Advances in Colloid and Interface Science 152 (2009) 2–13

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Advances in Colloid and Interface Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c i s

Theoretical models of sorption kinetics including a surface reaction mechanism:

A review
Wojciech Plazinski a,b,⁎, Wladyslaw Rudzinski a,b, Anita Plazinska c
a
Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek 8, 30-239 Cracow, Poland
b
Department of Theoretical Chemistry, Faculty of Chemistry, UMCS, pl. M. Curie-Sklodowskiej 3, 20-031 Lublin, Poland
c
Laboratory of Drug–Receptor Interactions, Medical University of Lublin, ul.K .Jaczewskiego 4, 20-081 Lublin, Poland

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

Available online 5 August 2009 A review of a certain class of theoretical models describing the kinetics of pollutants sorption onto various
sorbents is presented. These assuming the rate of surface reaction as the rate-limiting step are considered. A
Keywords: special attention is paid to possible theoretical grounds of the most commonly applied mathematical
Sorption expressions, such as the pseudo-second and the pseudo-first order equations. Simple theoretical
Modeling considerations based on some fundamental theories suggest that these two formulae do not correspond
Kinetics
to any specific physical model. They simply approximate well the behaviours predicted by many different
Pseudo-first order
theoretical approaches.
Pseudo-second order
Pollutants removal © 2009 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Models overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Langmuir kinetic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Statistical Rate Theory (SRT) approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. The pseudo-second, the pseudo-first and the Elovich equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.1. The pseudo-second order equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.2. The pseudo-first order equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3.3. Some considerations on the correlation of the experimental data by using the pseudo-first and the pseudo-second order equations . . . 9
2.3.4. The Elovich equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.4. Other models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

1. Introduction description of sorption kinetics is a much more complicated problem

Predicting the rate at which the pollutants removal takes place in a
given solid/solution system is one of the most crucial factors for the
effective sorption system design. Many attempts have been made to
formulate general mathematical expressions, which would be able to
adequately describe the kinetics of sorption in such systems. The
progress in this field appears to be limited by the fact that the
⁎ Corresponding author. Institute of Catalysis and Surface Chemistry, Polish Academy
of Sciences, ul. Niezapominajek 8, 30-239 Cracow, Poland. Tel.: +48 81 537 5519; fax:
+48 81 537 5685.
E-mail address: wojtek_plazinski@o2.pl (W. Plazinski).
than the theoretical description of sorption equilibria. This is because
the expressions describing the thermodynamic quantities at equilib-
rium are only limiting forms of those describing the time evolution of
these quantities under non-equilibrium conditions.
According to the present state of knowledge [1], the sorption
process can be described by the following consecutive steps (i)
transport of solute in the bulk of the solution; (ii) diffusion of solute
across the so-called liquid film surrounding sorbent particles; (iii)
diffusion of solute in the liquid contained in the pores of sorbate
particle and along the pore walls (intraparticle diffusion); (iv)
adsorption and desorption of solute molecules on/from the sorbent
surface. The overall sorption rate may mainly be controlled by any of

0001-8686/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.cis.2009.07.009
 W. Plazinski et al. / Advances in Colloid and Interface Science 152 (2009) 2–13
these steps; a combined effect of a few steps is also possible. In many
experimental sorption systems the effect of transport in the solution is
eliminated by rapid mechanical mixing, thus, it is not assumed to be
involved in controlling of the overall sorption rate and can be ignored,
as a rule. In order to determine the contribution of the remaining
steps, numerous kinetic models have been compared to predict the
behaviour of the experimental data. The most widely used are those
assuming that step (iv) makes a significant contribution in the
kinetics of a process. Here, this step is referred to as the “surface
reaction”. The “surface reaction” term may not necessarily mean the
actual chemical reaction occurring on the adsorbent surface involving
the formation of chemical bonds. Interactions of physical nature (van
der Waals forces, for instance) may also play a role. The crucial
assumption behind this model is that the rate of the transfer of solute
molecules from the solution (located in the direct vicinity of the
surface) to the adsorbed phase either governs the overall rate of
sorption process or at least is partially involved in it.
The development of an appropriate model can be based on
accepting a certain fundamental approach to interfacial kinetics, such
as the Langmuir model, for instance, and its further modification in
order to adopt it for a given sorption system. This method has led to
propose many expressions related to the concept of a chemical
reaction occurring on the surface and its order [1]. These include
Langmuir kinetics [2], first order [3] and second-order [4] reversible,
and first-order [5] and second-order [6] irreversible reactions based
on the solute concentrations. Simultaneously, many simple, compact
formulas, such as the pseudo-first (Lagergren), pseudo-second or
Elovich equations have been applied for correlating kinetic data
measured in many different systems [7]. These formulae have usually
been associated with the surface-reaction kinetic step as controlling
the sorption rate. Their main advantage is simplicity and easiness
when applying to correlate the data without necessity of using
advanced computational procedures. Most often many different rate
equations are tested in parallel and the appropriate best-fit proce-
dures are used to verify whether one is better than another. The linear
least-squares method, applied to the transformed kinetic data is
usually adopted for this purpose.
An overview of the papers reporting on the applicability of such
expressions as the pseudo-first or pseudo-second equations reveals
that they are able to describe well the data collected in the system
containing radically different kinds of solutes (metal ions, organic
compounds…) and sorbents (active carbons, inorganic minerals,
biosorbents…). This suggests that either very similar processes
determine the sorption kinetics in these systems or that the math-
ematical form of the applied equations makes their flexibility suf-
ficient to cover well the kinetic behaviour of most sorption systems.
This latter possibility is a more logical choice in view of the opinions
that the pseudo-first order equation, for instance, is only an approx-
imate solution of other, more complicated rate mechanisms [1]. A
similar statement has been formulated concerning other rate
equations [8]. Related papers, reviewing the experimental data,
have been published by Ho [9], Ho et al. [1], Ho and McKay [7,10]
and Febrianto et al. [11].
One of the objectives of this paper is to present some recently
developed models for description of sorption kinetics which assume
that the rate of surface reaction is one of the steps controlling the
overall sorption rate. Newly proposed insights into the existing
fundamental models (such as the Langmuir kinetic model) are also
briefly discussed. A particular attention is paid to the new SRT
(Statistical Rate Theory) approach, which has recently been applied to
describe the kinetics of pollutants sorption at solid/solution interfaces.
The second objective is to present some considerations on the
popular mathematical formulae, extensively applied for correlating the
kinetic data, e.g. the pseudo-first, pseudo-second or Elovich equations.
Their theoretical interpretations are shortly presented, together with
the assumptions which have to be made for this purpose. Further, an
3
inspection to the recently reported experimental data provides some
new insights to the issue of the applicability of the mentioned
expression. It should be noted that the selected data should not be
seen as an exhaustive review on the applicability of the pseudo-first or
pseudo-second order models to describe the kinetics of sorption in
solid/solution systems. Such reviews are available elsewhere [1,7,9–12].
This summary report is to stress some characteristic features of physical
systems and to connect the observations made on the basis of
theoretical approaches with those which can be drawn by qualitative
and quantitative analyses of experimental data.
A wide description of other types of sorption kinetics models,
including diffusion-driven kinetics, i.e. external film diffusion model,
intraparticle pore- and surface-diffusion models, shrinking core
model, their combinations as well as examples of their applications
can be found elsewhere [1,13–22].
2. Models overview
2.1. Langmuir kinetic model
The chronologically first model belonging to this category is that
proposed by Langmuir in 1918 [2] for description of the kinetics of
gases adsorption onto solid surfaces and adopted later for the solid/
solution systems. It reads:
dqðtÞ
= Ka cðqm −qðtÞÞ−Kd qðtÞ ð1Þ
dt
in which c is the solute concentration in the bulk solution, q(t) is the
amount adsorbed at time t, and qe =q(t→∞). Further, Ka and Kd are some
temperature-dependent constants and qm is the monolayer capacity, i.e.
the maximum amount that can be adsorbed. When dq(t)/dt=0, i.e. when
equilibrium is reached, Eq. (1) leads to the well-known Langmuir
adsorption isotherm. This model is rather rarely used in its form given
by Eq. (1), however, when some assumptions are made, it can reduce to
other expressions, commonly applied for the analysis of kinetic data. Its
details will be mentioned later in Sections 2.3.1 and 2.3.2.
Eq. (1) is related to the simple case of an ideal, energetically
homogeneous solid surface and one-site occupancy adsorption model.
The problem of incorporating the surface heterogeneity into the classical
Langmuir kinetics has been considered by Tovbin [23]. The existence of a
two-dimensional differential distribution of the Ka and Kd constants (or
of an analogical function related to the activation energies of adsorption
and desorption processes), normalized to unity (χ) has been proposed
[23]. The desired generalization would consist in averaging the rate in
Eq. (1) by using the accepted χ function to get the average rate for a
heterogeneous solid surface. Another solution consists in averaging the
integral form of Eq. (1) with a certain χ function. A serious complication
is the lack of information on how the Ka and Kd values may change from
one adsorption site to another [24].
A simple way to consider the heterogeneity effects has been
proposed [25,26] by accepting the following form of the so-called
kinetic Langmuir–Freundlich (LF) equation:
dqðtÞ ðLFÞ s ðLFÞ s
= Ka cðqm −qðtÞÞ 1 −Kd qðtÞ 2 ð2Þ
dt
in which s1 = s2. At equilibrium, when dq(t)/dt = 0, such expression
leads to the commonly known LF equilibrium adsorption isotherm,
which is able to reflect the surface heterogeneity. Eq. (2) can be
treated as a formula describing the heterogeneity only in an
approximate way. The reasons for that can be explained as follows.
From the point of view of statistical thermodynamics approach, the
case in which s1 = s2 = s N 1 corresponds to the dissociative adsorption
model, in which it is assumed that every adsorbing solute molecule
can be bound by any s sites present on the surface; these sites may not
necessarily be neighbouring [27]. In other words the (non-physical)
4 W. Plazinski et al. / Advances in Colloid and Interface Science 152 (2009) 2–13
model in which every solute molecule splits into s equivalent parts to
form s independent complexes has to be accepted. On the contrary, in
the case of multi-site occupancy (non-dissociative) adsorption the
s1 N s2 = 1 condition must be fulfilled, as can be shown by using the
theory of Nitta et al. [28,29] taking into account the correlations
between the neighbouring adsorption sites and the adsorbing species.
Advanced solutions for complications related to both the surface
heterogeneity and the multi-site occupancy effects are known in
literature on gas/solid systems [30] but, to our present knowledge,
have never been widely applied to the description of solution/solid
systems. The examples of application of the Langmuir kinetic model
and its various modifications can be found in [31–33].
Some new insights into the way of calculation of adsorption and
desorption rate constants characteristic of Langmuir kinetics were
proposed by Kuan et al. [34]. These authors developed the geometric
approach based on the observed linearity of the initial region of
kinetic adsorption isotherm plotted as q(t) vs. t. This approach was
further extended by taking into account the presence of surface
heterogeneity and the effect of decreasing solute concentration
during the adsorption process [35]. Both these methods were applied
for the analysis of experimental data [33–38].
Some other mathematical expressions, equivalent to Eq. (1) are
known in literature which may have a pronounced effect on the
theoretical interpretation of several empirical equations. Further
sections of this paper contain more details.
Let us also mention that the Langmuir kinetic model is also known
as the “Theory of Activated Adsorption/Desorption (TAAD)” approach
[39,40].
2.2. Statistical Rate Theory (SRT) approach
In the early 1980s a new family of theoretical approaches
appeared, linking the rate of adsorption/desorption to the chemical
potentials of the bulk and the adsorbed molecules. Among them the
SRT approach launched by Ward et al. [41,42] received the most
advanced theoretical background. More recently, it has been shown
how the SRT approach can further be generalized to describe the
kinetics of adsorption in the gas/solid [43–45] and solution/solid
[8,46] systems with energetically heterogeneous solid surfaces. To
describe the kinetics of adsorption the general rate expression can be
written in the following form:



