Chemical Engineering Journal xxx (xxxx) xxxx

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Chemical Engineering Journal

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Derivation of Pseudo-First-Order, Pseudo-Second-Order and Modified

Pseudo-First-Order rate equations from Langmuir and Freundlich isotherms
for adsorption
Rohollah Ezzati
Department of Physical Chemistry, Faculty of Chemistry, Razi University, P.O. Box: 6714967346, Kermanshah, Iran

HIGHLIGHTS GRAPHICAL ABSTRACT

• Kinetics study of Langmuir and

Freundlich isotherms by Statistical
Rate Theory.
• Derivation of Pseudo-First-Order and
Pseudo-Second-Order models.
• Derivation
Order model.
of Modified Pseudo-First-

• Derivation
adsorption.
of a new kinetics model for

• Simulation of Humic Acid adsorption

on Hematite and Kaolinite adsorbents.

ARTICLE INFO ABSTRACT

Keywords: The kinetics of adsorption for Langmuir and Freundlich isotherms has been explored theoretically on the basis of
Adsorption Statistical Rate Theory (SRT). The Modified Pseudo-First-Order (MPFO) and Pseudo-First-Order (PFO) models
Kinetics were derived from Freundlich isotherm on the basis of Statistical Rate Theory at c0 ce and at close to equi-
Freundlich librium respectively. Also, for a Langmuirian adsorption MPFO was derived at initial times of adsorption under
Langmuir
condition c0 ce and also Pseudo-First-Order (at close to equilibrium) and Pseudo-Second-Order (PSO) model
Statistical Rate Theory
(at close to equilibrium for c0 ce and e 1) were obtained based on SRT. It has been proven that from
Freundlich and Langmuir isotherms the fractional coverage is a linear function of t at very short initial times of
adsorption. Also an useful rate equation was derived at condition c0 ce from Freundlich isotherm. The theo-
retical obtained equations from Freundlich and Langmuir isotherms have been examined by several set of ex-
perimental data selected from literature.

1. Introduction been developed for studying thermodynamics of adsorption in solid/

Adsorption is an important method for pollutant removal from
wastewater [1] and gas separation [2–4]. Kinetics and Thermo-
dynamics study of adsorption process is very important in industry. It is
necessary to investigate the kinetics and thermodynamics of this pro-
cess for synthesis of various adsorbent [5]. It is well known that there
are many physical, mathematical and experimental equations that have
solution and solid/air interfaces [6–14]. Many different kinetics models
have been proposed for adsorption process. Either of them is used in
particular conditions for adsorption process at solid/solution or solid/
gas interface such as: Pseudo-First-Order (PFO) [15,16], Modified
Pseudo-First-Order (MPFO) [17–21], the Elovich model [22], Pseudo-
Second-Order (PSO) [23–32], Pseudo-Third-Order (PTO) [33], Avrami’s
fractional order [34,35] and the other kinetics models [20,36–44]. In

E-mail address: rohollah_ezzati@razi.ac.ir.

https://doi.org/10.1016/j.cej.2019.123705
Received 17 September 2019; Received in revised form 2 December 2019; Accepted 3 December 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Rohollah Ezzati, Chemical Engineering Journal, https://doi.org/10.1016/j.cej.2019.123705
R. Ezzati Chemical Engineering Journal xxx (xxxx) xxxx

2004 Azizian [5] derived PFO and PSO models by using theory of ac- d
tivated adsorption/desorption (TAAD). He derived PFO model under dt
the high initial concentration of adsorbate. Also, he derived PSO model µb0 + kTlnc µs0
kT
ln
under the low initial concentration of adsorbate. Liu et al. [45] in- = R exp m
exp
kT
troduced a new approach for derivation of PFO and PSO kinetics models
for a Langmuirian adsorption. They showed that the adsorption kinetics kT
µs0 + ln µb0 kTlnc
for Langmuir isotherm can be transformed to mixed first and second m

order model. Also, Wang et al. [46] applied a mixed kinetics model kT
(4)
consist of PFO and PSO models on the basis of Langmuir isotherm for
kinetics studying of adsorption. In 2010, Marczewski obtained an exact By rearrangement of Eq. (4) this equation can be written as:
solution of adsorption kinetics based on Langmuir isotherm [47]. 1
d c 1 m
Shahwan [48] represented a simple approach for derivation of PSO = R KF 1
dt KF c (5)
model according to a new formulation by utilizing the mass balance
m

