Journal of Molecular Liquids 288 (2019) 111100

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

A general kinetic model for adsorption: Theoretical analysis

and modeling
Xuan Guo a, Jianlong Wang a,b,⁎
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

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

Article history: Adsorption technology has been widely applied for water and wastewater treatment due its low cost and easy
Received 22 February 2019 operation. Understanding the adsorption kinetic could help to design the adsorption system. The pseudo-first-
Received in revised form 25 May 2019 order (PFO) and pseudo-second-order (PSO) kinetic models were usually used, however their specific theoretical
Accepted 29 May 2019
meanings and the application conditions were still unclear. In addition, for a practical adsorption system, the ki-
Available online 1 June 2019
netic process is complex, which may include both the PFO and PSO kinetic process. Therefore, it is necessary to
Keywords:
develop a general kinetic model to describe the whole adsorption process more accurately. In this paper, based
Adsorption on the Langmuir kinetics, and the theoretical analysis of the PFO and PSO models, a general form of adsorption
General adsorption kinetics kinetic model was developed. The experimental data from our previous studies and literature were used to fit
Pseudo-first-order kinetic the mixed-order (MO) model. The results showed that it is capable of describing both the PFO and PSO kinetic
Pseudo-second-order kinetic process and suitable for whole adsorption process, suggesting that it can describe the kinetics of whole adsorp-
Mixed-order kinetic tion process better. The MO kinetic model can be solved by using 4–5 order Runge-Kutta method, and the solving
program as well as the method illustration was provided in Appendixes, which can be used by the readers who
are interested in this model.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction
Adsorption is a process that the pollutants in solution transfer onto
the solid adsorbent, which is widely used in environmental pollution
control, such as water and wastewater treatment [1]. For the designa-
tion of the adsorption system, it is essential to study the adsorption ki-
netics, which can be used to predict the pollutants removal rate, to
establish the time dependence of the residual adsorbate in solution,
and to reveal the mechanisms involved in the adsorption process.
Various kinds of kinetic models have been applied to describe the
adsorption kinetics, e.g., the pseudo-first-order (PFO) model [2], the
pseudo-second-order (PSO) model [3,4], the Langmuir kinetic model
[5], and the Elovich model. Among these kinetic models, the PFO and
PSO models are most frequently used. Over the years, most of the stud-
ies described the adsorption kinetics by employing both the PFO and
PSO models in parallel, and concluded whether the PFO or PSO could
better describe the experimental kinetic data by analyzing the correla-
tion coefficient (R2) or other statistical parameters [6–17].
⁎ Corresponding author at: Energy Science Building, Tsinghua University, Beijing
100084, PR China.
E-mail address: wangjl@tsinghua.edu.cn (J. Wang).
Liu and Shen [18] derived the PFO and PSO models from the Lang-
muir kinetics, and suggested that the PFO and PSO kinetic was related
to the values of equilibrium fraction of adsorbent active sites and the
ratio of the pseudo-first- and -second-order rate constants. Azizian
[19] concluded that the PSO and PFO models were capable of modeling
the adsorption kinetic at low and high initial adsorbate concentration,
respectively. Ho [20] indicated that the PSO model can be used to repre-
sent chemisorption process. Simonin [21] concluded that the pseudo-
second-order rate constant k2 was unable to describe the steep rise of
the sorption capacity at short times. Hu et al. [22] found that at the initial
stage of adsorption, the PSO model could be approximated to the PFO
model. Accordingly, the PFO and PSO models can only describe some
specific adsorption conditions.
However, the specific theoretical meanings and the application con-
ditions for the PFO and PSO kinetic models have not been systematically
evaluated. In addition, for a practical adsorption system, the kinetic pro-
cess is more complex, and may include both the pseudo-first- and
-second-order kinetics processes. Therefore, the more general kinetic
model should be developed to represent accurately the experimental ki-
netic data and to predict the whole adsorption kinetic process.
The objectives of this study were (1) to develop a general kinetic
model (the mixed-order (MO) model) on the basis of the Langmuir,
PFO, and PSO kinetic models, and to provide the solving method and

