chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

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

A review of the kinetics adsorption models

and their application to the adsorption
of lead by an activated carbon

L. Largitte a,∗ , R. Pasquier b

a COVACHIM M2E, Université des Antilles de la Guyane, Campus de Fouillole, BP 250, 97157 Pointe-à-Pitre Cedex,
France
b C3I, Université des Antilles de la Guyane, Campus de Fouillole, BP 250, 97157 Pointe-à-Pitre Cedex, France

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

Article history: 10 kinetic models are studied in detail and used after to model the adsorption kinetics of
Received 20 July 2015 lead on an activated carbon. All the kinetics parameters are determined: coefficients of
Received in revised form 28 January diffusion, rate constants and maximum lead adsorption, then, compared to the literature
2016 data. The data are better simulated by the nonlinear models in the order: simpli-
Accepted 5 February 2016 fied Elovich > Elovich > Bangham > pseudo order n > Boyd, Crank long times > pseudo order
Available online 11 February 2016 2 > Crank > Weber and Morris > Langmuir, pseudo order 1 > pore volume and surface diffu-
sion model by Leyva Ramos > simplified Crank short times. It is one of the first times that the
Keywords: kinetics of adsorption are fitted by the entire true Crank model. The kinetics of lead adsorp-
Adsorption tion by the activated carbon are best described by the Elovich equation: Q = (1/ˇ) Ln (˛ˇt)
Kinetics with ˛ equal to 0.035 mg g−1 s−1 and ˇ to 0.134 g mg−1 .
Modelling © 2016 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Heavy metal removal

1. Introduction In this study, the adsorbent used is an activated carbon

An adsorption process includes one or more than one adsor-
bate which is fixed though physical or chemical bonds onto
an adsorbent. Adsorption is widely used in wastewater treat-
ment process (Foo and Hameed, 2009) to remove the pollutants
from water because this technique is simple, efficient, eco-
nomically viable and socially acceptable (Sreejalekshmi et al.,
2009).
The adsorbents generally used are the activated carbons
because they possess large porous surface area, controllable
pore structure, thermo-stability, interesting acid/base proper-
ties and low cost if the preparation comes from byproducts.
The activated carbons are very efficient for the removal of a
broad type of organic and inorganic pollutants dissolved in
aqueous or in gaseous media (Li and Wang, 2009).
from Coconut shells, the adsorbate is lead and one of the
objective of this work is to study the kinetics of lead removal
in aqueous environment by this activated carbon.
It is essential to describe precisely the kinetics of adsorp-
tion (Gerçel and Gerçel, 2007), to compare the predicted
adsorption parameters calculated by models to the experi-
mental adsorbent behavior, in different adsorbent adsorbate
systems and in varied experimental conditions (Mishra and
Patel, 2009; Shekinah et al., 2002).
The determination of the models adsorption parameters
permits to optimize the adsorption mechanism pathways,
to express the dependence of the surface properties of the
adsorbent to the sorption results, to determine the adsorbent
capacities and design effectively the adsorption systems (Ho
et al., 1996; Thompson et al., 2001).