equation for a single stage batch-type system. In 2005, Yang and Al- where in this equation KF is adsorption equilibrium constant for
Duri proposed a new model based on PFO (Modified Pseudo-First-Order Freundlich isotherm and it is defined as:
model or MPFO) for explaining adsorption kinetics behavior over the
whole adsorption process for adsorption of reactive dyes on activated µb0 µs0
KF = exp
carbon [17]. Ward et al. [49–52] in 1982 developed the Statistical Rate kT (6)
Theory (SRT) which is based on statistical thermodynamics and 1
quantum mechanics for kinetics study in solid/gas interface. This Because at equilibrium time
d
= 0 then KF = e
m
; and on the other
theory can predict the rate of adsorption at the interfaces [53,54]. In dt ce
hand we have KF = that ka and kd are adsorption and desorption rate
ka
2008 Azizian et al. [19]derived the modified pseudo-first-order (MPFO) kd
kinetics model on the basis of SRT at close to equilibrium. In 2008 constants. therefore the rate of adsorption and desorption at equili-
1
Rudzinski et al. [18] by utilizing SRT approach showed that at the very brium are equal to ka ce and kd e
m
respectively. Then Eq. (5) can be
short initial times of adsorption is a linear function of t for a written as:
Langmuirian adsorption. In 2017, Ezzati [55] obtained the general so- 1 1
lution of SRT equation for Langmuir isotherm. In this research the PFO d e
m c kd m
= k a ce 1
and MPFO kinetics models for Langmuir and Freundlich isotherms (for dt ce m ka c
(7)
m = 1) and PSO model for Langmuir isotherm will be derived on the
basis of Statistical Rate Theory at different conditions. Also, adsorption By simplification of this equation we can write:
kinetics will have considered at very short initial times of adsorption for d 1 c
1
m
these isotherms. = ka e
m k d ce
dt 1
m c (8)
This is general rate equation for an adsorption system that it follows
2. Theory from Freundlich isotherm on the basis of Statistical Rate Theory. In the
near equilibrium limit the rate equation obtained from Statistical Rate
2.1. The general rate equation for Freundlich isotherm from Statistical rate Theory reduces to conventional rate equation that derived from
Theory Absolute Rate Theory approach [57]. Therefore, the conventional rate
equation for an adsorption system that it follows from Freundlich iso-
The general rate equation to calculate the rate of molecular trans- therm can be obtained from Eq. (8) in the near equilibrium limit; this
port between bulk phase and surface phase on the basis of Statistical rate equation can be written as:
Rate Theory approach is [49]:
d 1
= ka c kd m
dt (9)
d µb µs µs µb
= R exp exp
dt kT kT (1) Also, for m = 1 Eq. (8) can be written as:
d c
Where in this equation, µb and µs are the chemical potentials of the = ka e k d ce
(10)
dt c
adsorbate in the bulk phase and on the surface respectively. also, k is
the Boltzmann constant, T is absolute temperature, and R is the rate of The bulk concentration of the solute (or adsorbate in bulk phase)
adsorption or desorption process at equilibrium (at equilibrium the decreases by increasing surface coverage as [19]:
adsorption and desorption rate are equal). c = c0 (11)
According to the Freundlich model of adsorption, the chemical
potential of adsorbed particles ( µs ) can be expressed by [56]: where c0 is initial concentration of solute in bulk phase and is [5]:
ma qm c0 ce
kT = =
µs = µs0 + ln Mw V e (12)
m (2)
where in this equation ma , qm , Mw , V and ce are the mass of sorbent,
where µs0 , and m are standard chemical potential for adsorbed particle maximum adsorption capacity of sorbent, molar weight of adsorbate,
on surface, the fractional surface coverage and adjustable parameter of volume of solution and equilibrium concentration of adsorbate in bulk
Freundlich isotherm respectively. Also the chemical potential of the phase respectively. According to Eq. (12) maximum value of will
adsorbate in the bulk phase ( µb ) can be written as [19]: obtain at c0 ce condition and it is equal to c0 . Also, minimum value of
e

µb = µb0 + kTlnc (3) is for c0 ce and that is equal to 0 0 ( c0

e ).
By institution of Eq. (11) into Eq. (10) we can write:
where µb0 and c are standard chemical potential of adsorbate in solution c0
d
and concentration of adsorbate in bulk phase. By substitution of Eqs. (2) = ka e k d (c 0 e)
dt c0 (13)
and (3) into Eq. (1) we can write:

2
R. Ezzati Chemical Engineering Journal xxx (xxxx) xxxx

And by rearrangement of Eq. (13) we can write: = 2k a e c 0 t (23)

d c0 1 (c 0 e) According to Eq. (23) at the very short initial times of adsorption,
= ka e
dt KF c0 (14) is a linear function of t and the slope of it is 2ka e c0 . Rudzinski et al.
[18] derived Eq. (23) for a Langmuirian adsorption on the basis of
By institution of Freundlich equilibrium constant for m = 1
Statistical Rate Theory at very short initial times of adsorption.
(KF = c e ) into Eq. (14) this equation can be written as: Freundlich kinetics at 0 or c0 ce conditions
0 e

d c0 (c0 e)
2 Let us consider another case; we assume that the initial concentra-
= ka e tion of solute isn’t very high compared to its equilibrium concentration.
dt e (c 0 ) (15)
For this case we have c0 ce ; therefore we have 0 and by institution
By rearrangement of this equation it is converted to: of 0 into Eq. (16) we can write:
2 (c )2 2 (c 2
d e) d k c 2 2 ka c0 ( )( + )
e 0 0
= ka = a 0 e
= e e
= ka c0 e
dt e (c 0 ) (16) dt e e e

