutions.
The solving methods reported by the previous studies are also
complex and may lead to difficulties in parameters estimations. In the
following section, a convenient method is provided. In addition, Eq.
(64) is recommended to calculate the Langmuir adsorption rate.
Fig. 3. Statistical parameters of the adsorption kinetic models.
Langmuir rate = ka Ct (qe qt ) kd qt (64)

Runge-Kutta method with the initial condition of q0 = 0 based on

MATLAB or other programming software, which makes it difficult to 4.2. Phenomenological AAS model
apply. Efforts have been made to find the analytical solution of the
Langmuir kinetics. Liu and Shen (2008) reported that the Langmuir The Phenomenological AAS mode, which is developed based on the
kinetics could be solved by Eq. (17). The model coefficients kL1 and kL2 Langmuir kinetics model (Langmuir, 1918; Thomas, 1944), can be de-
are calculated as following: scribed by Eq. (65):

Table 6
List of the adsorption kinetic models.
Models Differential equation Integrated form or nonlinear form References

PFO model dqt qt = qe (1 e k1 t ) Lagergren, 1898

= k1 (qe qt )
dt
PSO model dqt qe2 k 2 t Ho et al., 1996
= k2 (qe qt )2 qt =
dt 1 + qe k2 t
MO model dqt – Guo and Wang, 2019a
= k1’ (qe qt ) + k2’ (qe qt )2
dt
Ritchie’s equation d
= (1 )n qt = qe (1 e t) (n = 1) Ritchie, 1977
dt
1
qt = qe qe [1 + (n-1) t ]1 n (n ≠ 1)
PNO model dqt Özer, 2007
= kn (qe qt )n 1
dt
qt = qe 1 (n ≠ 1)
(1 + (n 1) n 1kn t 1/(n 1) )
qe

Elovich model dqt bqt 1

qt = ln(1 + abt ) Elovich and Larinov, 1962
= ae b
dt
Boyd’s external diffusion dqt qt = q (1 e Rt ) Boyd et al., 1947
= R (q qt )
equation dt

F&S model – Ct 1 ms K
1 + ms K
k St Frusawa and Smith, 1973
= + e ms K F&S (Linear isotherm)
C0 1 + ms K 1 + ms K
M&W model – Ct
= e k M&W St Mathews and Weber, 1977
C0
EMT model dqt ks – Ruthven, 1984; Hines and Maddox,
= (Ct Cet ) = k ext (Ct Cet )
dt 1985
Boyd’s intraparticle diffusion – Boyd et al., 1947
(1 )
2F F 1/2
Bt = 2 2 (0 ≤ F ≤ 0.85)
model 3 3
2
Bt = ln (1 F ) (0.86 ≤ F ≤ 1)
6
W&M model – qt = kW&M t 1/2 Weber and Morris, 1963
IMT model qt – Glueckauf and Coates, 1947; Yang,
= kint (qet qt )
t 1987
PVSD model V
dCt
= mSp kF (Ct Ctr |r=r0 ) – Leyva-Ramos and Geankoplis, 1985
dt
t = 0, Ct = C0

p
Ctr
t
+
qt
p t =
1
r2 r (
r 2 Dp
Ctr
r
+
qt
p Ds r )
t = 0,0 r r0, Ctr = 0
Ctr
| =0
r r= 0
C q
Dp tr |r = r 0 + p Ds t |r = r 0 = kF (C Ctr )|r = r 0
r r
Langmuir kinetics model dqt – Langmuir, 1918
= ka Ct (qe qt ) kd qt
dt
d
= ka Ct (1 ) kd
dt
AAS model – Langmuir, 1918; Thomas, 1944
dqt
dt
= k a C0 ( mqt
V ) (q
max qt )
ka
q
KL t

