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Karbala International Journal of Modern Science 4 (2018) 244e254
http://www.journals.elsevier.com/karbala-international-journal-of-modern-science/

Critical of linear and nonlinear equations of pseudo-first order

and pseudo-second order kinetic models
Hamou Moussout*, Hammou Ahlafi, Mustapha Aazza, Hamid Maghat
Laboratory of Chemistry and Biology Applied to the Environment, Faculty of Sciences, Moulay Ismaïl University, BP 11201-Zitoune,
Mekn
es, 50060, Morocco
Received 30 November 2017; revised 4 April 2018; accepted 5 April 2018
Available online 4 May 2018

Abstract

The experimental adsorption equilibrium of Cd(II) onto chitosan (Cd(II)/CS) and methyl orange onto bentonite (MO/Bt) were
studied in batch adsorption experiments at room temperature for an initial concentration of 236.5 mg/L for Cd (II) (pH ¼ 5) and
33 mg/L for MO (pH ¼ 3). The adsorption rate increases rapidly for t < 30 min, and the equilibrium is reached after this contact
time for both systems. The values of the experimental maximum amount of Cd(II) and MO adsorbed are qe ¼ 56.70 and 56.55 mg/g
for Cd/CS and MO/Bt, respectively. The obtained experimental data were analysed using the linear and the nonlinear forms of
pseudo-first and pseudo-second order kinetic models (LPFO, NLPFO, LPSO, NLPSO). The appropriate model to describe the
adsorption kinetics of each system was determined based on the comparison of R2 and the standard deviation Dq (%). It was found
that the adsorption process of Cd(II)/CS followed NLPFO and that of MO/Bt can be described by both of NLPSO and LPSO. The
results show that the nonlinear forms (NLPSO and NLPFO) are suitable for describing the kinetics adsorption reactions in the liquid
phase and the LPSO (qt ¼ f(1/t) model can also be suitable for some systems, depending on the experimental conditions. Because of
qt values, determined from these models correspond well to the experimental data as confirmed by the error analysis values of R2
and Dq (%), it is noticed that the determination of R2 alone is insufficient to decide among the kinetic models.
© 2018 The Authors. Production and hosting by Elsevier B.V. on behalf of University of Kerbala. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: Adsorption kinetics; Linear and nonlinear models; Pseudo-first order; Pseudo-second order

1. Introduction a good condition, industrial wastewater must be treated

Environmental degradation due to the release of
different pollutants into receiving environments by
industrial and agricultural activities has become of
great importance. Thus, to maintain our environment in
* Corresponding author.
E-mail addresses: moussouthammou@gmail.com, h.moussout@
edu.umi.ac.ma (H. Moussout).
Peer review under responsibility of University of Kerbala.
before it is discharged. Among several methods cited
in the literature for treatment of wastewaters [1e3], the
adsorption is the most widely used method, in com-
parison to other ones, to eliminate both organic and
inorganic pollutants [4,5], because it has several ad-
vantages regarding cost, efficiency and ease of use
[6,7]. Generally, whatever the nature of the used ad-
sorbents and the pollutants to be treated, the adsorption
process is always controlled by two important aspects:
kinetics and thermodynamics. In order to better