This is general rate equation for an adsorption system that it follows (24)
from Freundlich isotherm (for m = 1) on the basis of Statistical Rate This is a new rate equation (called the SREF model (Statistical Rate
Theory. In next section we will apply this equation for derivation of Equation based Freundlich isotherm)) for modelling of adsorption ki-
PFO and MPFO models by accepting some assumptions. netics on the basis of Freundlich isotherm. We are going to apply this
Freundlich kinetics at close to equilibrium equation for modelling of Humic Acid adsorption kinetics on Hematite
For derivation of PFO kinetics model from Freundlich isotherm we and Kaolinite.
should expand the Eq. (16) into the Taylor series around = e , after Until this time we considered the adsorption kinetics for an ad-
simplification, the result can be written as: sorption that it follows from Freundlich isotherm at very short initial
c0
times, at times close to equilibrium, at 0 and at conditions.
d 2k c e
lim = a 0( e ) + O (( e )2) By accepting these conditions four different rate equations obtained
e dt e (17)
from general rate expression (Eq. (16)). We showed that for Freundlich
By forgoing of O (( e )2) respect to first term we can write: isotherm (for m = 1) is a linear function of t at very short initial
d 2k c times and adsorption kinetics follows from Pseudo-First-Order model at
lim = a 0( e ) times that system is close to equilibrium; also for interval times if
c0
e dt e (18) e
adsorption kinetics follows from Modified-Pseudo-First-Order model
By definition of PFO rate constant as k1 =
2k a c 0
Eq. (18) can be and if 0 adsorption kinetics follows from SREF model.
e
written as: A profound thought on Eq. (12) guides us to discovery of conditions
that they cause that value limits to c0 and 0 . On the basis of Eq. (12)
d e
lim = k1 ( e ) high mass of adsorbent, high adsorption capacity of adsorbent, low
e dt (19)
volume of solution and finally low molecular weight of adsorbate cause
where this equation is Pseudo-First-Order (PFO) kinetics model that the value limits to c0 and also, low mass of adsorbent, low ad-
[16,54,58]. e
sorption capacity of adsorbent, high volume of solution and finally high
Freundlich kinetics at or c0 ce conditions
c0
e molecular weight of adsorbate cause that the value approaches to 0 .
Let us consider one typical case; we assume that the initial con- For example, according to Eq. (12) at the same conditions; for an ad-
centration of solute (adsorbate in bulk phase) is very high compared to sorbate with very low molecular weight the MPFO is more appropriate
c0
its equilibrium concentration; therefore we have and by in-
e than SREF model and for an adsorbate with a very high molecular
stitution of this value for into Eq. (16) we can write: weight SREF is better than MPFO for kinetics modelling.
d k c Integrated forms of obtained rate equations from Freundlich iso-
= a 0 e
( e ) therm for m = 1
dt e (20)
By integration of Eq. (16) and the imposition of initial condition
Eq. (20) is Modified Pseudo-First-Order (MPFO) kinetics model that (t = 0) = 0 and by simplification of obtained equation we can write:
it has been introduced by Yang and Al-Duri for adsorption kinetics
modelling [17]. In 2008, Azizian et al. [19] derived MPFO model from
Statistical Rate Theory for an adsorption system that it follows from
2
+
(
c02ln 1
2
c0
+
e ) + ln 1 =
2k a c 0
t
c0 2 e (c 0 2 e)
2
e e (25)
Langmuir isotherm at close to equilibrium condition while we derived
c0
this equation for a Freundlich adsorption at c0 ce or condi- where this is integrated form of general rate equation on the basis of
e
tions. SRT for a Freundlich adsorption isotherm (for m = 1). According to this
Freundlich kinetics at very short initial times of adsorption c02ln 1
2
+
We are going to consider the behavior of Eq. (16) at very short in- equation plot of c0
2
2 e
+
(c 0
c0
2 e )2
e
+ ln 1 ( e ) vs t is a
itial times of adsorption; for this purpose we must expand Eq. (16) into c0
straight line with slope of
2k a c 0
. For 0 and Eq. (25) reduces
the Taylor series around = 0 . After simplification, the result is as to:
e e

follows:
2 2k a c 0
d k c ka (c0 e) ln 1 + + ln 1 = t
lim = a e 0 ka e + O ( 2) e e e (26)
0 dt e c0 (21)
And:
According to the Eq. (21) and by forgoing
ka (c 0 2
e)
ka e + O( 2)
compared k a e c0
we can write: ka c0
e c0 + ln 1 = t
d k c e e e (27)
lim = a e 0
0 dt (22) Where Eqs. (26) and (27) are integrated forms of MPFO (Eq. (20))
By Integrating Eq. (22) and imposition of initial condition and SREF (Eq. (24)) respectively. According to Eq. (26) plot of
(t = 0) = 0 the result can be written as: (
ln 1 +
e ) + ln (1 e ) vs t is a line with slope of 2k a c 0
e
. Also, from