12
J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

dqt ka 2019; Stähelin et al., 2018; Sari et al., 2017; Gunasundari and Kumar,
= ka Ct (qmax qt ) q
dt KL t (65) 2017; Lou et al., 2019; Guo et al., 2019a, 2019b; Yin et al., 2018; Wang
et al., 2018b; Gogoi et al., 2018; Xia et al., 2019; Islam et al., 2019;
Substitution of Eq. (38) into Eq. (65) yields:
Tang et al., 2019; Gao et al., 2019; Ahmed and Theydan, 2013; Öztürk
dqt mqt ka and Malkoc, 2014; Fu et al., 2012, 2015; Panday et al., 1986; Choy
= ka C0 (qmax qt ) q
dt V KL t (66) et al., 2004; Erdoğan and Ulku, 2012; Dávila-Guzmán et al., 2013;
Šljivić et al., 2011; Sausen et al., 2018; Ofomaja, 2010; Albadarin et al.,
Eq. (66) can be solved by the Runge-Kutta method with the initial
2012; Al-Muhtaseb et al., 2011; Sartape et al., 2017; Cantuaria et al.,
condition of q0 = 0. The AAS model has been adopted to study the
2016; Tan et al., 2016; Freitas et al., 2017; Danmaliki and Saleh, 2016;
adsorption mechanism (Blanco et al., 2017; Marin et al., 2014; Suzaki
Archin et al., 2019; Tsibranska and Hristova, 2011; Álvarez-Gutiérrez
et al., 2017; Hu et al., 2019; Guo et al., 2019b; Sausen et al., 2018).
et al., 2017; Sreńscek-Nazzal et al., 2015; AkankshaKalra et al., 2019;
Riahi et al., 2017; Saadi et al., 2015; Devi and Murugappan, 2016;
5. Model validity evaluation
Tanzifi et al., 2018; Dastkhoon et al., 2017; Karimi et al., 2016; Karri
and Sahu, 2018; Siyal et al., 2019), as shown in Fig. 3. Fig. 3 indicated
In the past decade, various statistical parameters, such as R2, adjR2,
2 that R2 and adjR2 are two of the most frequently calculated parameters.
χ , SSE, MSE, and HYBRID were used to evaluate the performance of
Over 60 % of the literature has compared the values of R2 and adjR2 to
the kinetic models (Eqs. (67)–(72)).
evaluate the kinetic models. The values of χ2, SSE, and HYBRID are also
(qmean qcal )2 calculated in some studies. The proportions of the above statistical
R2 =
(qcal qmean )2 + (qcal qexp ) 2 (67) parameters are 11 %, 11 %, and 10 %, respectively. Few studies
adopted MSE for the evaluation of their models. However, the values of
(Nexp 1) R2 of different kinetic models always have small difference. For ex-
AdjR2 = 1 (1 R2 )
(Nexp Npara 1) (68) ample, Delgado et al. (2019) reported that the values of R2 of the PFO
and PSO models were 0.998 and 0.999, respectively. Burakova et al.
2
(qexp qcal ) 2 (2018) found that the values of R2 of the PFO and the W&M models
=
qcal 2
(69) were 0.88 and 0.899, respectively. Therefore, we recommend calcu-
lating more statistical parameters to evaluate the fitting results thor-
SSE = (qexp qcal ) 2 (70) oughly and rigorously.

1
MSE = (qexp qcal ) 2 6. Solving methods for adsorption kinetic models
Nexp (71)

100 qexp qcal The adsorption kinetic models reviewed in this paper are summar-
HYBRID = ized in Table 6. In this paper, a convenient UI for solving the kinetic
Nexp Npara qexp (72)
models was developed based on Excel (see in Supplementary Informa-
Here we summarized the application of the statistical parameters based tion). The Runge-Kutta method is employed to solve the differential
on literature (Guo and Wang, 2019a; Blanco et al., 2017; Hu et al., equations (such as the MO model and the Langmuir kinetics model),
2019; Suzaki et al., 2017; Wang et al., 2008; Ma et al., 2018; Ersan and the solver add-in is applied for the calculation of the model para-
et al., 2019; Shang et al., 2019; Delgado et al., 2019; Darwish et al., meters. The statistical parameters (R2, adjR2, χ2, SSE, MSE, and HY-
2019; Sabarinathan et al., 2019; Khan et al., 2019; Gamoudi and Srasra, BRID) are calculated based on Eqs. (67)–(72). Readers can download

Fig. 4. The interface of the UI (left) and the data input window (right). (For interpretation of the references to colour in this figure text, the reader is referred to the
web version of this article.)