https://doi.org/10.1016/j.kijoms.2018.04.001
2405-609X/© 2018 The Authors. Production and hosting by Elsevier B.V. on behalf of University of Kerbala. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 H. Moussout et al. / Karbala International Journal of Modern Science 4 (2018) 244e254
Nomenclature
C0 Initial concentrations in liquid solution
(mg.L1)
Ce Equilibrium concentrations in liquid
solution (mg.L1)
qe Amount adsorbed at equilibrium (mg.g1)
qt Amount adsorbed at time t (mg.g1)
V Volume of the solution (L)
mads Mass of the adsorbent (g)
qt,exp Adsorbed amounts experimental
qt,cal Adsorbed amounts calculated
kn Rate constant for a kinetic with order n
k1 Rate constant for a kinetic of the pseudo
first order (min1)
k2 Rate constant for a kinetic model of pseudo
second order (g.mg1.min1)
teq Equilibrium time (min)
NLPFO Nonlinear pseudo first order model
LPFO Linear pseudo first order model
NLPSO Nonlinear pseudo second order model
LPSO Linear pseudo second order model
SD Standard deviation
understand the interactions between adsorbents and
adsorbates at equilibrium, several parameters (qt:
adsorbed amount, teq: equilibrium time, qe: adsorbed
amount at equilibrium, and Ea: activation energy)
were, thus, determined, using various kinetic and
isothermal models, especially those of Lagergren, and
Blanchard et al. (1984) and Ho for pseudo-first order
(PFO) and pseudo-second order (PSO), respectively
[8e10]. Langmuir and Freundlich models [11,12],
which are based on the solution concentration, were
commonly used to describe adsorption isotherms.
In most cases, the kinetic and the isothermal pa-
rameters were deduced by a simple confrontation of
the experimental data with the linearized equations of
these models. Accordingly, the constants can be ob-
tained from the slope and the intercept of a straight t
line plot, and the appropriate model which fits the
experimental data is the one whose coefficient of
determination (R2) is close to the unity. However,
several articles related to this field [13e17], have
shown that the incorrect application of the linear
equations for the kinetic models of PFO and PSO lead
to the erroneous values of the intrinsic kinetic param-
eters. This problem was related to the various used
mathematical expressions and to the unknown value of
qe [14,18]. Plazinski et al. [19] portrayed that PSO's
245
wide applicability over PFO does not necessarily stem
from a physical basis, but from a mathematical one. On
the other hand, The PFO model has been demonstrated
to be valid only at the initial stage of adsorption [20].
Similarly, in the case of adsorption isotherms, crit-
icisms have been reported concerning the application
of the linear equations of the Langmuir and Freundlich
isotherms, which are the most often used to predict the
maximum adsorption capacity (qm) at equilibrium and
the affinity of the adsorbents for the adsorbates.
Vasanth Kumar and Sivanesan [21] recommended that
the use of equilibrium data covering the complete
isotherm was the best way to obtain the parameters in
isotherm expressions; equilibrium data with a partial
isotherm was insufficient. Moreover, for the best fit of
experimental kinetic and isotherm data, both in batch
and column experiment or in other systems involving
the transfer of fluids, several studies [22e28] have
displayed that the application of the nonlinear method
is more suitable than the linear one [22,23,29e35],
because it allows a better adjustment of the different
parameters. Recently, the inconsistencies of linearized
forms of different models, and their negative impact on
parameter values, involved in the liquid phase
adsorption process were reviewed [14,29].
The aim of this work is to compare the two forms of
the usually used kinetic models (PFO and PSO) for a
better interpretation of batch adsorption experiments of
Cadmium (Cd (II)) onto chitosan (CS) and methyl
orange (OM) onto bentonite (Bt). The results were
discussed to support the different criticisms appeared
in literature concerning these two models.
2. Experimental part
2.1. Material and methods
The chitosan used in this study was obtained from the
deacetylation of chitin extracted from shrimp shells
collected in Morocco. Its degree of deacetylation is 76%
as it was described in the previous work [36]. Bentonite
was purchased from Rh^one-Poulenc (France) and used
without any pre-treatment. The salt Cd(NO3)2 was
purchased from Across Organics (USA) and methyl
orange (99%) from Fisher Scientific International
Company. All working concentrations of solutions of
each pollutant were prepared with distilled water.
A mass m ¼ 0.1 g of each adsorbent, CS or Bt, was
first mixed with V ¼ 20 mL of a synthetic solution of
Cd(NO3)2 or MO, with initial concentrations
C0 ¼ 236.5 and 33 (mg/L) respectively. Then, the
mixture was agitated during a given contact time t and
246 H. Moussout et al. / Karbala International Journal of Modern Science 4 (2018) 244e254
at pH ¼ 5for the adsorption of Cd(II) onto CS and
pH ¼ 3 and for the adsorption of MO onto Bt. The
temperature was controlled by taking the mixtures in a
water circulation bath. After a definite adsorption time,
the adsorbent was separated from the liquid phase by
filtration over 0.45 mm micro-porous membrane. The
remaining concentrations of Cd(II) or OM in the so-
lution were analysed with ICP (Induced Chemical
Plasma) and UV/Visible Spectrophotometer (Shimadzu
UV-1240) at l ¼ 500 nm, respectively. The adsorbed
amount of each adsorbent was calculated according to
the following equation:


C0  Ce mg
qe ¼  Vsol ; ð1Þ
mads g
where qe (mg/g) is the equilibrium concentration of the
adsorbate in a solid phase, C0 and Ce are the initial and
the equilibrium concentrations in a liquid phase (mg/L),
respectively. mads is the mass of the adsorbent (g) and V
is the volume of solution in L.
Kinetic adsorption experiments were carried out to
establish the effect of time on the adsorption process.
The linear and the nonlinear models were used to
describe the kinetics curves. Their validities can be
determined by the calculation of the standard deviation
(SD) Dq (%), and the coefficient of determinationR2.
The best-fit model is the one with the lowest value of SD
and the one in which the value of R2is closer to unity. The
expression of SD equation is given as follows:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P  
qt;exp  qt;cal qt;exp
Dqð%Þ ¼
n1
Where qt,exp and qt,cal are, respectively, the experi-
mental and calculated adsorption capacities, and n is the
number of data points.
2.2. Theory
The adsorption kinetics reflect the evolution of the
adsorption process versus time. The latter is an
important parameter, which must be taken into
consideration. In addition, in the treatment of aqueous
solutions, the adsorption process is intimately depen-
dent on the other experimental parameters, such as pH,
ionic strength, temperature, concentration of solute,
sorbent dose, the texture of adsorbents…, that affect
the kinetics of adsorption of an adsorbate onto any
adsorbent. Therefore, the contact time where the
adsorption process approaches a true equilibrium must
be determined according to these parameters.
In batch adsorption systems, several models
describing the diffusion of solutes at the surface and in
the pores of adsorbent, have been developed (film
diffusion model, intra-particular diffusion model,
extra-particular diffusion model, pore diffusion model,
etc ...) to explain the adsorption kinetics. However,
PFO and PSO models have been widely used to
describe the rate of adsorption in liquidesolid in-
teractions. The expressions of those two models were
obtained by integrating the following general equation:
dqt
¼ kn ðqe  qt Þ ; ð3Þ
n
dt
Where qe and qt are the adsorbate amounts uptake per
mass of adsorbent at equilibrium and at any time t
(min), respectively; while, kn (1/min) is the constant
rate of the pseudo-n-th order kinetic model.
2.2.1. Pseudo first order expression
Lagergren presented the expression of the pseudo
first order reaction model for n ¼ 1 [10] as follows:
dqt
¼ k1 ðqe  qt Þ; ð4Þ
dt
Where qe and qt are the amounts of adsorbate uptake per
mass of adsorbent at equilibrium and at any time t
(min), respectively, and k1(min1) is the rate constant of
the PFO equation.
Integrating equation (4) for boundary conditions
2 (t ¼ 0, qt ¼ 0 and t ¼ t, qe ¼ qt) leads to the following
 100; ð2Þ linear equation:
lnðqe  qt Þ ¼ lnqe  k1 t; ð5Þ
Which can be rearranged in a nonlinearized form:
 
qt ¼ qe 1  ek1 :t : ð6Þ
2.2.2. Pseudo second order expression
The expression of the PSO adsorption reaction
model proposed by Ho et al. [9] was obtained from
equation (3) for n ¼ 2:
dqt
¼ k2 ðqe  qt Þ ; ð7Þ
2
dt
The integration of this equation for the boundary
conditions (t ¼ 0, qt ¼ 0 and t ¼ t, qe ¼ qt) gives the
formula below:
q2e k2 t
qt ¼ ; ð8Þ
qe k 2 t þ 1
 H. Moussout et al. / Karbala International Journal of Modern Science 4 (2018) 244e254 247