3
R. Ezzati Chemical Engineering Journal xxx (xxxx) xxxx

Eq. (27) plot of

e
+ ln 1 ( e ) vs t is a straight line with slope of very short initial times) of adsorption so that 1 1 while this
equation has been derived by Azizian et al. [19] at times that system is
ka c0
. We will apply MPFO and SREF models for kinetics study of
e close to equilibrium. Unfortunately, their derivation cannot be valid.
Humic Acid adsorption on Hematite and Kaolinite as two different For proving our claim we expand Eq. (31) into the Taylor series around
adsorbents. = e . The result is as follows:
The general rate equation for Langmuir isotherm from Statistical
Rate Theory d
lim
For Langmuirian adsorption the chemical potential of adsorbed e dt
substance on the surface calculates from [56]: = k a (c 0 e )(1 e) kd
(c 0 2
e )(k a (c 0 e )(1 e) + kd e )
µs = µs0 + kTln e + ( e )+O
1 (28) e (c 0 e )( e 1)

On the other hand, equilibrium constant for a Langmuirian ad- (( e ) 2) (37)

sorption follows from: Because ka (c0 and by forgoing of
e )(1 e) kd e =0
k O (( e )2) we can write:
KL = a = e
kd (c0 e )(1 e) (29) d
lim = k1 ( e )
Also, at equilibrium the forward rate (adsorption rate at equili- e dt (38)
brium) follows from: This is PFO kinetics model and k1 is PFO rate constant and it is
R = k a (c 0 e )(1 e) (30) defined as:
(c 0 2)(k
By institution of Eqs. (3), 28, 29 and 30 into the general equation of e a (c 0 e )(1 e) + kd e )
k1 =
SRT (Eq. (1)) the general rate equation for a Langmuirian adsorption e (c 0 e )( e 1) (39)
will be obtained on the basis of Statistical Rate Theory. This equation
Consequently, the Langmuirian adsorption kinetics would not be
can be written as:
readily simplified to the MPFO model at close to equilibrium on the
d e (c 0 )(1 ) (c 0 e )(1 e) basis of Statistical Rate Theory. We showed that not only MPFO model
= ka kd
dt (c 0 )(1 ) (31) cannot be obtained from SRT approach at close to equilibrium but also
this model can be obtained from SRT at short initial times of adsorption
By using equilibrium constant definition for Langmuir isotherm (at a low fractional coverage) by assuming
c0
. Although MPFO
(K L = k a = (c ) we can rewrite Eq. (31) as the form below:
k e e
d )(1 ) 0 e e model can explain adsorption kinetics behavior at entire times of ad-
2 (c )2 (1 )2 2 (c 2 (1 2 sorption, this model cannot be derived from SRT at close to equilibrium.
d e 0 0 e) e)
= ka There is a reasonable proof that it shows MPFO model can explain
dt e (c 0 )(1 ) (32)
adsorption kinetics behavior at times close to equilibrium; the MPFO
In next subsections we are going to derive the PFO, PSO and MPFO model that it has been introduced by Yang et al. follows from [17]:
models from this equation.
d e
Derivation of Pseudo-First-Order model from Langmuir kinetics at = kM ( e )
(40)
dt
close to equilibrium
If we expand Eq. (32) into the Taylor series around = e the result where kM is rate constant. If we expand this equation into the Taylor
is as follows: series around = e and by forgoing the term of O (( e )2) the result
2)
is as follows:
d 2k ( c
lim = a 0 e
( e ) + O (( e ) 2) d
e dt e (33) lim = kM ( e )
e dt (41)
By forgoing of O (( e )2) vs first term we can write:
Where this equation is PFO model. This proof shows that the MPFO
2k ( c 2)
d converts itself to PFO model at times close to equilibrium.
lim = a 0 e
( e )
e dt e (34)
where this is PFO model that it has been derived at times close to 3. Derivation of Pseudo-Second-Order model from Langmuir
equilibrium. In 2004 Azizian derived this model for Langmuir isotherm kinetics at close to equilibrium
by assuming c0 ce from theory of activated adsorption/desorption
(TAAD) while we derived this model at close to equilibrium for any For derivation of Pseudo-Second-Order (PSO) model we expand Eq.
initial concentration of adsorbate. (35) into the Taylor series around = e . By forgoing the term of
Langmuir kinetics at
c0
or c0 ce conditions O( e )3 we have:
e
Let us assume that the initial concentration of solute is very high d k c (1 e) ka c 0
compared to its equilibrium concentration; therefore we have
c0
lim = a 0 ( e )+ ( e )2
e e dt e e
2
(42)
and by institution of this value for into Eq. (32) we can write:
For a specific adsorption with 1 e 0 or e 1 Eq. (42) converts
d k c
= a 0 e
( e )(1 ) to:
dt e (35)
d k c
At short initial times of adsorption we have 1 1 (or 0) lim = a 20 ( e )2
e dt e (43)
then under this condition Eq. (35) converts to:
where this is Pseudo-Second-Order (PSO) model that it was derived
d k c
= a 0 from Statistical Rate Theory for a Langmuirian adsorption at times close
e
( e )
dt e (36) to equilibrium and under condition
c0
or c0 ce and e 1. We
e
where this equation is MPFO kinetics model. In fact, we obtained the know that c0 ce condition means a not very high initial concentration
MPFO model from a Langmuirian adsorption on the basis of Statistical of adsorbate (at a very high initial concentration of adsorbate c0 ce ).
c0
Rate Theory by assuming or c0 ce for short initial times (not Azizian derived PSO model from theory of activated adsorption/
e