∗
Corresponding author. Tel.: +33 590 590483403; fax: +33 590 590483403.
E-mail address: lucie.largitte@univ-ag.fr (L. Largitte).
http://dx.doi.org/10.1016/j.cherd.2016.02.006
0263-8762/© 2016 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
496 chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504
Nomenclature
t time (s)
Q amount of adsorbate sorbed at instant t
(mg g−1 )
Qmax maximum amount of adsorbate sorbed
(mg g−1 )
Qr amount of adsorbate sorbed at t in the particle
of adsorbent at a distance r (mg g−1 )
Qexp experimental amount of adsorbate sorbed at
instant t (mg g−1 )
Qmean mean of experimental amount of adsorbate
sorbed at instant t (mg g−1 )
Qcalc amount of adsorbate sorbed at instant t pre-
dicted by the model (mg g−1 )
C0 initial concentration of adsorbate in solution
(mg L−1 )
C concentration of adsorbate in solution at the
moment t (mg L−1 )
Cr concentration of adsorbate in the particle of
adsorbent at a distance r (mg cm−3 )
k constant (Fick constant, simplification Crank
short times constant, Weber and Morris con-
stant, Bangham constant)
Ds diffusion coefficient at the surface (cm2 s−1 )
Dep diffusion coefficient in the pore volume
(cm2 s−1 )
kL external mass transfer coefficient (cm s−1 )
kad adsorption rate constant (L mg−1 s−1 )
k ad pseudo adsorption rate constant (unit for
order 1: s−1 , order 2: g mg−1 s−1 , order n:
mg1−n gn−1 s−1 , unit for Langmuir: s−1 )
kd desorption rate constant (s−1 )
˛ initial sorption rate in the Elovich model
(mg g−1 s−1 )
ˇ constant related to the extent of surface cover-
age and activation energy for chemisorption in
the Elovich model (g mg−1 )
 order of reaction to the adsorbate
n order of reaction to the adsorbent in the pseudo
order n model or parameter in the Crank model
ϑ parameter in the Bangham model
S surface of adsorbate (cm2 g−1 )
V volume of adsorbate (mL)
r distance in radial direction of adsorbent;
0 < r < R (cm)
D adsorbent dose (g L−1 )
ε void fraction in the adsorbent
P particle density of adsorbent (g cm−3 )
m weight of adsorbent (g)
Ea activation energy (J mol−1 )
R gas constant (8.314 J mol−1 K−1 ) or Radius of the
particle of adsorbent in the Crank model (cm)
T temperature (K)
N number of experimental data
Over the years, a wide variety of kinetics models (Langmuir,
Pseudo order 1, Pseudo order 2, Pseudo order n, Elovich, Crank,
Boyd, Bangham, Weber and Morris, pore volume and surface
diffusion) have been formulated.
This paper presents an explained and detailed state of
the art review of adsorption kinetics modelling by linear
and nonlinear analysis, their application on the study of
lead adsorption by an activated carbon derived from Coconut
shells, the determination of the kinetics parameters and their
comparison with the literature data and finally the selection
of the best model to fit the kinetics experimental data.
2. Materials and methods
2.1. Reagents
The 69.4% HNO3 solution and the NaOH used to fix the pH,
the Pb(NO3 )2 which is the lead ions source and the NaNO3
used to fix the ionic strength of the solution are AR grade and
all obtained from Prolabo. All the solutions are prepared with
deionized water.
2.2. The activated carbon
The activated Coconut shell carbon is a commercial carbon,
NC60, from the PICA Company. It is prepared by physical acti-
vation with carbon dioxide and water vapor. The activated
carbon sample, as received, is dried at 105 ◦ C for 2 days prior
to the sorption experiments.
2.2.1. Characterization
2.2.1.1. Texture. The texture of the activated carbon is charac-
terized via adsorption of nitrogen at 77 K using a Micromeritics
ASAP 2010 apparatus. About 0.30 g of sample is outgassed at
250 ◦ C for 48 h, prior to the adsorption measurements.
The BET surface area (SBET ) (Brunauer et al., 1938), the DR-
micropore volume (Vmi ) (Dubinin, 1960), the mesopore volume
(Vme ) and the DFT pore size distribution of the activated car-
bon are determined from the N2 adsorption isotherm. The
mesopore volume is calculated as the volume of N2 adsorbed
at P/P◦ = 0.99 minus the micropore volume and the density
functional theory (DFT) pore size distribution is calculated by
assuming a slit like geometry for the micropores (Olivier, 1995).
2.2.1.2. Surface properties. The surface properties of the acti-
vated carbon are characterized via the well-known Boehm
method (Boehm, 1994). The pHPZC of the activated carbon
is determined using the potentiometric titration method as
described by (Noh and Schwarz, 1990). All the titrations for
Boehm and pHPZC are performed on a 809 SM Titrino auto-
matic titrator (Metrohm) and the maximum titrant dosing rate
selected is 0.25 mL min−1 . Duplicates are performed for each
sample and the relative standard error is equal or less than
3%.
2.3. Kinetic sorption studies
All glassware is presoaked in a 5% HNO3 solution, rinsed with
deionized water and oven dried. All the batch sorption tests
and the absorption measurements are duplicated.
In the operating mode, 1 g of activated carbon is put in
contact with 1 L of lead ion solution, at pH 5 (the adsorbent
dose D is equal to 1 g L−1 ). The flask is put in a stirred water
bath maintained at a constant temperature of 30 ◦ C. The initial
concentration of lead is 150 mg L−1 .
At regular intervals, 5 mL of solution is removed from the
flask, filtered through a Whatmann 32 filter paper and the con-
centration of the remaining lead in solution (C) is measured.
Note that the stirring is stopped before each removal and that
 chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504
the total volume removed does not exceed 10% of the initial