https://doi.org/10.1016/j.molliq.2019.111100
0167-7322/© 2019 Elsevier B.V. All rights reserved.
2 X. Guo, J. Wang / Journal of Molecular Liquids 288 (2019) 111100

program; and (2) to validate the kinetic models using the experimental
data from our previous studies and literatures.
2. Theoretical analysis and mathematical modeling
Adsorption is a selective mass transfer process that the adsorbate in
solution transfers to the solid phase. Considering the adsorption and de-
sorption, the adsorption kinetic process can be described by Eq. (1):
occupations of adsorbent active sites. If the initial adsorbate concentra-
tion is far greater than the occupied active sites, namely, a few active
sites are occupied compared with the adsorbate concentration, βθ can
be generally neglected. There are several conditions for this hypothesis:
(a) At the initial stage of adsorption, the fraction of occupied active
sites of the adsorbent approaches to zero.

nA þ a ↔nAa ð1Þ The linear forms of the PFO model (Eq. (9)) and the PSO model
(Eq. (10)) can be rewritten as follows [22]:
where A is the adsorbate in solution; a is the vacant sites of the adsor-
bent; n is the stoichiometric coefficient of the reaction. ln ðqe −qt Þ ¼ lnqe −k1 t ð9Þ
The adsorption kinetic model is then presented by Eq. (2), which is
also known as the Langmuir kinetic model [4]: ln ðqe −qt Þ ¼ lnqe − ln ð1 þ k2 qe t Þ ð10Þ

dq where k2 (g/(mg·min)) is the pseudo-second-order rate constant.

¼ ka C t ð1−qÞ−kd q ð2Þ If t approaches zero:
dt

where θ (0 ≤ θ ≤ 1) is the coverage fraction; Ct (mg/L) is the adsorbate ln ð1 þ k2 qe t Þ ≈ k2 qe t ð11Þ

concentration in the liquid phase at time t; ka and kd are the adsorption
and desorption rate constants, respectively. By definition of:
The expression of Ct can be given by Eqs. (3)–(4) [19]:
k1 ¼ k2 qe ð12Þ
C t ¼ C 0 −βθ ð3Þ
Substitution of Eq. (12) into Eq. (11) leads to:
mqm
β¼ ð4Þ
V ln ðqe −qt Þ ¼ lnqe −k1 t ð13Þ

where qm (mg/g) is the maximum adsorption capacity; C0 (mg/L) is the

The PSO model was transformed to the PFO model at the initial stage
initial adsorbate concentration in solution; m (g) is the adsorbent mass;
of adsorption [22], which confirmed our hypothesis.
V (L) is the solution volume.
Thus, Eq. (2) can be rewritten as Eq. (5): (b) A few active sites exist in the adsorbent.

dq
¼ ka ðC 0 −βθÞð1−θÞ−kd θ ð5Þ
dt Considering the mass transfer steps, the adsorption of the adsorbate
onto the active sites is not the main mechanism of the adsorption pro-
Eq. (5) is usually adopted as the basic equation to analyze the ad- cess (external and/or internal diffusion may dominate the adsorption
sorption kinetics. process).

2.1. The PFO model (c) The initial adsorbate concentration in solution is very high.

The PFO model has been frequently used to describe the kinetic pro-
cess under un-equilibrium conditions, which can be presented as a dif- Azizian [19] summarized the adsorption data in literatures, and con-
ferential equation [1]: cluded that with high initial adsorbate concentration in solution, the
PFO model gave better prediction for the kinetic data than the PSO
dqt model.
¼ k1 ðqe −qt Þ ð6Þ
dt For these conditions, βθ can be neglected. Eq. (5) is transformed to
Eq. (8), and Eq. (8) can be derived to the PFO model.
where qt (mg/g) and qe (mg/g) are the adsorbate concentration in the
solid phase at time t and at equilibrium, respectively; k1 (1/min) is the
2.2. The PSO model
pseudo-first-order rate constant.
Integrating Eq. (6) with the initial condition of q0 = 0 at t = 0, the
The PSO model is the most widely used kinetic model in adsorption.
PFO model can be rewritten as Eq. (7):
The PSO model is described by Eq. (14) [2,3]:


qt ¼ qe 1−e−k1 t ð7Þ dqt
¼ k2 ðqe −qt Þ2 ð14Þ
dt
Considering the basic model (Eq. (5)), if C0 is very high compared to
βθ (C0 ≫ βθ), Eq. (5) can be simplified to Eq. (8): Integrating Eq. (14) with the initial condition of q0 = 0 leads to:

dθ q2e k2 t
¼ ka C 0 ð1−θÞ−kd θ ð8Þ qt ¼ ð15Þ
dt 1 þ qe k2 t

Then Eq. (8) can be derived to the PFO model [19].
To further analyze the physical meanings of the PFO model, we re-
discuss (C0-βθ) in Eq. (5). For a given adsorption process, the variable
β is approximately a constant, thus, the value of (C0-βθ) is related to
C0 and θ. C0 is the initial adsorbate concentration, and θ represents the
The PSO model can be derived from Eq. (5) if the initial adsorbate in
solution is low and βθ cannot be neglected [19].
Here we discuss the (C0-βθ) in Eq. (5). If most of the adsorbent active
sites are occupied, βθ is not negligible. Several conditions should be con-
sidered for this hypothesis:
 X. Guo, J. Wang / Journal of Molecular Liquids 288 (2019) 111100 3

(a) At the final stage of adsorption. At adsorption equilibrium, dθ/dt becomes zero, solving Eq. (19) for
The fraction of occupied adsorbent active sites increases with the equilibrium fraction of the occupied adsorbent active sites (θe)
time. Thus, βθ is not negligible at the final stage of adsorption. yields:
(b) The adsorbent is abundant with active sites.
0 pffiffiffiffi
The adsorption onto the active sites is the main mechanism and n2 M
rate-controlling step of the adsorption process. Bm1 n1 M VNA þ βÞ þ kd1 θ þ kd2 θ þ Δ
θe ¼ ka1 B
@ VN þ ð20Þ
(c) The initial adsorbate concentration in solution is low. A 2ka β
Azizian [19] found that when initial adsorbate concentration in
solution is low, the PSO represents adequately the adsorption ki-
netic data. where Δ is given by:
" 
2
2.3. The mixed-order (MO) model m1 n1 M n2 M n1 M n2 M
Δ ¼ ka1 þ þ βÞ þ kd1 θ þ kd2  −4ka βka þ Þ
VNA VNA VNA VNA
We concluded from Sections 2.1 and 2.2 that the PFO and PSO
ð21Þ
models represent the relationship between the adsorbate in solution
and the occupations of the adsorbent active sites in the adsorption pro-
cess. Specifically, the PFO model describes a few occupations of the ad- Substitution of Eq. (18) into Eq. (17) yields:
sorbent active sites, while the PSO model represents most occupations
dθ 0 0
of the adsorbent active sites. However, for a real adsorption process, ¼ k1 ðθe −θÞ þ k2 ðθe −θÞ2 ð22Þ
the occupations of the adsorbent active sites are more complex. For ex- dt
ample, at the initial stage of adsorption, a few active sites are occupied,
where k1′ (1/min) and k2′ (g/(mg·min)) are the pseudo-first- and
and the PFO model could represent this phenomenon. At the end stage
-second-order rate constants of the MO model, respectively:
of adsorption, most of the active sites are occupied, and the PSO model
may describe this process. Thus, the PFO and PSO models only describe 0
pffiffiffiffi
some special conditions in adsorption process, but not the overall ad- k1 ¼ Δ ð23Þ
sorption process. Therefore, a more general adsorption kinetic model,
0
which can describe all conditions and whole adsorption process, should k2 ¼ ka β ð24Þ
be developed.
We assume that the total number of adsorbate ions/molecules/ Moreover, θ is the ratio of qt and qm, and θe is the ratio of qe and qm:
atoms at the initial stage of adsorption is ntotal. Then ntotal could be di-
vided into m1n1 and n2 qt
θ¼ ð25Þ
qm
ntotal ¼ m1 n1 þ n2 ð16Þ
qe
where n1 is the number of the active sites; m1 is the average number of θe ¼ ð26Þ
qm
adsorbate ions/molecules/atoms on one active site, and n2 is the number
of adsorbate that could not be adsorbed on active sites. where qm (mg/g) is the maximum adsorption capacity.
Then the initial concentration of adsorbate is described by Eq. (17) Substitution of Eqs. (25)–(26) into Eq. (22) leads to:

dq 0 0
ntotal M ðm1 n1 þ n2 ÞM ¼ k1 ðqe −qÞ þ k2 ðqe −qÞ2 ð27Þ
C0 ¼ ¼ ð17Þ dt
VNA VNA

where M (g/mol) is the molar mass of the adsorbate, V (L) is volume of Eq. (27) is the general form of the MO kinetic model.
the solution, NA (6.02 × 1023 1/mol) is the Avogadro's number. This equation has similar form with the hybrid kinetic equations re-
Substitution of Eq. (17) into Eq. (5) yields: ported by Liu and Shen [18] and Marczewski [23], however, the equa-
tion from Liu and Shen [18] was associated with the occupied fraction

dθ ðm1 n1 þ n2 ÞM of active sites, but not the overall adsorption process; the equation
¼ ka −βθð1−θÞ−kd ð18Þ from Marczewski [23] was simplified based on some assumptions, and
dt VNA
may cause lower precision of the fitting results.
Eq. (18) is then transformed to Eq. (19): Moreover, the MO model can represent the following conditions:

   (a) At any stage of the adsorption process.

dθ m1 n1 M n2 M (b) Considering the mass transfer steps, the diffusion of adsorbate
¼ ka −βθÞð1−θÞ−kd1 θ þ ka ð1−θÞ−kd2 θ ð19Þ
dt VNA VNA and/or the adsorbate adsorption onto the active sites dominates
the adsorption process.
where kd1 and kd2 are desorption rate constants. kd1 and kd2 are sum up (c) Arbitrary initial adsorbate concentration in solution.
to kd.
Eq. (19) is a kinetic model, which combines the pseudo-first- and
-second-order kinetics. It has the following interpretation:
The MO model (Eq. (27)) can be solved by using 4–5 order Runge-
(1) For n1 of the adsorbate, the occupations of the active sites have Kutta method. The experimental kinetic data from our previous studies
the same order of magnitude as the number of the adsorbate. and from literature were fitted by using the nonlinear least square
The adsorption onto active sites is the rate limiting step for this method. Moreover, the value of qe is obtained by the kinetic experimen-
part of adsorbate. tal data.
(2) For n2 of the adsorbate, few free active sites exist in the adsorp- The Matlab R2014 (b) was used in this paper, the solving program
tion system; the adsorption onto active sites is not the rate- and the method were provided in Appendixes A and B, respectively,
limiting step. which are available online and can be used for readers.
4 X. Guo, J. Wang / Journal of Molecular Liquids 288 (2019) 111100

X
2
2.4. Model validity evaluation SSE ¼ qexp −qcal ð30Þ

To assess the fitting results of the kinetic models to the experimental 2
2

data from literature, the statistical parameters (i.e. the adjusted correla- 6X qexp −qcal 2ðp þ 1Þðp þ 2Þ
tion coefficient (adjR2), the chi-square (χ2), the residual sum of squares AICc ¼ N ln 4  þ 2ðp þ 1Þ þ ð31Þ
N N−p−2
(SSE), and the Akaike information criterion correction (AICc)) were cal-
culated by Eqs. (28)–(31):
where qexp (mg/g) is the experimental adsorption capacity; qcal (mg/g)
P
2 is the adsorption capacity calculated from the models; qmean (mg/g) is
qexp −qcal ðN−1Þ
2
adjR ¼ 1−
the average experimental adsorption capacity; N is the number of the
P 2  ð28Þ
ðN−P Þ experimental data, P is the number of the parameters of the models.
qexp −qmean

3. Experimental data fitting

2
X qexp −qcal
χ2 ¼ ð29Þ In order to test the MO model, six sets of experimental data from
qcal literatures [24–29] were modeled using the MO model and shown