4
R. Ezzati
desorption (TAAD) for Langmuir isotherm under a not very high initial
concentration of adsorbate [5]. And now, we derived PSO under this
condition from SRT. Ward studied the effects of reactants and products
concentration on reaction rate according to Statistical Rate Theory and
he proved that the rate equation based on SRT converts to rate equation
based on Absolute Rate Theory (ART) at close to equilibrium [57].
Because TAAD approach is based on ART therefore adsorption rate
equation obtained from SRT will transform to rate equation based on
TAAD at close to equilibrium. For this reason PFO and PSO models were
obtained from SRT at e condition by us.
Langmuir kinetics at very short initial times of adsorption
If we expand Eq. (32) into the Taylor series around = 0 and by
forgoing the term of ka c0 e ka e + O ( ) compared to ka e c0 and
then by integrating obtained equation and imposition of initial condi-
tion (t = 0) = 0 the result is as follows:
= 2k a e c 0 t
This equation shows that the fractional coverage is a linear function
of t for a Langmuirian adsorption at very short initial times of ad-
sorption. A summary of obtained adsorption kinetics models for
Langmuir and Freundlich isotherms at different times and conditions
has been shown in Fig. 1.
In summary, it has been shown that the PFO, PSO and MPFO models
for Langmuir isotherm and PFO and MPFO models for Freundlich iso-
therms can be obtained at different conditions and also adsorption ki-
netics of these isotherms has been considered theoretically at very short
initial times of adsorption. These results have been shown at table 1.
4. Results and discussion
For Langmuirian adsorption, It is proven from our approach that
when the fractional coverage at equilibrium is near to unity ( e 1) (or
when qe increases) , then the adsorption process obeys Pseudo-Second-
Order kinetics, and when e away from unity (or when qe decreases)
then the
adsorption follows from Pseudo-First-Order. Several set of experi-
mental data selected at literature have been reported in table 2 and 3
for proving these results. Reported data in Table 2 and 3 show that by
increasing the equilibrium adsorption capacity (qe ) for various
Fig. 1. Adsorption kinetics for Langmuir and Freundlich isotherms at different times and conditions on the basis of Statistical Rate Theory.
Chemical Engineering Journal xxx (xxxx) xxxx
adsorbate on different adsorbent, the correlation coefficient (R2) of
fitting to the Pseudo-Second-Order model increases and it decrease for
Pseudo-First-Order model and this conclusion is in agreement with our
theoretical approach.
In this section, we are going to analyze the accuracy of the MPFO,
SREF models and Eqs. (23) for an adsorption system that it follows from
Freundlich isotherm with m = 1. For this purpose, a set of experimental
data selected at literature. El-Sayed et al. [59] studied the adsorption of
Humic acid (HA) on Kaolinite and Hematite as two different adsorbents
under various conditions. They studied the influence of pH and ionic
strength on the adsorption rate. Their research showed that the ad-
sorption rate on the Hematite and Kaolinite increase with decreasing
pH and increasing ionic strength. Also, adsorption of HA on the He-
matite and Kaolinite adsorbents follows from Freundlich isotherm and
Pseudo-Second-Order kinetics model. Because the values of parameter
m for the Freundlich model are close to 1 for HA adsorption on He-
(44) matite and Kaolinite, the heterogeneity of surface of these two ad-
sorbent could be assumed to be less important. The results of fitting of
HA adsorption data with Freundlich isotherm model that reported at
their paper is listed at Table 4.
For kinetics study of this system, we simulated adsorption experi-
mental data on the basis of Stochastic Numerical Simulation (SNS). This
technique has been applied for kinetics study of adsorption at several
papers [19,60]. For stochastic numerical simulation of adsorption we
used the Chemical Kinetics Simulator (CKS) software that developed by
Houle et al. [61]. In this method the mechanism of reaction is con-
sidered as a set of several steps. We assume that adsorption process has
only a reversible elementary step. The input data for numerical simu-
lation are adsorption mechanism, the adsorption rate constant, initial
concentration of HA and concentration of empty sites of adsorbent. In
our approach the adsorption rate constant values at first were taken
from El-Sayed experimental report, then this rate constants values were
adjusted until an acceptable reproduction of the kinetics data points
(q; t ) were obtained. The reported adsorption rate constants by El-
Sayed et al. and adjusted adsorption rate constants values were tabu-
lated in Table 5. Also, the plots of q (t ) vs time for experimental and
simulation results have been shown in Fig. 2. Parts a, b and c of Fig. 2
are for adsorption of HA on Hematite at pH 5, 6 and 7 respectively. It is
obviously that adsorption rate increases by decreasing pH . Also, parts
5
R. Ezzati Chemical Engineering Journal xxx (xxxx) xxxx

Table 1
The results of our theoretical study for adsorption kinetics on the basis of Langmuir and Freundlich Isotherms.
Isotherm General Rate Equation Specific Rate Equation Conditions