Where qe (mg/g) and qt (mg/g) are the adsorbate amount and differentiable on IRþ. For all x value in IRþ as
adsorbed at equilibrium and at any t(min), respectively shown below:
and k2 (g/mg min) is the PSO equation constant rate.   0
Equation (8) can be rearranged to obtain the linear f 0 ðxÞ ¼ a 1  ebx ¼ abebx > 0;
form:
t 1 1 Hence, the function f(x) is strictly increasing on IRþ
¼ þ t; ð9Þ and represented as follows:
qt k2 q2e qe
 
lim f ðxÞ ¼ lim a 1  ebx ¼ a
Beside the linear equations given here, several other x/∞ x/∞
linearized forms have been used in the interpretation of
the experimental data [14]. So, the straight (D) line of equation y ¼ a is a
horizontal asymptote off(x) in the neighbourhood of
2.3. Mathematical study þ∞. As for any value of x in IRþf ðxÞ  a ¼ 
aebx 30, which means that the function f(x) is always
The nonlinear forms of PFO and PSO models (eqs. below (D) asymptote on IRþ. This indicates that the
(6) and (8)) can be, mathematically considered, as an true value of a ¼ qe, cannot be precisely determined.
equivalent to the following equations (10) and (11): For the function g(x) (PSO model), which is a homo-
  graphic, this difficulty does not occur. This finding
f ðxÞ ¼ a: 1  eb:x ; ð10Þ explains why, in most cases, experimental data for
c2 :d:x adsorption kinetics followed the linear PSO model
gðxÞ ¼ : ð11Þ rather than the linear PFO model (see Table 1).
c:d:x þ 1

The study of the two functions f(x) and g(x) leads to
the curves represented in Fig. 1. It is observed that for
low values of x (x ¼ xe), the PFO and PSO curves are
superimposed; whereas, when x increases, the PFO
curve turns out to D asymptote; meanwhile, the PSO
curve continues to increase, without ultimately moving
towards an asymptote. This behaviour is usually ob-
tained in the adsorption kinetics experiments [18,20].
McKay et al. also reported that the PFO equation and
experimental data did not correlate well within the
whole contact time range and was generally appro-
priate for the first 20e30 min of adsorption process
[37]. Mathematical equation (10) is defined continuous
(Δ)
80
60
f(x),g(x)
3. Results and discussions
Adsorption kinetics studies of Cd(II) onto CS and
OM onto Bt were made in batch adsorption systems,
according to the experimental conditions presented in
section 2.1. Fig. 2 shows the experimental kinetics
adsorption of Cd(II) onto CS (Fig. 2a) and MO onto Bt
(Fig. 3a) at room temperature. It can be observed that
the experimental points can be divided into two regions
(I and II). In the region (I), the uptake (qt) of Cd(II) and
MO increased rapidly in a similar way for the contact
time t ¼ 30 min; then, after (region II), the experi-
mental points evolve differently. The qt values
increased gradually and become almost constant for
the adsorption of Cd(II) onto CS (qe ¼ 57 mg/g at
saturation); while, in the case of the adsorption of MO
PSO
onto Bt, the qt values continue to increase as the
PFO
contact time increases. This difference can be related
to the number and the availability of the adsorbing sites
over time of the adsorbents.
From the Figs. 2a and 3a, it was noted that the ki-

40 netics curves’ profiles are similar to those obtained

above (Fig. 1), using the NLPFO and NLPSO models.
Thus, the kinetics data of Figs. 2a and 3a were ana-
20
lysed with these models, using the equations (6) and
(8). The adsorption kinetic parameters, determined
0
from these equations, are presented in Table 3 and are
0
xe 20 40 60 80
x compared for each case with those that are obtained
from the slopes and the intercepts of linear equations
Fig. 1. Mathematical presentation of the equations (10) and (11). of the previous models (LPFO and LPSO).
248 H. Moussout et al. / Karbala International Journal of Modern Science 4 (2018) 244e254