volume of lead ion solution.
The concentrations of lead are measured with an atomic
absorption spectrometer AA240FS from Varian. The amount
of lead adsorbed at a time t, Q is calculated by the difference
between the initial (C0 ) and the instantaneous lead concentra-
tion (C):
  C0 − C
Q mg g−1 =
D and the second one to the equation
Qmax (mg g−1 ) is the maximum amount of lead adsorbed by
the activated carbon.
3. Adsorption kinetics models
3.1. Kinetics models
There are three steps in an adsorption process. First, the exter-
nal mass transfer of the adsorbate from the bulk solution to
the external surface of the adsorbent, followed by the inter-
nal diffusion of the adsorbate to the sorption sites and finally
the sorption itself. Some models are based on the fact that the
sorption is the rate limiting step in the adsorption process,
others suppose that the diffusion is the rate limiting step. So,
the fitting to the models permits elucidation of the adsorption
mechanism.
3.1.1. Diffusional models
The diffusional models assume that the diffusion is the rate
limiting step. They are divided in two parts, the external mass
transfer model and the internal diffusional models.
3.1.1.1. External mass transfer model. Mass transfer from the
bulk liquid to the solid surface is assumed to be the slowest
step. It is characterized by a mass transfer coefficient. How-
ever, it seems implausible to the authors that for an adsorption
process the approach of the adsorbate to the surface of the
adsorbent is the slowest step. Moreover, the effect of trans-
port is eliminated by mechanical mixing with the rapid and
constant stirring of the solution.
3.1.1.2. Internal diffusional models. The mass transfer into the
interior of the particle, characterized by an intraparticle diffu-
sion coefficient, can be the slowest step.
3.1.1.2.1. Crank model (Crank, 1956). The equation
describing homogeneous diffusion of an adsorbate in an
adsorbent modelled as a sphere and assuming a constant sur-
face diffusivity Ds at all points in the particle is
∂Q DS ∂
 ∂Q 
2
= 2 r ,
∂t r ∂r ∂r
r being the distance in the radial direction.
Crank gives an exact solution to this equation for the aver-
age concentration in the solid at any given time for the case
where the sphere is initially free of solute and the concentra-
tion of the solute at the surface remains constant (that is to
say in the absence of external mass transfer).
For short times, or more precisely for Q/Qmax < 0.3, this
equation may be simplified, idem for long duration (more
precisely for Q/Qmax > 0.85). The simplified Crank long times
equation is also known as the Boyd equation (Boyd et al., 1947).
The different Crank equations are given in Table 1.
497
3.1.1.2.2. Weber and Morris model (Weber and Morris,
1963). Weber and Morris have studied the batch adsorption
of alkyl benzene sulfonates by activated carbon. They have
shown that the plot of Q/Qmax versus t1/2 could be decomposed
in two linear plots, the first one corresponding to the equation
Q
= Cte × t1/2 (3)
Qmax
(1)
Q
= Cte × t1/2 + Cte. (4)
Qmax
Some authors suggest for the Weber and Morris model that
the first part of the plot also must be modelled by Eq. (4). They
explain the presence of the term Cte by the external mass
transfer which is not negligible. The authors are not convinced
this is true as there is no apparent reason for the amount of
lead adsorbed at t = 0 to be different from zero.
3.1.1.2.3. Bangham model. The Bangham model can be
understood as the generalization of the Weber and Morris
model or the application of the Freundlich and Helle (1939)
model to kinetics. The equation is given in Table 1.
3.1.1.3. Complex diffusional model. More realistic models for
the solid phase can be used to describe the diffusion pro-
cess. However, their greater complexity makes their use
mathematically more difficult. An example of a complex dif-
fusional model is the pore volume and surface diffusion model
(PVSDM) suggested by Geankoplis and Leyva-Ramos (1985).
It is a complex diffusional model which takes into account
adsorption, external mass transfer and intraparticle diffusion.
It is assumed that the intraparticle diffusion is due both to
pore volume diffusion and surface diffusion. All the equations
needed to solve the model are given in Table 1.
3.1.1.4. Adsorption models. In the adsorption models, the
adsorption is considered to be the slowest process. This is usu-
ally the case when the adsorbate uptake on the adsorbent is
of chemical nature (i.e., chemisorption).
In the following equations S is the adsorption sites, M is the
adsorbate, C is the concentration of the adsorbate in solution,
, the order of reaction to the adsorbate, SM is the concentra-
tion of adsorbate bound to the sorbent, kad is the adsorption
rate constant and kd the desorption rate constant. The sorp-
tion rate is equal to dQ/dt.
3.1.1.4.1. Pseudo first order model (Lagergren, 1898).
The pseudo first order model is described by the non-reversible
equation:
(2) S + M → MS (5)
The kinetic equation rests on five assumptions:
1. Sorption only occurs on localized sites and involves no
interaction between the sorbed ions.
2. The energy of adsorption is not dependent on surface cov-
erage.
3. Maximum adsorption corresponds to a saturated mono-
layer of adsorbates on the adsorbent surface.
4. The concentration of M is considered to be constant.
5. The metal ion uptake on the activated carbons is governed
by a first-order rate equation.
 498
Table 1 – Kinetic models of adsorption.
Process control Kinetic law Nonlinear form Linear form Linear plot