Langmuir d 2
e (c 0 )2 (1 )2 2 (c
0
2
e ) (1 e)
2 Pseudo-First-Order model (PFO) at close to equilibrium
= ka
dt e (c 0 )(1 ) Pseudo-Second-Order model (PSO) at close to equilibrium and at
c0
or c0 ce and e 1
e
Modified Pseudo-First-Order (MPFO) at
c0
or c0 ce and 1 1
e

lim
d
=
ka e c0 at very short initial times of adsorption
0 dt
Freundlich d 2
e (c 0 )2 2 (c
0 e)
2 Pseudo-First-Order model (PFO) at close to equilibrium
= ka
dt e (c 0 )
lim
d
=
ka e c0 at very short initial times of adsorption
0 dt
Modified Pseudo-First-Order (MPFO) at
c0
orc0 ce
e
SREF model at 0 orc0 ce

Table 2 Table 4
The relationship between equilibrium adsorption capacity (qe ) and accuracy of The results of fitting of HA adsorption data with Freundlich isotherm model.
Pseudo-First-Order kinetics model.
Adsorbent
adsorbent Adsorbate qe mg /g ) R2 reference
CaCl2 concentration (mol/Lit ) R2 K ( )(mg
g
mg
Lit
1
) m
m

CTAB/NaOH/flyash composite Resorcinol 153.68 0.9825 [25] Hematite 0.01 0.988 0.873 1.09
217.9 0.9583 Kaolinite 0.998 0.46 0.998
Resin D301 Glyphosate 181.44 0.9786 [66]
364.24 0.9262
Volcanic tuff Basic Blue 41 7.58 0.9791 [67] Table 5
11.69 0.9740 Experimental and Simulated rate constants for the Adsorption of HA on
19.57 0.9599 Hematite and Kaolinite at different Solution Conditions at temperature 298 K.
Kaolinite Humic Acid 18.4 0.91 [59]
44.4 0.808 Adsorbent CaCl2 pH Experimental Rate Simulated Rate
54.4 0.77 concentration Constant (g/min.mg) Constant
Fe3O4/TiO2–SiO2 modifed with As(III) 0.313 0.984 [68] (mol/Lit ) (g/min.mg)
zinc (FTSZ) 0.767 0.971
2.150 0.937 Hematite 0.01 5 0.026 0.027
2.800 0.849 6 0.0277 0.029
Humic Acid Derived from U(VI) 28.60 0.986 [69] 7 0.035 0.036
Leonardite 29.96 0.971 Kaolinite 0.01 5 0.0119 0.0121
CB-FM CO2 0.302 0.931 [34] 6 0.0171 0.0174
0.342 0.927 7 0.0114 0.0119
0.383 0.875
0.465 0.821
0.577 0.802
Kaolinite are 35.81 and 17.2 m2 / gr respectively; for this reason HA
adsorption rate on Hematite is greater than its Kaolinite. According to
Table 3 Fig. 2, there is a good agreement between the experimental and simu-
The relationship between equilibrium adsorption capacity (qe ) and accuracy of lated data at different times. Hereafter we are going to examine the
Pseudo-Second-Order kinetics model. accuracy of the Eqs. (23), 26 (SREF model) and 27 (MPFO model) for
adsorbent Adsorbate qe mg /g ) R2 reference HA adsorption on Hematite and Kaolinite on the basis of generated data
that obtained from simulation. Because of the higher specific surface
CTAB/NaOH/flyash composite Resorcinol 83.28 0.9878 [25] area for Hematite the maximum capacity of adsorption for this ad-
153.68 0.9976
Activated Carbon p-Xylene 187.18 0.997 [70]
sorbent is greater than its Kaolinite; therefore parameter for Hematite
219.76 0.999 is greater than Kaolinite ( H > K ). For this reason we expect that HA
resin D301 glyphosate 161.29 0.9910 [66] adsorption kinetics on Hematite follows from MPFO model that this
c0
166.67 0.9948 model has been derived by assuming a maximum value for or .
e
Volcanic tuff Basic Blue 41 7.70 0.9998 [67]
Also, we expect that HA adsorption kinetics on Kaolinite follows from
11.72 0.9999
Fe3O4/TiO2–SiO2 modifed As(III) 0.313 0.987 [68] SREF model that derived for a minimum value for or 0 . We should
c0
with zinc (FTSZ) 0.767 0.996 say this is an approximation that we assume H and K 0 . The
e
4.000 0.999 results of fitting of the generated data obtained from simulation and
natural zeolite (Clinoptilolite) Salt ion in 20.00 0.999 [26] SREF and MPFO models are presented in Fig. 3. The solid boxes are
seawater 34.29 1
Humic Acid Derived from U(VI) 29.96 0.994 [69]
generated data obtained from simulation, and the red and black solid
Leonardite 34.79 0.999 lines are MPFO and SREF models respectively. Parts a, b and c of Fig. 3
are for adsorption of HA on Hematite at pH 5, 6 and 7 respectively.
These parts show that there is a good agreement between simulated
data and MPFO model while there is not a reasonable agreement be-
of d, e and f of Fig. 2 are for HA adsorption on the Kaolinite at pH 5, 6 tween simulated data and SREF model. These agreement and dis-
and 7. For this process the rate of adsorption increases by decreasing agreement are reasonable because we assumed that H > K according
pH . According to the paper results Hematite has a specific surface area to physical characterization of Hematite and Kaolinite. Also, Parts d, e
greater than Kaolinite. The specific surface area for Hematite and and f of Fig. 3 are for adsorption of HA on Kaolinite at pH 5, 6 and 7