dqðtÞ μ ðcÞ−μads ðqðtÞÞ μ ðqðtÞÞ−μsol ðcÞ
= Re exp sol − exp ads
dt kT kT
where μsol and μads are the chemical potentials of the solute molecules
in the bulk solution and in the adsorbed phase, respectively, under
non-equilibrium conditions, and Re is the exchange rate at equilibrium
to which the system would evolve after being closed and equilibrated;
k and T have their usual meanings. One essential assumption inhered
in the SRT approach is that of a quasi-equilibrium on the solid surface.
Namely, it is assumed that all correlation functions in the adsorbed
phase are the same functions of surface coverage which one would
observe at full equilibrium and the same surface coverage. Thus, the
chemical potential of the adsorbed molecules should be the same
function of surface coverage as under full equilibrium conditions. In
the Langmuir model of adsorption one may consider the whole
adsorption system as a collection of subsystems being only in thermal
and material contact [8]. This assumption allows for solving the
problem of expressing μads of the adsorbed phase localized on the
energetically heterogeneous surface.
The first attempts to apply the SRT approach to describe the sorption
rate at the solution/solid interfaces were made by Rudzinski and Plazinski
by accepting the simplest (Langmuir) model of one-site-occupancy
adsorption on an ideally homogeneous surface [8,47]. In comparison to
the previously known expressions describing the kinetics of gases
adsorption on solids, the main complication had its source in the effect
of decreasing solute concentration in the course of the process. This causes
that in most cases an analytical solution for dependence of the amount
adsorbed on time cannot be obtained without further approximations.
The assumption of a quasi-equilibrium enables to arrive at exact
expressions for μads; only the equation of equilibrium adsorption
isotherm describing a given system well has to be known and no
further assumptions about the distribution of affinity constant, for
instance, have to be made [8]. This way of generalization of the SRT
approach was investigated by accepting the most commonly applied
equilibrium-related expressions, such as the Langmuir–Freundlich,
Toth [46] or Temkin equations [8]. Further, this approach was
employed to explain the possible theoretical grounds of many kinetic
expressions, i.e. the pseudo-first order (Lagergren) [8,48–50], pseudo-
second order [8,46,51], Elovich [8,49] and modified-pseudo-first order
(MPFO) [52,53] equations. These issues will be considered below in a
more detailed way.
One of the most general SRT related expressions which can describe
the rate of sorption on both homo- and heterogeneous surfaces can be
written as follows:



1 = ν 
dqðtÞ q q −qðtÞ 1 = ν 1 qðtÞ
= Kls ce 1− e KL c m − ð4Þ
dt qm qðtÞ KL c qm −qðtÞ
where Kls is a constant which can be associated with the reaction rate
constant, KL is the constant describing the equilibrium in the system and
can be determined from the experimental equilibrium isotherm (in the
case of ν = 1, KL became the Langmuir constant) and ν is the so-called
“heterogeneity parameter”, appearing also in the Langmuir–Freundlich
equation. For physical reasons, the values ν can vary from 0 to 1 in such a
way that the degree of surface heterogeneity increases when the value
of ν decreases and ν = 1 corresponds to the ideally homogeneous
surface. When equilibrium is assumed to be reached (dq(t)/dt = 0),
Eq. (4), similarly to Eq. (2), yields the Langmuir–Freundlich equation.
As the necessity for obtaining simple compact expressions is of
primary importance when considering the procedure of correlating the
measured, kinetic data, several attempts were made for that direction. It
was noted that the effect of the time-dependent value of c has very
limited influence on the course of q(t) plots calculated by using the
model of a homogeneous solid surface [46,52]. Further, it has been
shown that the MPFO equation can serve as a good approximation of the
SRT model (for the case of a homogeneous surface) [52]. Similar
ð3Þ
investigations have been performed by Azizian and Bashiri [53] who
provided theoretical interpretation for the MPFO equation based on SRT
and developed a new simple kinetic equation derived for the initial
times of adsorption. Moreover, all above mentioned derivations of the
popular kinetic equations are partially related to this problem — when
their theoretical interpretations (obtained on the grounds of SRT) as
well as the physical meaning of parameters appearing in them are
known, then they can be treated as approximations of the (exact)
kinetic models originating from the SRT approach (compare [51]).
As the rate of the surface reaction can be only one of the kinetic
steps involved in controlling of the overall sorption kinetics, it seems to
be reasonable to combine SRT with the previously mentioned family of
diffusional models. It has been done in an approximate way by using
the pore-diffusion model (IDM) as shown in [52] and [54]. The main
assumption was that the kinetics of sorption can be considered as a
two-step process. The first (initial) kinetics is governed mainly by the
rate of surface reaction and, therefore, can be expressed in terms of
SRT. When the adsorbed amount reaches a certain ratio of the
equilibrium surface coverage “switching” takes place to another
kinetics governed mainly by the rate of solute diffusion in pores of
the sorbent, expressed by IDM. Eq. (3) and the expression originating
from IDM has been used to calculate the whole composite kinetic
isotherm and a numerical procedure has been proposed to use these
 W. Plazinski et al. / Advances in Colloid and Interface Science 152 (2009) 2–13
equations in the quantitative analysis of experimental data [54].
Further, the modified pseudo-first order (MPFO) equation has been
used as an approximation of the SRT model in order to simplify some
analytical procedures. One of the main advantages of this latter
method is the possibility of applying linear representations with
respect to time, which seems to be a convenient tool for distinguishing
between the surface reaction and the diffusional kinetics [48,52]. Both
mentioned approximated methods have their sources in the potential
computational complications connected with the direct combination
of SRT and IDM approaches. This would require developing an efficient
numerical procedure enabling solving the set of coupled partial
differential equations. This issue has not been resolved yet.
A much simpler question is to combine both the external film
diffusion (FDM) and the SRT models as shown in [55]. The rate of solute
diffusion in the subsurface region has the most significant effect on the
sorption kinetics monitored at short adsorption times. A model
investigation has shown that the concave character of dependence of
the amount adsorbed on the square-root of time may be due to a
combined effect of the rate of surface reaction (expressed in terms of
SRT) and that of the solute transport from the bulk to the surface [55].
The proposed approach is exact, computationally convenient and can be
easily generalized for the case of energetically heterogeneous surfaces.
Recent studies by Azizian et al. have concerned the description of the
kinetics of competitive adsorption at the solid/solution interfaces by
using the SRT approach. These authors at first derived the chemical
potential of adspecies for competitive adsorption based on general
principles of statistical thermodynamics (canonical ensemble) and then
developed kinetic equations for competitive adsorption which were
able to describe quantitatively the experimental data. As an alternative
method of avoiding the necessity of solving the derived, complex rate
equations, a stochastic numerical simulation approach for modeling of
experimental data has been proposed by using the SRT expressions [56].
Another issue, which can be considered as a special case of two-
component competitive adsorption, is connected with the description
of the pH effect on kinetics of metal ions adsorption at energetically
heterogeneous solid/solution interfaces. Then, the metal ions compete
with protons for the available surface sites. Rudzinski and Plazinski
[57] have introduced a concept of “effective” heterogeneity which was
found to represent very well the combined effects of surface energetic
heterogeneity and the electrostatic lateral interactions between ions
in the adsorbed phase, described by using the Mean Field approxi-
mation. This let reduce the number of parameters and derive the
expressions similar to those presented in [56], but corresponding to
the more general case of an energetically heterogeneous surface
combined with the presence of repulsive interactions between the
adsorbed ions.
The classical, competitive adsorption model, seems to be over-
simplified to represent adequately both the equilibrium and kinetics of
metal ion adsorption in many technologically-important systems. This
observation led to propose an approximation expressed by the so-
called Non-Competitive Adsorption Model (NCAM) [58,59], used for
description of pH influence on the equilibrium and kinetics of heavy
metals biosorption. The cases of both homogeneous and heteroge-
neous surfaces have been taken into account. Although this model can
be interpreted in mechanistic terms, the suggestion has been launched
that it is very probable that the NCAM approach can simulate well the
behaviour predicted by far more complicated and sophisticated
models representing some other mechanisms of biosorption. The
combination of the NCAM model with the SRT approach has led to
arriving at the pH-related expressions for biosorption kinetics which
are very similar to those previously proposed; the main difference is
the theoretical interpretation of some coefficients, which are pH-
dependent now [60].
It is also worth noting that very recently SRT has been applied by
Azizian and Bashiri for the description of desorption kinetics at the
solid/solution interface [61].
5
The main advantages of the SRT approach as a tool for modeling
the kinetics of sorption processes at the solid/solution interfaces can
be summarized as follows.
1. SRT-related kinetic expressions can be developed directly from the
equations describing the equilibrium state in the investigated
system; this is especially useful in the case of heterogeneous
surfaces as it eliminates the necessity of making detailed assump-
tions about the character of this heterogeneity. This also causes
that the mathematical expressions developed by using SRT reduce
to the corresponding equilibrium adsorption isotherm equations at
dq/dt = 0 (see more details in [46,62]).
2. Usually, the analysis of experimental data by using Eq. (4) requires
adjusting the value of only one best-fit parameter (Kls). This
parameter can be identified with the reaction rate constant,
appearing in the classical Langmuir model. The values of remaining
parameters are known from the equilibrium measurements,
accompanying the kinetic experiment (e.g. the Langmuir constant)
or they represent the operational condition (e.g. cin, volume of the
bulk solution).
3. In spite of the complicated mathematical form of SRT-related
expressions, there exist many methods leading to their approxi-
mate but much simpler form.
4. Recently, a simple procedure of expressing some constants
appearing in the SRT kinetic equations through the value of qe has
been proposed and applied [51,60]. Its advantages are following:
• reducing the number of parameters which have to be estimated
from the experimental equilibrium isotherm; this is especially
important when (i) the kinetic experiment is not accompanied
by the equilibrium one or (ii) when the experimental error is
supposed to be significant in the case of equilibrium isotherm;
• the possibility of estimating the actual values of the equilibrium
amount adsorbed when only the experimental kinetic isotherms
are at disposal.
2.3. The pseudo-second, the pseudo-first and the Elovich equations
This section contains description of expressions not being the
actual models of sorption kinetics in their physical sense. In fact, they
may correspond to many different kinetic models, approximating
them well. However, their enormous popularity and common use give
reasons for focusing on them. At present, the most popular are the
pseudo-first and the pseudo-second order equations. As noted by Liu
and Liu [63], these two expressions are commonly “employed in
parallel, and one is often claimed to be better than another according
to marginal difference in correlation coefficient”. Current understand-
ing of the theoretical grounds of these equations is discussed below.
2.3.1. The pseudo-second order equation
The pseudo-second order kinetics is usually associated with the
situation when the rate of direct adsorption/desorption process (seen
as a kind of chemical reaction) controls the overall sorption kinetics. In
fact, the mathematical expression corresponding to this model was
proposed by Blanchard et al. [64] to describe the kinetics of heavy
metal removal by natural zeolites. There was accepted the assumption
that the rate of the ion exchange reaction occurring on the surface is
responsible for the removal kinetics and that the kinetic order of this
reaction is two with respect to the number of adsorption sites available
for the exchange.
The most commonly-applied form of the pseudo-second order
equation is that presented by Ho [65,66]. It can be written in its differential
form as:
dqðtÞ 2
= k2 ðqe −qðtÞÞ ð5Þ
dt
6 W. Plazinski et al. / Advances in Colloid and Interface Science 152 (2009) 2–13
or, after integrating the above expression with the boundary con-
dition q(t = 0) = 0 and then rearrangement:
t 1 t to represent the kinetics of sorption in the systems for which not only
= +
qðtÞ k2 qe qe
where k2 is a constant. The procedure of applying the above
expression for the analysis of the monitored kinetic data is usually
based on plotting of t/q(t) against t which should give a linear
relationship. The above mentioned coordinates are suggested by the
mathematical form of Eq. (6). However, there exist other, less popular,
linear dependencies associated with the pseudo-second order model
presented by Ho [67], which are less frequently used [68,69]. When
accepting Eq. (6), the qe and k2 parameters can be determined directly
from the slope and the intercept of the t/q(t) against t plot.
Many experimental studies and the extensive use of the pseudo-
second order model have revealed that the value of k2 strongly
depends on the applied operating conditions. Here, the influence of
experimental factors on the k2 is discussed on the basis of sorption
systems for which such dependencies have recently been reported.
The initial solute concentration, pH of solution, temperature and
agitation rate have been taken into account.
The k2 constant value is usually strongly dependent on the applied
initial solute concentration. It decreases with the increasing cin as a
rule, which is a commonly known fact related to the interpretation of
k2 as a time-scaling factor (obviously, the higher is the cin value, the
longer time is required to reach an equilibrium) [11,70–76]. This is in
agreement with the results of most theoretical interpretations,
predicting such dependence of k2 on cin (further details are given
below). Only very few systems for which k2 is cin-independent or
increases with the cin value have been reported [77–83].
The influence of pH and temperature on the k2 value has not yet
been theoretically studied, due to the complexity of the problem and
numerous different factors, importance of which can vary from one
system to another. A general inspection of the experimental results
indicates that the tendency in changes of k2 value cannot be crudely
estimated by using only the dependence of the equilibrium adsorption
isotherm on a given factor. The change in a parameter of the system
(pH or temperature) results in the change in the equilibrium state, i.e.
in increase or decrease of the qe value. Usually, the higher value of qe is
correlated with the higher value of k2. This situation can be compared
to those previously discussed; when considering the increasing value
of cin, one can notice that then the higher value of qe requires a longer
time for the system to reach an equilibrium and, in turn, the k2 value
decreases. The opposite behaviour speaks for the conclusion that the
influence of both pH and temperature is not restricted to the
equilibrium features of the system but these factors play an important
role in the course of kinetic processes. Some examples of the
mentioned behaviour can be found in [68,72,78,79,84–86].
Let us consider the case of sorption systems for which the kinetics of
solute removal from solution was monitored at different values of
agitation rates. While considering all the processes which may control
the sorption rate, the significance of the transport of sorbate in the
subsurface region can be identified by using different degrees of
mechanical mixing during the experiment. Observable differences in the
q(t) vs. t kinetic curves corresponding to different agitation rates speak
for the significant influence of the solute diffusion in the liquid film on
the overall sorption process. At high agitation rates, the volume of the
subsurface layer reaches a constant minimum while the rate of solute
transport within it reaches a constant maximum value and can be
usually neglected. Nevertheless, differences in the experimental q(t)
data when the agitation rate is the only variable clearly indicate that the
contribution of different kinetic processes to controlling the sorption
kinetics is changing. The data presented in [87–100] show that the
pseudo-second order equation is not able to reflect this fact; it correlates
the q(t) data measured for different agitation rates equally well, in spite
of significant qualitative differences between them. Only the changes in
the qe and k2 values depend on the applied conditions. These examples
may be a convincing proof that the pseudo-second order equation is able
ð6Þ
the rate of surface reaction governs the overall process rate. Moreover,
on the basis of only simple best-fit procedure performed by accepting
Eq. (6), distinguishing between two different kinetic mechanisms is not
possible, as the differences between the obtained correlation coeffi-
cients are marginal, as a rule.
Regardless of applying some fundamental theoretical approaches,
there have been some attempts made to find an empirical correlation
between the obtained values of k2 and the most important operational
conditions. One of such examples is the paper by Ho and McKay [101],
reporting the kinetics of sorption of divalent metal ions onto
sphagnum moss peat at different initial metal ion concentrations. A
compact empirical two-parameter formula has been found to predict
the dependence of k2 on cin for copper, nickel and lead ion satis-
factorily well. One of the major advantages of such a method is the
possibility of obtaining generalized predictive expressions which can
be used directly to derive the amount of solute adsorbed at any given
solute concentration and the reaction time without the necessity of
developing complicated theoretical models, based on some more
fundamental assumptions. A similar procedure has been also applied
for the data collected in other systems [102–105].
As it can be easily proved, the k2 constant plays a role of time-
scaling factor, i.e. when its value is relatively high, the time required to
reach an equilibrium state by the system is relatively short; an
opposite situation occurs for small k2. Recently, Rudzinski and
Plazinski have connected the k2 constant with another parameter,
described as a degree of reaching the equilibrium state by a sorption
system after elapsing of a certain period of time [51]. This relationship
has been expressed by using a very simple and compact mathematical
expression and appeared to be very useful in model investigations
dealing with the issue of estimating the amount of solute sorbed at
equilibrium on the basis of kinetic data [51]. More detailed theoretical
interpretations of k2 are inherent in possible derivations of the
pseudo-second order equation. This will be discussed later in this
section.
Another parameter present in Eq. (6) represents the amount of
solute sorbed at equilibrium (qe). Generally, its value should be equal
to those determined from the measurements of the equilibrium
sorption isotherm, which can accompany the recording of the kinetic
data. Nevertheless, there arise uncertainties about the correctness of
the qe values, determined using solely the pseudo-second order
equation, in the case of lack of experimental equilibrium isotherm of
sorption. Detailed theoretical calculations have been performed by
Rudzinski and Plazinski in order to find connection between the
“actual” value of qe and those estimated by using Eq. (6). The SRT
approach has been applied for this purpose. According to our present
knowledge, no further attempts have been made to study this issue on
the basis of some other fundamental theories. There exist, however,
numerous comparisons, similar to those mentioned and based on the
experimental data which can be found in literature [11,93,94,106,107].
Currently, a few different theoretical interpretations of the
pseudo-second order equation are known in literature. One of the
earliest is that launched by Azizian in 2004 [108]. The derivation of the
pseudo-second order model proposed by this author is based on the
classical Langmuirian model of adsorption kinetics [2] in which
adsorption is seen as a chemical reaction occurring on the solid
surface. Under such assumption, the rate of sorption process is
proportional to the actual solute concentration in the bulk solution
and to the number of unoccupied adsorption sites whereas that of
desorption is proportional only to the number of sites occupied by
solute molecules. An important distinction has been made by Azizian:
the cases of solute concentration which changes in time or is nearly
constant have been considered. In the (more realistic) case in which
 W. Plazinski et al. / Advances in Colloid and Interface Science 152 (2009) 2–13
the effect of decreasing c value is taken into account, the Langmuirian
kinetics can be represented well by the pseudo-second order model.
(The situation when c is constant in time corresponds to the pseudo-
first order equation; this issue is discussed in Section 2.3.2). However,
in order to arrive at the mathematically compatible form of the
pseudo-second order equation, some approximations have to be
made (see [108] for more details), accuracy of which has not yet been
investigated. The Azizian's approach offers also the theoretical
interpretation of the k2 parameter; it is quite complicated function,
dependent on c0, qe as well as adsorption and desorption reaction rate
constants. In spite of the fact that this approach does not consider a
case of an energetically heterogeneous solid surface, Azizian has also
discussed the case of heterogeneous surfaces with two different sites
and proposed the so-called two-site pseudo-second-order (TS-PSO)
model [109].
In the approach proposed by Rudzinski and Plazinski in 2006 [8],
the pseudo-second order equation is treated as a special case of the
more general kinetic equation, developed for the model of a strongly
heterogeneous solid surface by using the SRT approach. One of the
assumptions was that the c value is constant in time. However, the
theoretical kinetic isotherms of sorption, generated by applying
models originating from SRT for different solid/solution ratios have
also obeyed the behaviour predicted by Eq. (6) very well. Further,
these authors have generalized this approach for the case of decreasing
value of solute concentration [46]. Recently, [51] some attempts have
been made to prove that the pseudo-second order equation can be
treated as a very flexible formula able to represent (in an approximate,
but still sufficiently effective way) almost every kinetic expression
derived by accepting the SRT approach. Models describing different
degrees of surface heterogeneity as well as different solid/solution
ratios have been taken into account. The most important conclusions
which can be drawn from the studies by Rudzinski and Plazinski are
following. (i) As noticed by Liu and Shen [110] and Liu and Liu [63],
“the pseudo second-order kinetic equation cannot be naturally
obtained” from the SRT approach, which is basically true if considering