External mass transfer Fick equation – – –

  ∞    
Internal diffusion Crank (Q/Qmax ) = 1 − 6/ 2
n=1
1/n 2
exp −DS n  t/R 2 2 2
– –
Ln (Q/Qmax )   1/2 
 1/2   1/2  = (1/2) Ln t + Ln −1/2 − (1/2) Ds t/R2
Crank (short times) (Q/Qmax ) = 6 Ds t/R2 −1/2 − (1/2) Ds t/R2 –
 

chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

Q/Qmax < 0.3
+ (1/2) Ln Ds /R 2
+ Ln 6
 1/2
Simplification Crank Q = kt1/2 with k = 6 Ds /R2 Ln Q = (1/2) Ln (t) + Ln (k) Ln Q = f(Ln t)
short times
Weber and Morris Q = kt1/2 + Cte – –
Bangham Q = ktϑ     Ln Q = ϑLn (t) + Ln (k)     Ln Q = f(Ln t)
Boyd, Crank long times: Q/Qmax = 1 − 6/2 exp −Ds 2 t/R2 Ln (1 − (Q/Qmax )) = Ln 6/2 − DS 2 t/R2 Ln (1 − cteQ) = f(t)
Q/Qmax > 0.85

Complex diffusional Geankoplis and V (dC/dt) = −mSkL (C − Cr |r=R ) – –

model Leyva-Ramos ε (∂Cr /∂t) + P (∂Q/∂t)
 

= 1/r2 (∂/∂r) r2 (Dep (∂Cr /∂r) + DS P (∂Q/∂r))


(∂Cr /∂t) =0
r=0
Dep (∂Cr /∂r) + DS P (∂Q/∂r) = kL (C − Cr |r=R )
t = 0 ; C = C0
t = 0 ; Cr = 0 ; 0 ≤ r ≤ R
Q(r) = f(Cr )
       
  
Adsorption Langmuir (1 site) Q = Qmax kad / kad + kd 1−e
− k +kd
ad
t Ln
1 − Q/Qmax kad / kad + kd Ln (1 − cteQ) = f(t)
= − kad + kd t
 
−k t
Pseudo order 1 Q = Qmax 1−e ad Ln (1 − (Q/Qmax )) = −kad t
     
Pseudo order 2 Q = kad Qmax
2
t/ 1 + kad Qmax t t/Q = (t/Qmax ) + 1/kad Qmax
2
t/Qt = f(t)
  
1/(n−1) 
Pseudo order n for n =
/ 0 Q = Qmax 1 − 1/ 1 + kad (n − 1) Qmax
n−1
t – –

Elovich Q = (1/ˇ) Ln (1 + ˛ˇt) Ln Q = Ln (1/ˇ) + Ln2 (1 + ˛ˇt) –

Simplification of Q = (1/ˇ) Ln (˛ˇt) Q = (1/ˇ) Ln (˛ˇ) + (1/ˇ) Ln t Q = f(Ln t)

Elovich: 1  ˛ˇt
 chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504 499

Then, the sorption rate can be written as Then, the adsorption rate constant kad can be written, using
the Arrhenius equation, as:
Q 2
kad C
max −Q
= kad (Qmax − Q) (6)
 Ea 
Qmax kad = Cte × exp − = ˛ × exp (−ˇQ) (14)
RT

and the resulting equation after integration is given in Table 1.

with
3.1.1.4.2. Pseudo second order model (Ho et al., 1996; Ho  Ea 
˛ = Cte × exp −
and McKay, 1999). The kinetics of metal ion removal are 0
(15)
described by the pseudo second order model as follows: RT

3. The concentration of M is considered to be constant.

2S + M → M(S)2 (7) 4. The metal ion uptake on the activated carbons is negligible
before the exponential (equivalent to a metal ion uptake
The assumptions are almost the same as for the pseudo governed by a zero order rate equation).
first order model except the metal ion uptake on the activated
carbons is governed by a second-order rate equation. Then, the sorption rate can be written as:
Then, the sorption rate can be written as
˛ × exp (−ˇQ) (16)
Q 
−Q 2
max
kad C = kad (Qmax − Q)2 (8) with
Qmax

The resulting equation by integration is given in Table 1. ˛ = C ˛ (17)

3.1.1.4.3. Pseudo n order model for n different from zero
(Ritchie, 1977). The kinetics of metal ion removal can be and the resulting integration is given in Table 1.
described by the pseudo n order model. The equation is
3.2. Fitting the kinetics models to the experimental
data
nS + M → M(S)n (9)

All these models are tested to describe the sorption of lead

The assumptions are the same as for the pseudo first order on the activated carbon from Coconut shells using a home-
model except the last one as the metal ion uptake on the made program. The experimental sorption data are fitted
activated carbons is governed by a rate equation of order n. to the linear and the nonlinear form of the models. So,
Then, the sorption rate can be written as linear and nonlinear least squares analysis is applied to
Q −Q
n each set of adsorption data using the Ceres solver library
max
kad C = kad (Qmax − Q)n (10) [ht*tp://co*de.go*ogle.co*m/p/ceres-solver/].
Qmax The root mean square error (E) is calculated by the expres-
sion:
The result of the integration is given in Table 1.

3.1.1.4.4. Langmuir model (Langmuir, 1918). The kinet-  N
1
E=
ics of metal ion removal are described by the Langmuir model 2
(Qexp − Qcalc ) (18)
using this reversible equation: N
i=1

S + M  MS (11) N being the number of experimental points. The best model

describing the experimental data is the one with the lowest E.
The four assumptions are the same as for the pseudo first- The correlation coefficient of determination R2 is also cal-
order model but now the rate of desorption is not negligible culated as
compared to the rate of adsorption.
SSres
Then, the sorption rate can be written as R2 = 1 − (19)
SStot
Q −Q
  Q 
max
kad C − kd = kad (Qmax − Q) − kd Q (12)
Qmax Qmax

N
2
With the residual sum of squares, SSres = (Qexp − Qcalc ) ;
and the integrated equation is given in Table 1.
i=1
3.1.1.4.5. Elovich model (Elovich and Larinov, 1962). The (20)
kinetics of metal ion removal is described by the Elovich model
as follows:

N
2
With the total sum of squares, SStot = (Qexp − Qmean )
S + M → MS (5)
i=1
(21)
1. Sorption only occurs on localized sites and there is inter-
action between the sorbed ions.
2. The energy of adsorption increases linearly with the sur- The Fisher test (FR2 ) of two models seem close to each other
face coverage according to the law: in order to discriminate without any doubt the best model.
F is determined through the ratio of the residual sum of
Ea = Ea0 + RTˇQ (13) squares (SSres ) of the two models.
500 chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

The P value (P value) is then calculated via the F cumulative

Table 2 – Characterization of the activated carbon.
distribution function (cdf):
Activated carbon
from coconut shells
P value = 1 − cdf(F, df1 , df2 ) (22)
SBET (m2 g−1 ) 1058
Vmi (cm3 g−1 ) 0.49
df1 , df2 is respectively the degree of freedom for each of the Vme (cm3 g−1 ) 0
two models. It is calculated as the number of experimental
Total of acid oxygenated surface groups 0.3
data less the number of parameters to estimate in the model.
(mmol g−1 )
Other error functions like E or R2 to compute the difference Carboxyl groups 0
between the experimental data and the predicted values are Hydroxyl groups 0.3
given in Foo and Hameed (2009). Lactone groups 0
Note that the modelling for the Crank model and the pore Total of basic oxygenated surface groups 0.9
volume and surface diffusion model suggested by Geankoplis (mmol g−1 )
pHPZC 9.2
and Leyva Ramos are explained with precision in other papers
(Largitte and Laminie, 2015; Largitte and Pasquier, 2016a).
Note that also the linear and nonlinear Boyd, Crank (long
times) modelling and linear pseudo order 1 modelling need to
fix a Qmax to begin the computation. Qmax is fixed at 52 mg g−1 ,
the next higher entire value than the experimental one.

Amount of lead adssorbed (mg.g-1)

50
4. Results and discussion
40
4.1. Characterization of the activated carbon short mes
30
long mes
The textural properties of the activated carbon have been
Weber and Morris
studied. The nitrogen adsorption/desorption isotherm for 20
Data
the activated Coconut shells carbon is shown in Fig. 1. The
isotherm is of type I according to the BDDT classification, 10

characteristic for microporous materials (Gregg and Sing,

0
1982).
0 1000 2000 3000 4000
The values of SBET , Vmi , Vme obtained from the isotherm are
Time (min)
listed in Table 2. The mesopore volume is negligible; the micro-
pore volume is in high agreement with such a high surface
Amount of lead adssorbed (mg.g-1)

50
area. The micropore size distribution of the activated carbon
is studied according to the DFT model. The DFT plot shows 40
that there are many micropores of size 6 Å, ´ close to the size of short
30 mes
the hydrated lead cation (Nightingale, 1959). long mes
The chemical surface properties of the activated carbon are
20 Bangham
also listed in Table 2.
The total number of acid groups on the surface of the
10
activated carbon is low (0.3 mmol g−1 ) compared to the total
number of basic groups (0.9 mmol g−1 ). The distribution of the
0
acidity is narrow because only alcohol groups are present. The 0 1000 2000 3000 4000
activated coconut shells carbon is a basic activated carbon Time (min)
with a pHPZC equal to 9.2.
Amount of lead adssorbed (mg.g-1)

50

40

30 short mes
long mes, Boyd
20 Crank
Data
10

0
0 1000 2000 3000 4000
Time (min)

Fig. 2 – Experimental kinetics adsorption (the points) and

Fig. 1 – Adsorption/desorption isotherm of N2 at 77 K on the (a) modelled kinetics adsorption by Weber, Morris
activated Coconut shells carbon. Pore size distribution of equations; (b) by Bangham equations and (c) by Crank
the activated carbon from Coconut shells by applying the equations using all the data and only the data at short
DFT method to the nitrogen adsorption isotherm at 77 K. times or long times.
 chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504 501

The kinetic results are fitted according to the linear and

50 nonlinear form of the kinetics models. The results of the fitting
Amount of lead adsorbed (mg.g-1)

are given in Table 3.

40
4.2.1. Comparison between the linear and the nonlinear
Data
30 models
Crank Globally, the order of magnitude of the root mean square error
20 Bangham E follows the same trend for the linear and the nonlinear mod-
Weber and Morris els except for the Boyd, Crank long duration model which has
10 Geankoplis the lowest E in the linear modelling and one of the worst in
the nonlinear modelling.
However, as the linearization is not possible for all the mod-
0
0 1000 2000 3000 4000 els, the comparison between the linear and nonlinear models
Time (min) is truncated.
Moreover, other authors have pointed that the linearization
bias the estimate of model’s parameter set (Ho, 2006). This
50
Amount of lead adsorbed (mg.g-1)

means that the use of nonlinear expressions must be favored.

Then, only the results obtained from nonlinear modelling will
40
be further discussed.