Table 1
Bibliographic data of the linear modelling of adsorption kinetics.
Adsorbent Adsorbate teq (min) Model R2 qexp (mg.g1) qcal (mg.g1) Ref.
st
Polydopamine microspheres Methylene Blue 120 1 0.949 90.70 92.68 [38]
2nd 0.998 99.60
Chitosan/Al2O3/magnetite nanoparticles Methyl Orange 200 1st 0.839 102.00 46.63 [39]
2nd 0.999 99.00
Magnetic graphene-carbon nanotube Methylene Blue 30 1st 0.690 54.60 12.94 [40]
2nd 0.990 54.64
Polyaniline/graft chitosan Cu(II) 180 1st 0.962 83.22 53.30 [41]
2nd 0.994 100.00
Activated carbons from rambutan acid yellow 17 dye 900 1st 0.958 220.60 212.16 [42]
2nd 0.993 225.29
Magnetic iron oxide nanoparticles Phosphate 1440 1st 0.897 5.03 3.03 [43]
2nd 0.994 5.48
Poly(cyclotriphosphazene-co-4,40 -sulfonyldiphenol) Methylene Blue 15 1st 0.753 69.16 18.56 [44]
nanotubes 2nd 0.999 74.85
Iron oxide activated redmud (IOARM) Cd(II) 90 1st 0.994 0.12 0.078 [45]
2nd 0.997 0.071
Activated carbon Methylene Blue 300 1st 0.882 270.27 933.30 [46]
2nd 0.980 263.20
Activated carbon Co(II) 90 1st 0.010 16.05 1.01 [47]
2nd 0.990 15.93
Cellulose-graft-polyacrylamide/hydroxyapatite anthraquinone dye 2880 1st 0.896 157.20 103.40 [48]
biocomposite hydrogel (EBH) 2nd 0.998 163.4
Silica-multiwall carbon nanotubes Hg(II) 120 1st 0.942 77.01 38.10 [49]
2nd 0.999 79.80
Breadnut peel Malachite green 120 1st 0.935 193.40 80.28 [50]
2nd 0.997 167.85
Polyacrylamide/cellulose Methylene Blue 240 1st 0.970 45.00 16.28 [12]
2nd 0.999 45.41
Agricultural waste (nFe-A) Pb(II) 60 1st 0.717 822.50 242.26 [51]
2nd 0.999 833.33
Copper oxide loaded on activated carbon Methylene Blue 30 1st 0.963 11.10 2.88 [52]
2nd 0.998 10.32
ZnO/Zn(OH)2-NP-AC Janus Green B 7 1st 0.410 107.19 2.543  108 [53]
2nd 0.999 120.48
Bamboo biochar acid black 172 300 – e 215.50 e [54]
2nd 0.987 238.09
Ferromagnetic ordered mesoporous carbon Orange II 300 1st 0.980 280.00 48.55 [55]
2nd 0.999 293.16
Chitosan beads Phosphate 180 1st 0.998 60.60 61.27 [56]
2nd 1.000 61.16
Biochars Methylene blue 120 1st 0.954 1.69 1.027 [57]
2nd 0.995 1.714
Magnetic ZnFe2O4 Acid Red 88 340 1st 0.962 96.55 61.1 [58]
2nd 0.997 99.0
Poly(methacryic acid)/zeolite hydrogel Basic yellow 28 2880 1st 0.994 62.12 30.28 [59]
2nd 0.755 52.47
Oxide/chitosan fibers Congo red 600 1st 0.982 121.48 136.27 [60]
2nd 0.974 144.93
Magnetic CoFe2O4 reduced Pb(II) 80 1st 0.902 122.00 133.9 [61]
2nd 0.993 123.3
Activated carbon (cow bone) Pb(II) 360 1st 0.891 42.33 22.925 [62]
2nd 0.994 45.455
2nd e 19.19
Zeolites U(VI) 120 1st 0.995 12.40 1.078 [63]
2nd 0.993 10.03
La(OH)3-modified phosphate 1800 1st 0.987 71.70 60.8 [11]
2nd 0.997 71.3
 H. Moussout et al. / Karbala International Journal of Modern Science 4 (2018) 244e254 249

Table 1 (continued )
Adsorbent Adsorbate teq (min) Model R2 qexp (mg.g1) qcal (mg.g1) Ref.
st
Olive pomace Basic green 4 120 1 0.357 19.55 6.41 [64]
2nd 1.000 19.58
Magnetic Cellulose/Graphene Oxide Composite Methyl ne Blue 840 1st 0.747 50.272 13.719 [65]
2nd 0.997 49.92