the direct, mathematical (symbolic) derivation and the concept of
sorption reaction order. Nevertheless, the convergence of both these
models is, in most cases, nearly perfect as shown by numerical
calculations. (ii) The observed goodness of t/q(t) vs. t linear plots does
not necessarily speak for the reliable estimation of the equilibrium
adsorbed amount. The qe values determined in this way are usually
smaller than the actual ones. However, the application of Eq. (6) can be
very useful for obtaining qe under the essential condition that there is a
significant part of the kinetic data measured close to equilibrium at
disposal. (iii) According to Rudzinski and Plazinski, it is possible to
propose a theoretical interpretation for k2 only for special cases of
sorption systems or in an approximate manner. This is fully
understandable as the direct mathematical derivation of the pseudo-
second order equation in terms of SRT has not yet been proposed;
numerical computations are required for this purpose.
Recently, Özer [111] and Liu and Shen [110] have proposed to treat the
pseudo-second order equation as a special case of the more general rate
law equation in which the order of sorption kinetics is not preset to a fixed
value. Following Liu and Shen the adsorption reaction order is expressed
with regard to the so-called effective concentration of the adsorption sites
available on the surface (which is a function of the amount adsorbed at a
given time and equilibrium). The simplicity of such an approach leads
directly to both the pseudo-first and the pseudo-second order equations
when the order of assumed reaction is preset to 1 and 2, respectively. The
rate equation for this model can be written as follows:
dqðtÞ x At the end of 19th century, Lagergren presented the empirical rate
= kx ðqe −qðtÞÞ ð7Þ
dt
in which kx is a constant and x is the adsorption reaction order with
regard to the effective concentration [110]. The x parameter value can
be both integral or rational nonintegral numbers.
7
Another approach, based on the well-known Langmuir rate Eq. (1),
is that presented by Liu and Shen [112]. It has been proved that that
the classical Langmuir kinetics can be transformed to a polynomial
expression depending on a difference between the equilibrium and
the actual (time-dependent) adsorbed amount:
dqðtÞ 2
= κ1 ðqe −qðtÞÞ + κ2 ðqe −qðtÞÞ ð8Þ
dt
in which κ1 and κ2 are the constants. Depending on the values of these
constants, expression (8) can reduce either to the pseudo-first or to
the pseudo-second order rate equations. The authors have also put
forward the conditions (which have appeared to be cin-dependent)
for simplification of the Langmuir kinetics to the mentioned
commonly-known expressions. Both papers [108] and [112] clearly
show that the pseudo-second order equation is only a special case of
Langmuir rate equation. The same is also true for the pseudo-first
order equation which is discussed below.
As noted by Azizian [113], the kinetic models appearing in the
papers by Liu et al. [63,110,114,115] are not restricted only to
biosorption studies as indicated by the authors but can be used for
other kinds of sorption systems.
Lin and Wang [116] interpreted the pseudo-second order equation
as a special kind of Langmuir kinetics for a two-site occupancy
adsorption model. This derivation, however, requires assumption that
(i) the solute concentration is constant in time and (ii) the total number
of binding sites (here: the qm value) depends on the equilibrium
amount of solute adsorbed.
The pseudo-second order equation can usually predict the actual
value of equilibrium adsorbed amount very well [11]. This can be
explained as follows: the expected value of tangent of the linear plot,
represented by Eq. (6) is equal to 1/q e. Let us consider the
corresponding behaviour of the theoretical models. While studying
the asymptotical behaviour of certain q(t) function one can show
that:
t = qðtÞ 1
lim = lim = 1 = qe ð9Þ
t→∞ t t→∞ qðtÞ
Thus, the interpretation of the tangent of the linear plot (9) which
comes from every kinetic isotherm equation having the physical limit
q(t → ∞) = qe is the same as that presented in Eq. (6). This fact can play
an important role in the analysis of the experimental kinetic data;
namely, it means that the qe value can be determined from the
pseudo-second order plot independently of the kinetic mechanism
which governs the adsorption process. The only essential condition
which has to be fulfilled is that a significant part of kinetic data must
be monitored at the times when the sorption system is close to
equilibrium, as postulated in [51].
A potential 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. The asymptotic relation
similar to those expressed by Eq. (9) can be written for various models
by using the differential form of the pseudo-first equation (compare
expansion (13)). In spite of the fact that the qe values estimated by
using linear representation (10) usually differ much from those
determined experimentally. This issue is discussed in Sections 2.3.2
and 2.3.3.
2.3.2. The pseudo-first order equation
equation for the adsorption of ocalic and malonic acids onto charcoal
[117]. This equation, called the pseudo-first order equation or the
Lagergren equation, is probably the earliest known one describing the
rate of sorption in the liquid-phase systems. Moreover, it has been one
8 W. Plazinski et al. / Advances in Colloid and Interface Science 152 (2009) 2–13
of the most widely used kinetic equations until now. Its differential
form has the following formulation:
dqðtÞ
= k1 ðqe −qðtÞÞ
dt
When solving Eq. (10) with the boundary condition q(t = 0) = 0, one
obtains:
lnðqe −qðtÞÞ = ln qe −k1 t:
The values of qe and k1 parameters are usually determined by
applying the commonly accepted linear regression procedure, based
on the above representation.
The k1 parameter is the time-scaling factor the value of which
decides how fast the equilibrium in the system can be reached (the
tendency of the increasing k1 value which results in shorter times
required for a system to reach an equilibrium is maintained). As the
similar observation has been made regarding the k2 constant, it is
worth noting that these resemblances are due to the mathematical
differential forms of both the pseudo-first and the pseudo-second
order equations.
The experimental studies have confirmed that the value of k1
parameter can be both dependent and independent of the applied
operating conditions. Similarly to the previous section, here we
present a brief discussion on the influence of experimental factors on
the k1 value. Also, some recently reported examples of physical
sorption systems are given for illustrative purpose.
The pseudo-first order equation is usually not able to describe the
kinetic data equally well as the pseudo-second order equation [11].
Examples of an opposite trend are rather sparse [118–120]. Most of
them include the data fulfilling both the following conditions: (i) the
influence of experimental random error is not significant (judging
from the scatter of the experimental points) and (ii) the data (or at
least their significant part) are collected when the system is not very
close to equilibrium. One of possible explanations for this fact is given
in Section 2.3.3 in this paper.
The dependence of the k1 constant value on the applied initial
solute concentration varies from one system to another. It usually
decreases with the increasing initial solute concentration in the bulk
phase [11,93,94,121,122]. This is understandable, as k1 can be treated
as a time-scaling factor. Nevertheless, there are also systems whose
behaviour can be predicted well by Eq. (11) and the obtained k1
values are independent of cin [123–129]. There exist approaches able
to offer theoretical interpretation of the pseudo-first order equation in
which k1 is or is not a function of cin. More details are given below.
When considering the influence of pH and temperature on the k1
value, conclusions similar to those mentioned in the previous section
can be drawn, i.e. that the estimation of the sorption rate cannot be
done when only the equilibrium data are at disposal (This observation
is supported by the data presented in [78,122,130], for instance). A
potential limitation is the significantly smaller number of papers
reporting good applicability of the pseudo-first order equation.
As it has been mentioned in the case of the pseudo-second order
rate equation, also Eq. (10) is usually associated with the situation
when the overall rate of sorption is determined by the rate of direct
solute transfer from the solution to the adsorbed phase. This is clearly
shown by the earlier-mentioned derivations by Azizian [108] and by
Liu and Shen [112] originating from the classical Langmuirian kinetics
and by Rudzinski and Plazinski [8] who have accepted the SRT
approach. In this latter case the necessary condition was that the
sorption system is relatively close to the equilibrium state; this
indirectly is connected with the acceptance of constant or nearly
constant solute concentration in the bulk solution (see also [48]). This
observation has also been confirmed by Azizian [108,113]. For all
these interpretations the k1 constant is dependent on the initial value
of solute concentration in the bulk phase. In particular, according to
the approach by Azizian, k1 is a linearly increasing function of cin,
while in the remaining cases, the value of k1 is given by more
complicated functions. It is worth mentioning that also Boyd et al.
ð10Þ
[131] have developed a rate equation, mathematically identical to the
integral form of the pseudo-first order equation, for the description of
the exchange sorption of ions from aqueous solution by organic
zeolites. This derivation requires accepting that the bulk concentra-
tions of both (replaced and replacing) type of ions are time-
ð11Þ independent. Moreover, the theoretical interpretation of the k1
indicates that it should be a linear combination of these two con-
centration values. Similarities of these observations with those drawn
from the Azizian's approach are obvious and it is interesting to note
that different kinds of adsorption mechanism (here: adsorption and
ion-exchange) may lead to the same kinetic equation.
Liu et al. [115] have interpreted the pseudo-first order equation in
terms of the kinetic process governed by the rate of first-order
reversible reaction, in which the rate of sorption process in inde-
pendent of the adsorbed amount present on the surface at a given time.
This latter assumption is reliable only for a very diluted solution and is
equivalent to accepting Henry's equation to represent the equilibrium
adsorption isotherm. Two major differences between this approach
and those mentioned earlier are following: (i) according to its
theoretical interpretation, now the k1 constant is independent of the
cin value; (ii) the assumption related to the constant (or nearly
constant) solute concentration in the bulk solution is not obligatory.
All of the previously mentioned theoretical interpretations of the
pseudo-first order equation have in common the assumption that the
overall sorption process is controlled by the rate of adsorption/
desorption processes seen in terms of a chemical reaction on the
adsorbent surface. Regardless of that, Eq. (11) can be also interpreted by
accepting the models in which the kinetics of sorption is determined
mainly by the rate of the diffusional transport of solute. For instance,
Boyd et al. [131] have represented a film diffusion model by the
expression having the same form as Eq. (11) (see also [132] and [133]
for more details). This, as noticed by Ho et al. [1], may create a potential
problems in differentiating between the mechanisms responsible for
the controlling of the sorption process kinetics. Nevertheless, a simple
method can be proposed based on analyzing the theoretical interpreta-
tions of the k1 constant (dependence of its value on the initial solute
concentration, for instance), as, according to the most known theoretical
interpretation of the pseudo-first order equation, the k1 constant
should, in general, be dependent on the initial solute concentration in
the bulk phase. (The only exception is the approach by Liu et al. [115]). In
spite of their mathematical forms, the expressions related to the
external film diffusion model have rather not been considered as
theoretical interpretation for the pseudo-first order equation.
Recently, it has been noticed [48] that the most commonly-applied
expression connected with the IDM (derived for the case of long times
and spherical sorbent particles), written in its differential form (i.e. as
a rate of sorption) is mathematically equivalent to the pseudo-first
order Eq. (10). Then, the theoretical interpretation of the k1 constant
is given by a very simple function of the apparent diffusion coefficient
and the sorbent particle radius as shown in [48]. In spite of identities
of their differential forms, the applicability of both Eq. (10) and IDM
model can be distinguished by considering abscissas of their linear
representation, i.e. the so-called pseudo-first order plots. The values of
these abscissas differ from each other by the constant value equal to ln
(6/π2) ≈ − 0.498. Methods originating from this difference have
already been applied in works [48,52,134].
Many existing theoretical interpretations of the pseudo-first order
model, which often come from accepting completely different models
of sorption kinetics have led us to the concept, according to which the
pseudo-first order equation should be treated as a general formula,
describing sorption kinetics in the systems which are not far from
equilibrium. This statement is in accordance with the results
 W. Plazinski et al. / Advances in Colloid and Interface Science 152 (2009) 2–13
presented in [8,46,48,108,113]. Regardless of that, this can be also
easily justified by considering the general rate equation written in the
following form:
dqðtÞ
= Fðqe ; qðtÞÞ;
dt
in which F is a function of the actual and the equilibrium adsorbed
amounts. Of course any given rate equation can contain many other
parameters, e.g. c, cin, ce. Most of them, however, can be lumped into q
or qe values by using appropriate relations, such as mass balance or the
equilibrium adsorption isotherm equations. Thus, introducing the above
expression has justification. After expanding the right-hand-side of this
equation into the Taylor series around q(t) =qe one obtains:
dqðtÞ 2 3 4 As mentioned, most of the existing papers in which both the
= β1 ðqe −qðtÞÞ + β2 ðqe −qðtÞÞ + β3 ðqe −qðtÞÞ + β4 ðqe −qðtÞÞ + …
dt
where β1, β2, β3 and β4 are some constants. When the system reaches
equilibrium, i.e. q(t) → qe, the first term of the above expansion
becomes a dominating one. This is due to purely mathematical features
of the r.-h.-s. of this expression. The lack of term independent of the
difference (qe −q(t)) at the r.-h.-s. of Eq. (13) is the result of existing
the physical condition that dq(t)/dt = 0 at q(t) = qe. This simple
qualitative evidence is mechanism-independent, nevertheless it can
be easily expanded into the quantitative one by accepting a certain
model of sorption kinetics, as it was shown in [8,48]. Moreover, it can be
proved experimentally: plotting the measured data in the coordinates
ln(qe −q(t)) vs. t one should observe a linearity of such plots for
relatively high adsorption times. Factors hindering the observation of
this effect can be divided into two following groups.
1. The enlarged influence of the random experimental error on the
data presented as ln(qe − q(t)) vs. t in comparison with the
traditional form of their presentation, i.e. q(t) vs. t. It is especially
significant in the range of high adsorption times interesting for us
when the value of the difference (qe − q(t)) is small. Then, even
relatively small contribution of random error to the q(t) data results
in a wide scatter of the (t; ln(qe − q(t))) data points. The reason for
that is high value of the derivative ∂ln(qe − q(t))/∂(qe − q(t)) for
small values of (qe − q(t)) difference. This issue is also discussed
below, in Section 2.3.3.
2. The commonly accepted procedure of treating qe as a best-fit
parameter, leads to the best linear correlation of data by accepting
Eq. (11). Obviously, the range of data correlated in this way may
not necessarily be the same for which the linear behaviour
predicted by Eq. (13) is observable. Thus, the value of qe may not
be the same as the “actual” one, i.e. that corresponding to the
equilibrium adsorption isotherm. Application of this method often
leads to the S-shaped pseudo-first order plots, the examples of
which can be found in [10]. Furthermore, the mentioned
differences between the qe values estimated by accepting different
methods can be seen as a quite common effect as shown in
[11,93,94,121,122], for instance. Another important question is the
problem of choosing proper qe value; it is worth noting that the
adjusted qe value cannot be lower than the maximum measured
value of q(t). On the contrary, the mathematical errors connected
with the logarithm of a negative numbers will appear.
The idea launched above can find a support from the brief analysis
of the experimental data reported in literature. As mentioned,
tendencies of changes in the value of k1 may be opposite depending
on the investigated system. This can be explained by the applicabil-
ities of different kinetic models, based on various mechanisms of the
sorption process, but reducing to the pseudo-first order Eq. (10) when
the system is close to equilibrium.
9
There are significantly less data at disposal when considering the
case of the experimental kinetic isotherms recorded at different
agitation rates and correlated well by the pseudo-first order equation.
However, there exist some exemplary systems [87,100,123] for which
one can observe, as it was possible in the case of the pseudo-second
ð12Þ
equation, that Eq. (11) also does not seem to be much sensitive to the
changes in the kinetic mechanism, influencing the kinetics of sorption.
Another important observation is that the application of linear
regression leads usually to the qe values completely different from the
actual ones, determined experimentally. The differences may be
significant in spite of relatively high quality of the obtained fits which
can be seen in [11,94,121,122], for instance.
2.3.3. Some considerations on the correlation of the experimental data by
using the pseudo-first and the pseudo-second order equations
pseudo-first and the pseudo-second order equations were applied to
ð13Þ analyze the kinetic data report the supremacy of the latter over the
former. The cases when the pseudo-first order equation appears to
correlate the data better are rather rarely met. Two following ex-
planations of that observation can be proposed.
1. The applicability of some physical models which are represented
better by the pseudo-second than by the pseudo-first order
equation (physical factors).
2. Mathematical forms of both considered expressions are at least
partially responsible for differences in the obtained correlations of
data (mathematical factors).
Obviously, both explanations are inseparably connected with each
other in most of the cases (physical factors influence the mathemat-
ical formulation of the model which, in turn, is closer either to the
pseudo-first or to the pseudo-second equation). Apart from this fact,
let us consider the case for which such separation is partially possible,
i.e. the case of the experimental the data measured close to equilibrium
and affected by significant random experimental errors. First, note that
Eq. (11) is then able to exhibit an non-physical behaviour when the
assumed qe value is lower than any of the measured q(t) values. This
situation is very probable when the system is close to equilibrium and
q(t) ≈ qe. Some solutions for that problem may be proposed, such as (i)
accepting the lowest possible qe value which does not generate errors;
(ii) rejecting data points for which q(t) is higher than the estimated qe
or (iii) applying the non-linear form of the pseudo-first order equation,
instead of Eq. (11). Further, the linear representation of the pseudo-
first order Eq. (11) seems to be more sensitive to the influence of
experimental errors in comparison with representation Eq. (6). It
can be proved, that in this latter case the estimated contribution of
errors inherent in t/q(t) data is not dependent on how close to
equilibrium the considered system is. A completely different behav-
iour is observed when the pseudo-first order equation is applied.
Then, errors in ln(qe − q(t)) data are inversely proportional to the
difference (qe − q(t)); thus, the most significant scatter of the exper-
imental ln(qe − q(t)) vs. t data is supposed when q(t) is close to qe.
The results of some illustrative calculations presented here have
rather exemplary character and are incorporated here to elucidate
better the mentioned issues. Complex and exhaustive studies related to
this problem have not been performed yet. An ideal system which obeys
the pseudo-first order behaviour was considered. The pseudo-experi-
mental (t, q(t)) data points were generated by accepting three different
values of qe. Then, random errors were introduced into these data by
applying the Gaussian distribution (see other details in the caption of
Fig. 1). In the next step, the pseudo-experimental points were
transformed to the pseudo-first or the pseudo-second representations,
i.e. (t, q(t)) → (t, ln(qe −q(t))) or (t, q(t)) → (t, t/q(t)), respectively, and
a simple linear regression was performed for them. An exemplary set of
data is presented in Fig. 1.
10 W. Plazinski et al. / Advances in Colloid and Interface Science 152 (2009) 2–13