30
4.2.2. Comparison between the time range for the kinetic
modelling
20 Data Order 1, Langmuir
Order 2 Order n = 2.8 As it can be seen from Figs. 2–4, the whole models are com-
Elovich Simplified Elovich pared in the entire time range available except for the Crank
10 short duration and long duration models which are, by default,
limited to a short duration range. However, restricting the
0 study to the beginning or the latest stage of the process, as
0 1000 2000 3000 4000
it can be seen in Fig. 2, is not representative for the whole pro-
Time (min) cess and can lead to an under or overestimation of the kinetics
Fig. 3 – Experimental kinetics adsorption (the points) and parameters. Then, the best way to obtain an average is to take
modelled kinetics adsorption (the lines); (a) by the the data for the entire uptake process.
diffusional equations (b) by the adsorption equations. Consequently, it is better to use the Crank model in the
entire duration range instead of the Crank short times or long
times models in short duration ranges as can be seen in Fig. 2.
4.2. Application of the kinetics models This result can be generalized and the models describing the
entire time range of the process must be favored. This is the
The experimental uptake rate of lead by the activated carbon case for the Crank, Bangham, Leyva Ramos, Langmuir, Elovich
from Coconut shell is studied at pH 5 for an initial lead concen- and Pseudo order 1, 2 and n models.
tration of 150 mg L−1 and an adsorbent dose of 1 g L−1 at 30 ◦ C.
The sorption is quite rapid as can be seen in Figs. 2–4: 16% 4.2.3. Comparison between the kinetics parameters
of the lead is removed within the first two hours followed by Fig. 3 presents the kinetics data and the fitting plots for all
a slow approach to equilibrium. Equilibrium is reached after the diffusional and all the adsorption models and Table 3, the
50 h and the value of the experimental maximum amount of kinetics parameters obtained from the modelling.
lead adsorbed is 50.2 mg g−1 . According to the diffusional models, that is to say,
the Crank, Bangham, Leyva Ramos, Weber and Morris and
Geankoplis models, the diffusion coefficient (Ds , Dep ) or the
rate constant k can be calculated. The maximum amount of
50 lead adsorbed Qmax predicted by the model can also be calcu-
Amount of lead adsorbed (mg.g-1)

lated and compared to the experimental maximum amount

40 which is 50.2 mg g−1 .
Data As it has been previously assumed, the diffusion coeffi-
30 n = 2.8 cient at the surface Ds is different in the Crank long times
n=6 model (here, underestimated) compared to the entire Crank
20 model. However, the maximum amount of lead predicted by
n = 40
the Crank long times model (52 mg g−1 ) is closer to the exper-
imental result.
10
On the contrary, the pore volume and surface diffusion
model suggested by Leyva Ramos shows that when one
0
0 1000 2000 3000 4000 assumes only diffusion inside the pore volume, Ds is equal
Time (min) to zero and Dep /R2 is 7.5E − 03 s−1 , a value four times higher
than the one obtained for Ds /R2 in the simplified Crank short
Fig. 4 – Experimental kinetics adsorption (the points) and duration model (1.71E − 03 s−1 ).
modelled kinetics adsorption by Pseudo order n equation The simplified Crank model and the Weber and Morris
(the lines). model can be compared to each other because they both use
502 chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

Table 3 – Kinetics modelling results.

Kinetics laws Nonlinear form Results for the E in the Results for the linear
nonlinear form linear form form
2
E R

Crank 2.600 0.923 Qmax = 46.8 mg g−1 ; – –

Ds /R2 = 4.74E − 06 s−1
Crank short times na na na na na
Q/Qmax < 0.3 (not
enough points)
Simplification Crank 10.469 na k = 0.140 mg g−1 s−1/2 = 15.674 Ln k = −1.708, then
 1/2
short times 6 Ds /R2 ; k = 0.181 mg g−1 s−1/2 ;
Ds /R2 = 2.86E − 03 mg2 g−2 s−1
Ds /R2 = 1.71E − 03 mg2 g−2 s−1
Weber and Morris: 2.694 0.917 k = 0.07 mg g−1 s−1/2 ; – –
kt1/2 + Cte Cte = 22.350 mg g−1
Bangham: kt 1.175 0.984 k = 4.639 mg g−1 s− ; ϑ = 0.198 1.288 Ln k = 1.398, then
k = 4.047 mg g−1 s− ;
ϑ = 0.210
Boyd, Crank long times 1.802 na Qmax = 52.05 mg g−1 ; 0.360 Ds /R2 = 1.61E − 06 s−1
Q/Qmax > 0.85 (only 4 Ds /R2 = 1.90E − 06 s−1
points)
Geankopolis and 6.774 0.479 Dep /R2 = 7.50E − 03 s−1 ; Ds = 0 cm2 s−1 ; – –
−1
Leyva-Ramos  −02 cm s 
kL = 4.60E
Langmuir (1 site) 3.785 0.837 Qmax kad / kad + kd = 45.76 – –
kad + kd = 1.03E − 04
Then, k ad Qmax = 45.13E − 04
Pseudo order 1 Qmax = 45.76 mg g−1 ; 10.795 k ad = 1.94E − 05 s−1
k ad = 1.03E − 04 s−1
Pseudo order 2 2.323 0.939 kad Qmax
2
= 0.0072; kad Qmax = 3.917 k ad Qmax 2 = 0.0041;
1.46E − 04 Qmax = 53.75 mg g−1 Then
Then, k ad = 2.96E − 06 g mg−1 s−1 ; k ad = 1.44E − 06 g mg−1 s−1
Qmax = 49.33 mg g−1