6
R. Ezzati Chemical Engineering Journal xxx (xxxx) xxxx

Fig. 2. Plot of q(t) vs Time (min) for Humic Acid adsorption on Hematite and Kaolinite as two different adsorbents. experimental data (red solid boxes) Simulated
data (black open circles). a, b and c for HA adsorption on Hematite at pH 5, 6 and 7 respectively. d, e and f for HA adsorption on Kaolinite at pH 5, 6 and 7
respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

respectively. There is an excellent agreement between simulated data
and SREF model that it shows the simulated data follow from this
model. Also, Fig. 3 shows that the HA adsorption obeys MPFO model at
a high adsorption rate condition, while it obeys SREF at low adsorption
rate. Also, the plots of adsorbed HA (q ) on Hematite and Kaolinite
(obtained from simulation) vs time at very short initial times of ad-
sorption are shown at Fig. 4. According to Fig. 4 there is a good
agreement between simulated data for HA adsorption on Hematite and
Eq. (23) ( = 2ka e c0 t ), while a large deviation is observed for fitting
of simulated data and Eq. (23) for HA adsorption on Kaolinite. These
agreement and deviation are for these reasons that the adsorption rate
on the Hematite is faster than its Kaolinite. At a very fast adsorption the
diffusion process in the subsurface region plays no role in the kinetics of
adsorption [19]; for this reason, the diffusion doesn’t have an effective
role in adsorption of HA on hematite, while the diffusion is an im-
portant step in adsorption mechanism for HA adsorption on Kaolinite. It
has been frequently reported at literature that at very short initial times
of adsorption, when < 10 the relationship between fractional cov-
3
e gradient respectively. According to the Eqs. (46) and (47) if electric
erage and time follows from [18]:
6 e Dt
= very short initial times the value of fractional coverage for HA ad-
r (45)
where D and r are intraparticle diffusivity and particle radius respec-
tively. This equation is similar to eq. (23) ( = 2ka e c0 t ) that it was
derived at very short initial times of adsorption. According to eq. (45) at
an adsorption system, the fractional coverage increases by increasing
diffusion coefficient and it decreases by increasing adsorbate size. The
diffusion coefficient of the molecules in solution depends on mobility
and concentration of molecules due to the interparticle interactions
[62]. Relation between mobility of an ion and its diffusion coefficient
follows from [63]:
kT
D=
|z| e (46)
where D , , k , T , e and |z| are diffusion coefficient, ion mobility, Boltz-
mann constant, absolute temperature, proton charge and absolute
coefficient of ion charge (z in ze ion charge) respectively. From physical
point of view the mobility of an ion with a charge ze that is moving in
an electric potential gradient is [63]:
=
V (47)
Where and V are ion velocity in solution and electric potential
potential gradient is large the ion mobility will be large then the value
of diffusion coefficient will become large. According to Figs. 3 and 4 at
sorption on Hematite is greater than its Kaolinite and according to Eq.
(45) this is due to a high value of diffusion coefficient for HA at HA
adsorption on Hematite respect to Kaolinite. The Hematite surface
morphology causes that it carries negative and positive charges at pH9
and 4 respectively, while at pH7 , the surface of natural hematite is