2.5

40 (a)
(b)
2.0

30
1.5
qt(mg/L)
qt(mg/L)

20
1.0
PFO
PFO
PSO
PSO
10 0.5 MO
MO

0 0.0
0 400 800 1200 1600 0 120 240 360 480 600
Time (min) Time (min)
30 0.6
(d)
(c)
25

20 0.4
qt(mg/L)

qt(mg/L)

15

PFO PFO
10 0.2
PSO PSO
MO MO
5

0 0.0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 0 300 600 900 1200 1500
Time (min) Time (min)
350 50
(f)
300 (e)
40
250

30
qt(mg/L)

qt(mg/L)

200

150
20
PFO PFO
100 PSO PSO
MO MO
10
50

0 0
0 3000 6000 9000 12000 0 120 240 360 480 600
Time (min) Time (min)

Fig. 1. Adsorption kinetic data from literature: (a) [24]; (b) [25]; (c) [26]; (d) [27]; (e) [28]; and (f) [29], predicted by the PFO, PSO, and MO kinetic model.
 X. Guo, J. Wang / Journal of Molecular Liquids 288 (2019) 111100 5

in Fig. 1. Moreover, the values of the kinetic parameters and the
statistical parameters were calculated from the MO model and
summarized in Table 1. The parameters of the nonlinear PFO and
the PSO models were also shown in Table 1 for the comparison of
the kinetic models.
By the graphical interpretation (Fig. 1) together with judging
the values of the statistical parameters of adjR 2 (≥0.95), χ 2 , SSE
(Table 1), we can see that the MO model had excellent prediction
for the kinetic data from literature. In addition, the MO model al-
ways shows lower AICc value than the PFO and PSO models,
which confirmed this result. As shown in Table 1, for the experi-
mental data from the references [24, 26–28], the values of the
pseudo-first-order rate constant k 1 ′ of the MO model were
0.0092, 0.0001, 0.0002, and 0.0921 1/min, respectively; and the
values of the pseudo-second-order rate constant k 2 ′ were 0.0029,
0.0001, 0.000005 and 0.2288 g/(mg·min), respectively, implying
that the adsorption is the combination of the pseudo-first- and
-second-order kinetic processes. The rate of the overall adsorption
process was calculated by the Eqs. (32)–(33):
0 model could reduce to the PFO model if there was no PSO kinetic
Pseudo‐first‐order‐rate ¼ k1 ðqe −qÞ
0
Pseudo‐second‐order‐rate ¼ k2 ðqe −qÞ2
The results are shown in Fig. 2. We can see from Fig. 2(a),
(c) and (e) that the PSO rate (the rate of adsorption on the active
sites) was much bigger than the PFO rate (the rate of other mass
transfer processes). The PSO kinetic was the main kinetic process.
Therefore, increasing the amount of the active sites by the modifi-
cation of the adsorbate may improve the sorption capacity. As
shown in Fig. 2(d), the PFO rate was in the same order of magnitude
as the PSO rate, indicating that the adsorption process was domi-
nated by multiple rate limiting steps. Fig. 2 also shows that the
highest values of the PFO and PSO rate were achieved at the begin-
ning of the adsorption process, and then decreased dramatically
with time until equilibrium.
For the experimental data from reference [29], both the MO and
the PSO models could provide good fit, by judging the R2 , χ2 , SSE,
and AICc values (Table 1). The values of k 1 ′ and k 2 ′ estimated by
the MO model were 0 and 0.00158 g/(mg·min), respectively
(Table 1), indicating that the adsorption process followed the
pseudo-second-order kinetic. This result also demonstrated that
the MO model could reduce to the pseudo-second-order model if
the adsorption on active sites was the rate limiting step. The
value of k 2 ′ (0.00158 g/(mg·min)) was similar with k 2 (0.00179
g/(mg·min)), the highest value of the adsorption rate was 3.31
mg/(g·min), which was reached the beginning of adsorption and
then decreased with time.
For the experimental data from reference [25], we can see from Fig. 1
(b) and Table 1 that both the MO and PFO kinetic models adequately
represent the data, with high R2 values (N0.99) and low χ2, SSE, and
AICc values. The rate constants k1′ and k2′ estimated by the MO model
were 0.0142 1/min and 0 g/(mg·min), respectively. The value of
the k 1 estimated by the PFO model was 0.0144 1/min, which was
similar to the value of k 1 ′. Therefore, the adsorption followed to
the PFO kinetics. The value of k 2 ′ of 0 indicated that the MO
ð32Þ
process in adsorption. The rate of the overall adsorption process
is shown in Fig. 2(b). The PFO rate decreased from 0.0325 mg/
ð33Þ (g·min) to 0 at the initial 7 h, while the PSO rate was 0 for the over-
all adsorption process (Fig. 2(b)). Thus, the adsorption onto the ac-
tive sites was not the rate-limiting step. The increasing of specific
areas and pore volumes of the adsorbate may increase the adsorp-
tion capacities controlled by the external/internal mass transfer.
These results suggested that the MO model could be regard as a
more general form of the PFO and PSO kinetic models. The MO model
was more practical and precise to predict the kinetics of complex behav-
iors of the adsorption process.
4. Conclusions
The MO kinetic model has been developed on the basis of the
Langmuir kinetics model, and the theoretical analysis of the PFO