Fig. 1. The influence of the pseudo-experimental random error on the quality of fits offered by the pseudo-first (panel (B)) and the pseudo-second (panel (C)) order equations. The
original (dimensionless) data (panel (A)) were generated by accepting three values of qe: 0.25 (♦), 0.5 (■) and 0.75 (●). The pseudo-experimental error was incorporated by
accepting normal (Gaussian) distribution with the mean θ(t) (calculated from Eq. (11)) and the standard deviation 0.025. It was assumed that tf is the value of time at which q(t)/
qe = 0.99. The obtained values of correlation coefficients for qe = 0.25, 0.5 and 0.75 are equal to: (B) r2 = 0.821, 0.948 and 0.909; (C) r2 = 0.984, 0.989 and 0.994, respectively.

The results fully confirm the hypothesis stating that not only the
correctness of the accepted model affects the quality of the obtained
data fits but also the experimental error and the range of time at
which the data were recorded. Moreover, it is interesting to note that
the pseudo-second order equation works better than the pseudo-first
order equation despite the fact that this latter expression was applied
for generating the data. Other results of this investigation (data not
shown) lead to the following conclusions. (i) The value of f coefficient,
estimating how close is the system to reach an equilibrium, is very
crucial (f is defined as a ratio of the maximum value of q(t) to qe). For
instance, the mentioned effect is observable when f N 0.9 (for the value
of standard deviation equal to 0.025). (ii) Only when the influence of
errors is relatively small the pseudo-first order equation works better
than the pseudo-second order equation. This is depicted by the low
values of standard deviation (b0.006 for f = 0.99) accepted when
generating (t, q) data points.
Further, the results of application of the pseudo-second order
linear representation Eq. (6) to correlate the experimental kinetic
data confirm that it is able to smooth the random experimental errors
quite well, i.e. the random noise is significantly reduced in com-
parison to the traditional q(t) vs. t coordinates (contrary to the case
of the pseudo-first order equation). It can be observed in [135], for
instance.
2.3.4. The Elovich equation
The Elovich equation is the rate equation, proposed by Roginsky
and Zeldovich [136] in 1934 to describe the kinetics of adsorption of
carbon monoxide on manganese dioxide. Its integral form reads:
1
qðtÞ = lnð1 + ABtÞ
B 2.4. Other models
a generalized form of Eq. (14) by accepting the SRT approach and the
model of a strongly heterogeneous surface [51]:
(sffiffiffiffiffiffi " sffiffiffiffiffiffiffiffiffiffiffiffiffi! #)
1 A A pffiffiffiffiffiffiffiffiffi
qðtÞ = ln tanh arccosh + AA2 Bt ð15Þ
B A2 A−A2
where the inequality A N A2 has to be fulfilled. The behaviour of
this expression is fully physical for the longer adsorption times, i.e.
q(t → ∞) = qe.
There exist many different theoretical interpretations of the
Elovich equation. Most of them are directly connected with the
assumption of strong heterogeneity of the sorbent surface. An
exhaustive analysis of existing rationalizations for the Elovich
equation found in literature and related to the case of heterogeneous
surfaces can be found in the review by Rudzinski and Panczyk [143].
Recently, it has been quantitatively proved that in spite of their
different mathematical form, both the pseudo-second order and the
Elovich equations exhibit essentially identical behaviour when
considering the values of fractional surface coverages lower than
about 0.7. The relations between the constants appearing in both
these expression are complicated and simple analytical formulae can
be found only in special cases (see [51] for more details). Moreover,
the pseudo-second order equation is practically identical with the
“generalized-Elovich” Eq. (15) up to 0.9 of the fractional surface
coverage. These observations lead to the conclusion that many of the
existing interpretations of the pseudo-second order equation may, in
some cases, relate also to the Elovich equation.
ð14Þ