Pseudo order n 1.686 0.968 k ad = 1.27E − 07 mg1−n gn−1 s−1 ; – –

Qmax = 54.18 mg g−1
for n = 2.8
0.839 0.992 k ad = 7.16E − 14 mg1−n gn−1 s−1 ;
Qmax = 76.83 mg g−1
for n = 6
0.462 0.99758 k ad = 4.14E − 103 mg1−n gn−1 s−1 ;
Qmax = 331.76 mg g−1
for n = 40
Elovich 0.468 0.99751 (1/ˇ) = 7.524; ˛ˇ = 0.004 – –
Then ˇ = 0.133 g mg−1 ;
˛ = 0.033 mg g−1 s−1
Simplification of 0.461 0.99758 1/ˇ = −39.77; ˛ˇ = 7.44 0.461 1/ˇ = −39.77; ˛ˇ = 7.44
Elovich: 1  ˛ˇt Then, ␤ = 0.134 g mg−1 ; ˇ = 0.134 g mg−1 ;
␣ = 0.035 mg g−1 s−1 ; ˛ = 0.035 mg g−1 s−1

the parameters k and t0.5 , however this is not the case for the
Bangham model which uses a dependence of k and t0.2 .
The parameter k is the double for the simplified Crank
model than for the Weber and Morris one (0.14 mg g−1 s−1/2
against 0.07 mg g−1 s−1/2 ).
The results obtained from the Weber and Morris modelling,
from the Crank long duration modelling and the Bangham
modelling are in agreement with the literature data found for
the sorption of lead by activated carbons (Sreejalekshmi et al.,
2009; Li and Wang, 2009; Gerçel and Gerçel, 2007; Mishra and
Patel, 2009; Shekinah et al., 2002; Ho et al., 1996; Nadeem et al.,
2006; Wang et al., 2010; Ayyappan et al., 2005).
Concerning the adsorption models, Langmuir, Elovich,
Pseudo order 1, 2 and n models, the pseudo adsorption rate
constant or the sorption rate and sometimes the maximum
amount of lead adsorbed Qmax can be calculated.
Note that the pseudo adsorption rate constant in the Lang-
muir model (k ad ) and the desorption rate constant kd cannot
be calculated solely with the results of the Langmuir kinetics
modelling because there are two unknown parameters and
only one equation.
A method to determine the constants k ad and kd is to
use Qmax exp = 50.2 mg g−1 or Qmax predicted by the Lang-
muir equilibrium model equal to 47.7 mg g−1 (Largitte and
Pasquier, 2016b). Knowing the sum of the constants k ad and
kd equal to 1.03E − 04 and k ad Qmax equal to 45.13E − 04, k ad
can be deduced. It is equal to 8.99E-05 (9.5E − 05) s−1 and kd to
1.31E − 05 (8.4E − 06) s−1 .
Considering that the value of k ad is higher than kd , one
can consider the adsorption to be easier than the desorption
on the surface of this activated carbon.
These results are near those of Machida et al. (2005) and
Sekar et al. (2004).
Note that he knowledge of the ratio kad /kd obtained though
the fitting of the isotherm data by the Langmuir equilibrium
model can also permit to determine kad . According to Largitte
and Pasquier (2016b), the ratio kad /kd is equal to 0.749. Solving
the equation yields kad equal to 9.8E − 06 (6.3E − 06) L mg−1 s−1 .
 chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504
The kinetics are better described by the pseudo order n
model and the pseudo order 2 model than by the pseudo 1
model.
For the pseudo second order model, the pseudo rate con-
stant k ad is equal to 2.96E − 06 g mg−1 s−1 and the maximum
amount predicted by the model is 49.33 mg g−1 .
In the case of the pseudo order n model, a higher value of
n gives a better fitting (see Fig. 4 and Table 3), but produces
predicted maximum amounts that are very different from the
experimental one. The most coherent result is obtained for
n equal to 2.8, which gives a predicted maximum amount of
54.2 mg g−1 .
Many data are available on the pseudo rate constant for
the pseudo first order model (Sreejalekshmi et al., 2009; Li and
Wang, 2009; Gerçel and Gerçel, 2007; Mishra and Patel, 2009;
Shekinah et al., 2002; Nadeem et al., 2006; Wang et al., 2010;
Ayyappan et al., 2005; Ibrahim et al., 2012; Inyang et al., 2012;
Largitte et al., 2012, 2014; Ricordel et al., 2001), pseudo second
order model (Sreejalekshmi et al., 2009; Li and Wang, 2009;
Gerçel and Gerçel, 2007; Mishra and Patel, 2009; Nadeem et al.,
2006; Wang et al., 2010; Ibrahim et al., 2012; Inyang et al., 2012;
Largitte et al., 2012, 2014] and pseudo nth order model (Ricordel
et al., 2001) which can be compared to our results.
Concerning the Elovich model, there is only a minor dif-
ference between the results of the Elovich model and the
simplified Elovich model. The initial sorption rate ˛ changes
from 3.3E − 02 to 3.5E − 02 mg g−1 s−1 and the constant related
to the extent of surface coverage and activation energy for
chemisorption, ˇ, from 0.133 to 0.134 g mg−1 . These results are
concordant with previous results from other authors (Li and
Wang, 2009; Wang et al., 2010; Ibrahim et al., 2012; Inyang et al.,
2012).
The initial sorption rate can also be calculated from the
pseudo second order model using the expression k ad Qmax 2
and can be compared to the value ˛ obtained by the
Elovich model. The result gives 7.2E − 03 mg g−1 s−1 and is
five times smaller than the value obtained from Elovich
(3.5E − 02 mg g−1 s−1 ).
To conclude, the value of the maximum amount of lead