Table 1
Adsorption kinetics parameters and statistical parameters.

Models Parameters Ref. [24] [25] [26] [27] [28] [29]

a b c d
Adsorbent nZVI/graphene Magnetic chitosan ALiCE PA DOSD-2 BCM@APTES-EDTAe
b c d
Adsorbate Co (II) Sr (II) MB SMX RB5G Sr (II)

PFO k1 (1/min) 0.0730 0.0144 0.0024 0.146 0.0009 0.0514

qe (mg/g) 34.0 2.27 24.8 0.400 284 40.3
adjR2 0.955 0.995 0.884 0.992 0.960 0.920
χ2 1.21 0.0653 14.8 0.00293 60.9 4.35
SSE 37.7 0.0321 181 0.00116 4760 118
AICc 24.4 −38.8 51.6 −78.6 94.6 33.9
PSO k2 × 102 (g/(mg·min)) 0.300 0.0635 0.01 62.1 0.00039 0.179
qe (mg/g) 35.9 2.61 28.03 0.412 320 43.0
adjR2 0.987 0.984 0.947 0.980 0.991 0.976
χ2 0.328 0.141 6.68 0.00822 13.0 1.20
SSE 10.8 0.0970 83.2 0.00286 1052 32.8
AICc 14.4 −28.8 36.0 −69.6 72.0 22.4
MO k1′ (1/min) 0.00920 0.0142 0.0001 0.100 0.0002 0
k2′ × 102 (g/(mg·min)) 0.290 0 0.01 22.88 0.0005 0.158
adjR2 0.991 0.994 0.950 0.992 0.990 0.983
χ2 0.285 0.0644 5.36 0.00284 15.1 0.759
SSE 9.14 0.0320 80.8 0.00107 1210 24.3
AICc 13.1 −38.6 36.0 −79.4 74.1 19.7
a
The full name of nZVI/graphene was shown in [24].
b
The full names of ALiCE and MB were shown in [26].
c
The full names of PA and SMX were shown in [27].
d
The full names of DOSD-2 and RB5G were shown in [28].
e
The full name of BCM@APTES-EDTA was shown in [29].
6 X. Guo, J. Wang / Journal of Molecular Liquids 288 (2019) 111100

0.4 4 0.04 0.15

(a) (b)

0.3 Pseudo-first-order rate 3 0.03

Pseudo-first-order rate

v (mg/(g·min))
0.10

v (mg/(g·min))

v (mg/(g·min))

v (mg/(g·min))
Pseudo-second-order rate Pseudo-second-order rate

0.2 2 0.02

0.05
0.1 1 0.01

0.0 0 0.00 0.00

0 100 200 1200 1300 1400 1500 0 150 300 450 600
Time (min) Time (min)
0.005 0.08 0.04 0.04
(c) (d)
0.004 Pseudo-first-order rate
0.06 0.03 0.03
Pseudo-second-order rate Pseudo-first-order rate
v (mg/(g·min))
v (mg/(g·min))

v (mg/(g·min))
v (mg/(g·min))
Pseudo-second-order rate
0.003
0.04 0.02 0.02
0.002