in which A and B are the constants. A simple form of this equation
triggered its wide use to describe the sorption of pollutants from
aqueous solutions in recent years [137–142]. Eq. (14) is often
connected with the linear representation based on the plot of q as a
function of ln(t + 1/AB). With a correctly chosen value of AB, the
experimental data should give a straight line. When the value of AB is
large in comparison to unity, then also the q vs. ln t plot should have a
linear character. One can easily observe the non-physical behaviour of
Eq. (14) for longer adsorption times, i.e. q(t → ∞) = ∞. According to
most of the theoretical interpretations of the Elovich equation, this is
due to neglecting the rate of simultaneously occurring desorption.
Thus, in practice, the applicability of the Elovich equation is restricted
to the initial times of sorption process, when the system is relatively
far from equilibrium. Rudzinski and Plazinski have recently proposed
Brouers and Sotolongo-Costa derived a universal function, which,
in particular, can be used for description of sorption kinetics of the
pollutants dissolved in the liquid phase onto solid surfaces [144]. The
generalized “fractal kinetics” approach was applied for this purpose.
The pseudo-(n,α) equation has been introduced in the following form:
n o
n−1 α − 1
qðtÞ = qe 1−½1 + qe ðn−1ÞKn;α t  n−1 ð16Þ
where α is so-called fractional time index, n is a non-integer
adsorption reaction order and Kα, n is a constant. The above expression
reduces to the pseudo-first order kinetics when n = 1 and α = 1 and
to the pseudo-second order kinetics for when n = 2 and α = 1. In the
case of n = 1 the asymptotical relation can be obtained.
 W. Plazinski et al. / Advances in Colloid and Interface Science 152 (2009) 2–13
Generalization of the pseudo-first order equation to a series of
parallel first order processes was proposed and called a multi-exponent
equation [145,146]. It reads:
" #
N
∑i = 1 ai expð−ki tÞ
qðtÞ = qe 1−
N
∑i = 1 ai
where N is the number of terms and ai describes the share of ith
process characterized by the rate coefficient ki. For N = 1 one obtains
the expression identical with the integral form of the pseudo-first
order equation. It is interesting to note that this equation may be also
considered as an approximate formula describing many different
kinetic mechanisms, such as diffusion driven sorption kinetic process
in a complex pore system (containing different kinds of pores) or in
the case of sorbent having particles of various sizes. When assuming
the discrete adsorption energy distribution, it may also describe
sorption kinetics on energetically heterogeneous surfaces [146].
Aharoni and Sparks [147] proposed an empirical equation called
the apparent first-order equation. Its integral form can be represented
as follows:
qðtÞ = qe ½1−β expð−k1 tÞ
where β is an adjustable parameter. This additional constant causes
significant improvement of the correlation of the measured data in
comparison to the classical pseudo first-order model. The differential
form of Eq. (18) is identical with the differential form of the pseudo-
first order Eq. (10). The difference lies in the boundary condition
which has to be applied; in the case of Eq. (18) one has to assume that
q(t = 0) = qe(1 − β), which, for β ≠ 1, does not correspond to the
most common experimental situation and leads to non-physical
results for β N 1. This may suggest a limited range of applicability of
Eq. (18). Moreover, for a special case when β = 6/π2, Eq. (18) reduces
to the expression derived by using the homogeneous pore diffusion
model (IDM), valid for long adsorption times [13].
The first order reversible model was introduced on the assumption
that the sorption process may be considered as a first order reversible
reaction [148]. Equation corresponding to this model can be
expressed in its traditional form as:


c −c
ln 1− in = −kBV t
cin −ce
where kBV is a constant, meaning of which is explained in [148]. The
above expression can be transformed into the form mathematically
equivalent to the pseudo-first order Eq. (11). The reason is the
proportionality of the differences (cin − c) and (cin − ce) to the q and
qe values, respectively. The only difference is connected with the
predicted values of abscissas in linear plots (11) and (19). Thus,
although the comparisons between the applicabilities of these two
expressions are known in literature, it is hard to expect any significant
differences between their behaviour. This can be seen in papers [149–
151]. The approach by Bhattacharya and Venkobachar assumes that
the rates of adsorption and desorption are proportional to the sorbate
concentrations in the bulk solution and on the adsorbent surface,
respectively. However, the effect of saturation of the surface is not
considered, thus, this approach differs from the classical Langmuir
kinetic model in which the limited adsorbent capacity is assumed.
Similar to this approach is that put forward by Liu et al. [115] in order
to propose a theoretical background for the pseudo first-order
equation. Very recently this model has been extended by Shi et al.
[152] who assumed that Zn adsorption/desorption on/from soil is
controlled by the reversible reaction with two groups of sites, for
which the adsorption and the desorption rate coefficients have
different values. Examples of the application of the first order
reversible reaction model can be found in [149–153].
11
An expression related to Eq. (19) was proposed by Natarajan and
Khalaf as cited by Pandey et al. [154]. It can be written in the following
form to stress its similarity to Eq. (19):