7
R. Ezzati
Fig. 3. Plot of q(t) vs Time (min) for Humic Acid adsorption on Hematite and Kaolinite as two different adsorbents. Simulated data (blue solid boxes) MPFO model
(red line) SREF model (black line). a, b and c for HA adsorption on Hematite at pH 5, 6 and 7 respectively. d, e and f for HA adsorption on Kaolinite at pH 5, 6 and 7
respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
almost neutral electrically or carries scantly negative charges [59].
Unlike hematite, Kaolinite surface morphology makes a small negative
charge due to substitution of Si(IV) by Al(III) in its structure [59,64,65].
Because of existence of a small and large negative charge on Hematite
and Kaolinite surface respectively there is a larger electric potential
gradient for adsorption of HA on Hematite towards the adsorption of
HA on Kaolinite then the mobility and diffusion coefficient of HA in
solution consist of Hematite is greater than its Kaolinite. Finally, on the
basis of Eq. (45) by a large value of diffusion coefficient for HA in so-
lution consist of Hematite the fractional coverage will be increased. In
other words, existence of a small negative charge on Kaolinite surface
make an electrostatic repulsion interaction between HA molecules
(these molecules have negative charge in aqueous solution because of
existence of carboxylic and phenolic groups in their structure) and
Kaolinite surface and for this reason a decreasing in Diffusion coeffi-
cient occurs for HA molecules in solution. This decreasing is negligible
for adsorption of HA on Hematite.
5. Conclusion
The Statistical Rate Theory (SRT) was applied for description of
adsorption kinetics at the solid/solution interface for Langmuir and
Freundlich (only for m = 1) isotherms. For a Langmuirian adsorption
the Pseudo-First-Order and Pseudo-Second-Order models at times close
to equilibrium and Modified Pseudo-First-Order model at short initial
times of adsorption (not very short initial times) were derived under
different conditions respectively. Also, we showed that the fractional
8
Chemical Engineering Journal xxx (xxxx) xxxx
coverage is a linear function of t at very short initial times of ad-
sorption for Langmuir isotherm.
For Freundlich isotherm (only for m = 1) adsorption kinetics has
been explored at two limiting conditions. One at very short initial times
of adsorption and the other one at times that system is close to equi-
librium. We concluded that for an adsorption that it follows from
Freundlich isotherm the fractional coverage is a linear function of t at
very short initial times of adsorption and Pseudo-First-Order (PFO) as
an important model derived at close to equilibrium. Both of obtained
models at two limiting conditions have been reported at literature
frequently. Also, by accepting some approximations about the general
SRT equation for Freundlich isotherm, the Modified Pseudo-First-Order
(MPFO) and a new rate equation (called SREF model) as two important
c0
models derived from SRT under conditions ( or atc0 ce ) and
e
0 (or atc0 ce ) respectively that appears as an parameter at
concentration of adsorbate in solution (c = c0 ). Finally, accuracy
of PFO and PSO models were considered by several set of experimental
data selected at literature. Also, a set of experimental data was selected
at literature for evaluating MPFO and SREF models for a Freundlich
isotherm. At selected paper, adsorption of Humic Acid (HA) on
Hematite and Kaolinite as two different adsorbents have been reported.
According to the results of this paper the adsorption rate of HA on
Hematite is higher than its Kaolinite. We simulated these adsorption
systems with Stochastic Numerical Simulation approach by using
Chemical Kinetics Simulator software. The results showed that there is a
good agreement between simulated data and MPFO and SREF models at
different condition.
R. Ezzati Chemical Engineering Journal xxx (xxxx) xxxx

Fig. 4. Plot of q(t) vs Time (min) at very short initial times for Humic Acid adsorption on Hematite and Kaolinite as two different adsorbents. Simulated data (blue
open boxes) Eq. (23) (black line). a, b and c for HA adsorption on Hematite at pH 5, 6 and 7 respectively. d, e and f for HA adsorption on Kaolinite at pH 5, 6 and 7
respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Appendix

In order to simulation of adsorption of Humic acid by Hematite and Kaolinite as two different adsorbents, we used the Stochastic Numerical
Simulation. Adsorption simulations were carried out by Chemical Kinetic Simulator (CKS) software. In this simulation method the mechanism of
reaction is considered as a set of several elementary reactions:
nN + mM Products (A.1)
In this simulation method, the input data are the elementary steps, rate constants of any step and number of particles. The algorithm of this
simulation is based on the reaction probability density function which is procured by:

P ( , i ) = ki ci exp ( ki ci ) (A.2)
where P(τ,i), ki, ci and are probability density function, rate constant, number of particles and time respectively. The function of P(τ,i) can be
written as:
P ( , i ) = P ( ) P (i ) (A.3)
According to this algorithm, P (d ) is the probability of occurrence of the next reaction between t + and t + + d . Also, P (i ) implies the
probability that the next reaction occurs at t + . Also, P ( ) is attained by summating of P(τ,i) at entire values of i . That means:
L
P( ) = P ( , i)
i=1 (A.4)
Also, by combination of A.3 and A.4 P (i ) will obtained:
P ( , i)
P (i ) = L
i=1
P ( , i) (A.5)
Equations (A.4) and (A.5) represent the two one-variable density functions in equation (A.3). In this algorithm, P ( ) and P ( i) have another
simple forms that follow as:
P ( ) = a exp( a ) (A.6)

9
R. Ezzati Chemical Engineering Journal xxx (xxxx) xxxx

And
ai
P (i ) =
a (A.7)
L
where in these equations 0 < and i = 1, 2, …, L and also, ai = ki ci and a = ki ci .when the two-variable probability density function is wrote
i=1
as two one-variable density functions P (i ) is independent of . Also, both of these probability density functions are standardized over their respective
explanation. That means:

P ( )d = 1
0 (A.8)
And also,
L
P (i ) = 1
i=1 (A.9)
The groundwork of stochastic numerical simulation is making a random value of in agree with P ( ) in equation (A.6), thereafter it produce a
random integer i in agree with P (i ) in equation (A.7). finally, from random values of and i the P(τ,i) will be obtained. For simulation of adsorption
process we used the Chemical Kinetics Simulator. In this simulator, the mechanism, rate constant and number of particles should be put as input
data. The results of simulation will be shown as concentration versus time curves as output of simulation. The snapshots of CKS- Data Entry for a
hypothetical reaction ( A + S AS ) has been presented in Fig. A.1.

Fig. A1. The snapshots of CKS- data entry and concentration versus time curves as output of simulation for a hypothetical reaction ( A + S AS ).

10
R. Ezzati
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