0.02 0.01 0.01

0.001

0.00 0.00 0.00

0 1000 2000 3000 4000 0 20 40 60 1480 1500
Time (min) Time (min)
4 30 0.15 4
(e) (f)
25
3 Pseudo-first-order rate Pseudo-first-order rate 3
v (mg/(g·min))

20
v (mg/(g·min))

Pseudo-second-order rate

v (mg/(g·min))
0.10 Pseudo-Second-order rate
v (mg/(g·min))

2 15 2

10 0.05
1 1
5

0 0.00 0
0 3000 6000 9000 12000 0 40 80 520 560 600
Time (min) Time (min)

Fig. 2. The overall adsorption rate of the kinetic data from literature: (a) [24]; (b) [25]; (c) [26]; (d) [27]; (e) [28]; and (f) [29].

and the PSO kinetic models. This model can be considered as a more PSO rate were achieved at the beginning of the adsorption process,
general form of the PFO and PSO kinetic models, which can describe and then decreased dramatically with time until equilibrium.
all the adsorption process. The MO model represented the condi- These results confirmed that MO model can be satisfactorily used
tions of (a) at any stage of adsorption process, (b) any mass trans- to describe the kinetics for whole adsorption process.
fer controlling steps and (c) arbitrary initial adsorbate
concentration. The experimental data from our previous studies Acknowledgments
and literature were fitted by the MO kinetics. The results showed
an excellent agreement between the MO model and the experi- The research was supported by the National Key Research and De-
mental data, with high R 2 values (N0.95) and low χ 2 , SSE, and velopment Program (2016YFC1402507) and the Program for
AICc values. The overall rate of the adsorption process could also Changjiang Scholars and Innovative Research Team in University (IRT-
be calculated by the MO model. The highest values of the PFO and 13026).
 X. Guo, J. Wang / Journal of Molecular Liquids 288 (2019) 111100
Appendix A. The program to solve the MO kinetic model
Appendix B. The method for the program
The program in Appendix A provides a versatile method to solve the
differential equation model and estimate the parameters in the model.
The steps to use the above program are listed as follows:
(1) Open the Matlab software and create a new M. file.
(2) Copy the program in Appendix A to the new M. file, and rename
the M. file as ‘modelfit’, as shown in Fig. S1.
(3) Save the ‘modelfit’ file to the path of Matlab software.
(4) Input the values of adsorption time and the uptakes of adsor-
bate by adsorbent at time t in matrix t [] and y [], respectively.
Input the initial condition of y0 = 0. An example is given in
Fig. S2.
(5) Give the initial values, low limit values and high limit values of
the parameters (k1′, k2′), and store in matrix beta0 [], lb [], and
ub [], respectively (Fig. S3). The choice of the initial values of
the parameters is crucial to estimate the parameters in the
7
kinetic models, so one may try several times to choose the
proper initial values of the parameters.
(6) Input the value of qe. Define the model equation, as shown in
Fig. S4. (Note that if one wants to fit the experimental data
to a new model, please edit the model equation to a new one).
(7) Input ‘modelfit’ in the command window of the Matlab soft-
ware and press enter. The fitting results are shown in the com-
mand window (Fig. S5), where k 1 and k 2 are the frist- and
second-order rate constants, the value of the residual sum of
squares (SSE) is also presented in the command window.
The figure result is depicted in the figure window (Fig. S6).
(8) If you want to get the plot information of the figure result,
please input the following program in the command window.
The results will be presented in the work space (Fig. S7):
h = get (gca,'children');
Xdata = get (h,'Xdata');
Ydata = get (h,'Ydata').
8 X. Guo, J. Wang / Journal of Molecular Liquids 288 (2019) 111100
Appendix C. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.molliq.2019.111100.
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