13
J. Wang and X. Guo Journal of Hazardous Materials 390 (2020) 122156

the UI attached in Supplementary Information and input their experi- complicated and cannot be solved by the Excel software. And the
mental data, then the fitting results will show in the sheet of Excel. Boyd’s intraparticle diffusion model is a piecewise function, which
Detailed instructions for this UI are explained as follows. can be simply solved by the linear regression method.
(6) The full names of the abbreviation of the kinetic models in this UI
(1) Download the UI in Supplementary Information. can be seen in the nomenclature table in this paper.
(2) Open the UI, activate Solver Add-in. Then press Alt + F11 to get
Visual Basic Editor, go to the Tools menu and select References
7. Concluding remarks and perspectives
from the drop-down menu. Select “Visual Basic For Applications”,
“Microsoft Excel 16.0 Object Library”, “OLE Automation”,
This review aimed to study the physical meanings, applications, and
“Microsoft Office 16.0 Object Library”, “Microsoft Forms 2.0 Object
solving methods of 16 adsorption kinetic models, including 6 adsorp-
Library”, “Solver”, and “Ref Edit Control”.
tion reaction models and empirical models, 8 diffusional models, and 2
(3) The model selection interface is shown in the Excel (Fig. 4 (left)).
models for adsorption onto active sites.
Readers can choose one kinetic model, and click the “OK” button.
For the adsorption reaction models and empirical adsorption kinetic
(If the model selection interface is not displayed, please enable the
models, the most widely used PFO model and PSO model can be de-
edit view.)
duced by the Langmuir kinetics. The theoretical analysis and the review
(4) After click the “OK” button, the data input window is shown in the
on literature indicated that the PFO model represented the conditions of
Excel (Fig. 4 (right)). Please input the adsorption time t and the
(1) at high initial concentrations of adsorbate; (2) at the initial stage of
experimental adsorption capacity qt, as well as other data based on
adsorption, and (3) few active sites exist in the adsorbent material. In
the kinetic models used, and click the “Fit” button. Please note that
some cases, the PFO model can describe the diffusional kinetics process.
each t and qt should be separated by a comma. (Fig. 4 (right))
The PSO model could represent the conditions of (1) at high initial
(5) The results are shown in “a1” sheet (Fig. 5). If this UI fails to solve
concentrations of adsorbate; (2) at the final stage of adsorption, and (3)
your kinetic model, please close the Excel and re-open it, and then
the adsorbent is abundant with active sites. The PSO model reveals the
try another initial value of the parameter. You may have to try
mechanism of adsorption in active sites in most cases. The MO kinetics
several times to get the proper initial value of the parameters.
can describe the whole adsorption processes. The empirical Elovich and
(6) After solving one kinetic model, please record the parameters of the
the PNO models are applied in some studies, but they are lacking of
models and export the figure of the fitting results (Fig. 5) in a new
specific physical meanings and cannot offer important information
Excel. Then close the UI and re-open it. You can choose another
about the mass transfer mechanisms.
kinetic model for calculation.
For the mass transfer models, the external diffusion process can be
described by the Boyd’s external diffusion equation, F&S, M&W, and
Several points should be noticed when using the UI for calculation:
phenomenological EMT models. These models have specific physical
meanings (external diffusion), and they are more suitable to model the
(1) In the data input window, if the background of the input position is
external mass transfer processes. The Boyd’s intraparticle diffusion
yellow (Fig. 4 (right)), this value is related to the experimental data
model, M&W, and phenomenological IMT models can represent the
or the data calculated by the isotherms. These values will not
intraparticle diffusion process. For the adsorption in active sites pro-
change in the solving process.
cess, the Langmuir kinetics, Ritchie’s equation and the phenomen-
(2) For the Ritchie’s equation, the value of n is assumed to be larger
ological AAS models can describe this process. These models can give
than 1, because calculation errors are generated when 0 < n < 1.
the mass transfer mechanisms more accurately. The chosen of the ki-
(3) Eqs. (39) and (42) are used as the equations of the F&S and M&W
netic models should be based on the mass transfer processes.
models.
In addition, the statistical parameters R2, adjR2, χ2, SSE, MSE, and
(4) For the EMT, IMT, and AAS models, the Langmuir isotherm is
HYBRID are widely used to evaluate the performance of the kinetic
adopted to describe the adsorption equilibrium phenomenon.
models. In which R2 and adjR2 are the most frequently applied statis-
(5) Please note that the PVSD and the Boyd’s intraparticle diffusion
tical parameters. To rigorously evaluate the fitting results of the kinetic
models are not included in this UI. Because the PVSD model is
models, we recommend calculating all the above statistical parameters.

Fig. 5. Fitting results of the adsorption kinetic model.

14
J. Wang and X. Guo
The adsorption kinetic models include the nonlinear kinetic models
(such as the nonlinear PFO, PSO models and the Elovich model) and the
differential kinetic models (such as the MO model, the phenomen-
ological EMT, IMT, and AAS models, and the Langmuir kinetics model).
The solving methods for these models are required. In this paper, an UI
for solving the kinetic models is developed based on Excel solver add-in
and the Runge-Kutta method, which can be used conveniently to solve
the models reported in this review.
In recent years, some other novel kinetic models, such as the
Largitte double step model (Largitte and Pasquier, 2016), the film-pore
mass transfer (FPMT) model (Guo and Wang, 2019d), Gaulke’s unified
kinetic model (Gaulke et al., 2016), and the fractal-like adsorption ki-
netic models (El Boundati et al., 2019) have also been proposed. Al-
though these novel models are not frequently used by researchers, they
are expected to help to investigate the adsorption mechanisms, and to
model the adsorption systems.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence 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 material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2020.122156.
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