3.1. Adsorption of Cd(II) onto CS [14,16,27,66,67]. In their conclusions, the authors

recommended the use of nonlinear forms (NLPFO and
The plots of NLPFO, NLPSO, LPFO and LPSO NLPSO) to describe the kinetic of adsorption curves
models are demonstrated in Fig. 2a, b. It was clearly because due to the transformation of nonlinear forms to
appearing that the experimental points conform with linear forms, the units of the Y and X axes changed
NLPFO model rather than the NLPSO. Table 3 dis- remarkably. The advantage of nonlinear methods is
plays that the values of R2 is almost equal to 1 and the that the error distribution does not alter as it does in
value of SD (Dq ¼ 0.98%) is very low. In addition, a linear methods. Table 2 summarises some examples of
NLPFO expression reasonably predicts the qe value literature using NL models. In our case, the NLPFO
(qe(exp) zqe(cal) ¼ 57 mg/g). However, the process- model seems to be the most appropriate to describe the
ing of the same experimental data by the LPFO and adsorption of Cd (II) onto CS. The obtained values of
LPSO models leads to a result that contradicts the R2, SD and qe (Table 3) did not indicate that the LPSO
previous one. From Fig. 2 and Table 3, it is deduced model properly fitted. However, from Fig. 2, the PSO
that when LPSO was applied straight line, the value of model can be applied for t < 30 min (region I); while,
R2 is higher than 0.99 and the lower value of the NLPFO model describes the adsorption kinetics of
SD ¼ 0.012% were obtained. This contradiction does Cd (II) on CS over the whole range of time considered
not allow a priori to decide between the two models (regions I and II) [19]. On the other hand, according to
(NLPFO and LPSO). Indeed, the application of these the theoretical approach of Azizian [13], when the
models to describe the adsorption kinetics in aqueous initial concentration of solute (C0)is high, like in this
solution has been the subject of several criticisms study (C0 ¼ 236.5 mg/L), its sorption kinetics better

a b
4
60 Exprimental points
LPFO
2
ln(qe-qt)

50 0

-2

40
-4
Experimental points
NLPFO
qt(mg/g)

NLPSO -6
30 0 20 40 60 80 100 120 140 160 180 200
t(min)
3,5
Experimental points
3,0 LPSO
20
2,5
t/qt(min.g/mg)

2,0

10 1,5

1,0

0,5
0
0,0
0 50 100 150 200 250 0 20 40 60 80 100 120 140 160 180 200
t(min) t(min)

Fig. 2. Nonlinear (a) and linear (b) PFO and PSO models for the adsorption kinetics of Cd(II) onto CS.
250 H. Moussout et al. / Karbala International Journal of Modern Science 4 (2018) 244e254

60 a 5 b
4 Experimental points
LPFO
3

50 2

ln(qe-qt)
1
0

40 -1
-2
Exprimental points
NLPFO
-3
qt(mg/g)

NLPSO 0 20 40 60 80 100 120 140 160 180 200

30
t(min)
3,5 Experimental points
LPSO
3,0
20
2,5

t/qt(min.g/mg)
2,0

10 1,5

1,0

0,5
0 0,0
0 50 100 150 200 250 0 20 40 60 80 100 120 140 160 180 200
t(min) t(min)

Fig. 3. Linear (b) and nonlinear (a) PFO and PSO models for the adsorption kinetics of MO onto Bt.

Table 2
Bibliographic data for nonlinear modelling of adsorption kinetics.
Adsorbant Adsorbat teq (min) Model R2 qexp (mg.g1) qcal (mg.g1) Ref.
st
Cellulose acetate blend salicylic acid 60 1 0.862 2.12 2.0513 [68]
[CA/SPS(90/10) þ [BMIM]Cl-NIM] 2nd 0.990 2.1484
Alginate/carboxymethyl Uranium 900 1st 0.981 101.76 115.09 [69]
cellulose sodium composite 2nd 0.973 167.69
NeS-doped mesoporous carbon (NSMC) Ibuprofen 90 1st 0.972 54.27 52.55 [70]
2nd 0.997 55.69
Black rice husk ash Chromium 60 1st 0.996 2.92 2.19 [71]
2nd 0.999 3.13
Ulvalactuca algae Cadmium 150 1st 0.979 127.00 114.29 [72]
2nd 0.931 122.91
Silica nanohollowsphere methylene blue 1440 1st 0.972 28.00 19.11 [73]
2nd 0.950 24.39
Pecan nutshell Lead 300 1st 0.995 179.00 171.40 [74]
2nd 0.997 196.00
MesoporousNiO nanoparticles Chromium 50 1st 0.999 4.50 4.48 [75]
2nd 0.999 4.74
Hydrochar Methylene blue 400 1st 0.733 96.56 91.29 [76]
2nd 0.939 98.35
Banana stalk activated carbon Bentazon 1200 1st 0.984 50.63 48.98 [7]
2nd 0.998 51.84
Pongamiapinnata Methylene blue 1440 1st 0.613 75.30 65 .57 [77]
2nd 0.994 77 .99
Magnetic biochar composite Lead 180 1st 0.975 3.29 3.17 [78]
2nd 0.997 3.38
Mesoporous-activated carbon Methylene blue 360 1st 0.996 101.15 100.13 [79]
2nd 0.995 103.31
Bamboo charcoals activated with nitric acid direct yellow 161dye 1800 1st 0.659 1.92 1.66 [80]
2nd 0.998 1.78
Candida utilis zinc 360 1st 0.820 23.12 21.41 [81]
2nd 0.950 23.66
 H. Moussout et al. / Karbala International Journal of Modern Science 4 (2018) 244e254 251