adsorbed obtained for this activated carbon, from the experi-
ment or from the fitting, is really well compared to literature
data. This result is in agreement with the high surface area
of the activated carbon, the high micropore volume and the
presence of alcohol groups on its surface which can promote
the complexation of lead to the carbon surface.
4.2.4. Comparison between the error values
The values of the error E and R2 are presented in Table 3 and
Fig. 3 presents the fitting of the different diffusional and sorp-
tion models to the experimental data. The lowest value of E
and the best coherent fitting of the models is for the simplified
Elovich model and the error increases in the order: sim-
plified Elovich < Elovich < Bangham < pseudo order n < pseudo
order 2 < Crank < Weber and Morris < Langmuir, pseudo order
1 < pore volume and surface diffusion model by Leyva Ramos.
According to these error results, Elovich is the best
model which describes the experimental data. However, the
E value for Bangham and Elovich are very proximate. So
a F test is made to choose undoubtedly the best model.
F = SS(Bangham)/SS(Elovich) = 6.30517; then, the calculated
P value is equal to 0.0087. The P value, inferior to 0.01, shows
that the Elovich model is statistically better than the Bangham
model with a false-rejection probability inferior to 0.01.
503
55
y = 7.5474x - 10.173
Amount of lead adsorbed (mg.g-1)
50 R² = 0.98
45
40
35 y = 7.9469x - 12.069
R² = 0.992
30
25
20
4 5 6 7 8 9
Ln(t+t0) With t0 = 1/(αβ)
Fig. 5 – The two types of sorption sites implied in the
sorption process according to Elovich model.
From these results, a simplified Elovich model can be put
forward for the sorption of lead by the activated Coconut shells
carbon. This means the rate limiting step in the process is the
chemical sorption between the lead and the active sites of the
carbon and that the activation sorption energy increases with
the process.
So, the experimentally demonstrated observation of the
sorption rate slowing down with time is explained by the
Elovich model that explains, at first, the lower energy surface
sites of the carbon saturate, and then, the adsorption shifts to
the higher energy surface sites, resulting in a decrease of the
sorption rate.
According to the Elovich model assumptions and to the
break of slope in the derivative Elovich plot (Fig. 5), there are
two types of sorption sites implying in this sorption process.
Two sorption sites, probably relative to the both ways of sorp-
tion of lead cations on the adsorbent surface, one with the
oxygen of the alcohol surface groups by complexation and the
other one with the ␲ electrons of the graphene layers of the
activated carbon by electrostatic interaction.
Consequently, the kinetics of the adsorption of lead by the
activated carbon from Coconut shell can be described though
the equation:
1
Q= Ln (˛ˇt) (23)
ˇ
with ˛ equal to 0.035 mg g−1 s−1 and ␤ to 0.134 g mg−1 .
5. Conclusion
This paper aims to study in detail the different existing models
of kinetics adsorption and to apply them to the sorption of lead
onto an activated carbon. The kinetics is studied at 30 ◦ C, ini-
tial pH 5, initial lead concentration 150 mg L−1 and adsorbent
dose 1 g L−1 for an activated carbon from Coconut shells. The
objectives are to explain, with precision, all the kinetics mod-
els, to determine all the kinetics parameters, to compare them
to the literature data and finally to find the model that can bet-
ter describe the experimental results of adsorption kinetics of
the activated carbon. The screening is made via the root mean
square error and the correlation coefficient of determination.
So, 10 mathematical models of adsorption are studied
and several kinetic parameters (coefficient of diffusion, rate
constant, sorption rate and maximum of lead adsorbed) are
calculated.
The results show that the Crank, the Bangham, the pore
volume and surface diffusion by Geankoplis and Leyva Ramos,
504 chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

the Langmuir, the Elovich, the pseudo order 1, 2 and n models from aqueous solution by biochars derived from anaerobically
fit the experimental data quite well over a wide time range. digested biomass. Bioresour. Technol. 110, 50–56.
This is in contrast to the Crank short or long times (simplified Lagergren, S., 1898. Zur theorie Der Sogenannten adsorption
geloster stoffe, Kungliga Svenska Vetenskapsakademiens.
or not). So the first group of models cited must be preferred to
Handlingar 24, 1–39.
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In the case of this activated coconut shell carbon, the sorp- 2012. Influence of the surface properties of the Bois Carré
tion data are better simulated by the nonlinear models in the seeds activated carbon for the removal of lead from aqueous
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