Table 3
Kinetic parameters of linear and nonlinear modelling of Cd(II)/CS and MO/Bt.
Lagergren(PFO) Ho et al. (PSO)
Polluant/Solid qexp. k1 qt cal. R21 Dq (%) k2 qt cal. R22 Dq (%)
(mg/g) (min1) (mg.g1) (g.mg1.min1) (mg.g1)
Linear equations Cd(II)/CS 56.70 0.041 8.49 0.713 7.60 0.008 57.60 0.999 0.012
MO/Bt 57.55 0.034 42.93 0.973 2.09 0.001 61.42 0.999 0.007
nonlinear equations Cd(II)/CS 56.70 0.204 56.79 0.987 0.98 0.005 61.28 0.941 2.607
MO/Bt 57.55 0.070 54.93 0,940 3.98 0.001 62.44 0.991 1.510

fits the pseudo-first order model, instead of the pseudo-
second order kinetics.
3.2. Adsorption of MO onto Bt
The experimental points of adsorption kinetics of
MO onto Bt at room temperature is given in Fig. 3. The
adsorption rate was rapid during the first 30 min and
then continued at a slower rate from 30 to 200 min.
The kinetic data were analysed by the LPFO, LPSO,
NLPFO and NLPSO models (Fig. 3). According to
Fig. 3a, for the NLPFO model, the theoretical curve
does not follow the experimental points, unlike its
linear form. However, both of the LPSO and NLPSO
models seems to fit well with the experimental points.
Moreover, the coefficient correlation R2 and Dq (%) as
well as the calculated qe values (Table 3) confirm the
validity of these models. In addition, the same values
of K2were found. This finding confirms that in the case
of the linearization of the NLPSO form, the kinetic
parameters were not affected. Indeed, the advantage of
the pseudo-second order equation as an expression
estimating the qe values is its small sensitivity for the
influence of the random experimental error, as it is
illustrated in the mathematics section. Kumar [16]
found that the most popular form of PSO (t/q vs. t)
was not the best form, unlike other authors [82,83].
This Difference shows that the accuracy of the line-
arized and the nonlinearized forms are dependent on
the adsorbent/adsorbate type and experimental condi-
tions, as indicated in the current paper.
4. Conclusion
CS and Bt adsorbents were used on Cd(II) and MO
removal, respectively, from aqueous solution. The
removal of Cd (II) and MO was fast and the equilib-
rium was reached in 30 min for both systems. The
processing of experimental data by the linear and
nonlinear pseudo-first order and pseudo-second order
models depicted that the adsorption kinetics of Cd
follows the NLPFO model and that of MO can be
described by both the NLPSO and LPSO models.
However, the study has shown that to decide between
the linear and non-linear models, for a given system, is
sometimes difficult because the kinetic parameters
deduced from these models are identical and the error
computations (R2 and SD) are reasonable in both cases.
Taking into account, the debates undertaken in litera-
ture, it briefly appears that the nonlinear forms of these
models are more suitable than their linear forms for the
modeling of the kinetics of adsorption in liquid phase.
However, the nature of the studied systems and the
exact determination of the qe value remain crucial
variables to decide.
Acknowledgement
This work was supported by MESRSFC and
CNRST  Rabat-Morocco, within the framework of
the PPR2 project.
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