c −c
ð17Þ ln 1− in = −kNK t: ð20Þ
cin
Moreover, similarity to the pseudo-first equation can be noticed. The
above expression can be transformed to the linear form, analogical to
Eq. (11), in which qe is replaced by qtot, i.e. by the total amount of
solute present in the system. Nevertheless, as the qtot value is always
known, these two models can be easily distinguished.
Bahr and Rubin [155] proposed the mathematical formulation for
the model of transport in porous media, involving both the rate of
solute diffusion in pores and the rate of surface reaction. Their
approach includes the separation of an additional “kinetically
influenced” term, responsible for the rate of surface reaction and
present in PDE, defining the diffusional transport. The reversible first
order rate equation was considered as the expression describing the
kinetics of surface reaction. According to our present knowledge, this
approach has never been widely applied for description of the kinetics
ð18Þ of pollutants sorption at solid/solution interfaces.
Koopal and Avena [156] proposed a simple model taking into
account two main kinetic steps: (i) transport of molecules toward the
surface expressed in terms of diffusion through the liquid film (see
[133]) and (ii) the rate of adsorption (“attachment”) on the surface.
The additional assumption is that the flux of molecules through the
diffusion layer is equal to the rate of their adsorption on the surface.
This leads to a steady-state situation and, contrary to a more general
approaches, let arrive at much simpler kinetic expressions. Koopal and
Avena derived a general expression, by accepting that (i) the rate of
adsorption is proportional to the solute concentration in the
subsurface region (cs) and a function of q and (ii) the rate of desorption
is a function of q. The overall rate of sorption is then given by:


dqðtÞ ks κ1 ϕðqðtÞÞ κ ψðqðtÞÞ
= c− 2
dt κ1 ϕðqðtÞÞ + ks κ1 ϕðqðtÞÞ
where ϕ(q(t)) and ψ(q(t)) are the functions of q(t), expressing the
rate of adsorption and desorption, respectively, κ1 and κ2 are the
constants and ks is the rate coefficient of solute transport in the
ð19Þ
boundary layer. The main advantages of this approach are following:
(i) it does not consider any specific surface reaction rate model, thus,
it has a very general character but can easily be adopted to describe a
given system when assuming certain forms of ϕ(q(t)) and ψ(q(t))
functions; (ii) as claimed by the authors, it can be applied for
description of sorption kinetics of any substance: a molecule, an ion or
a colloid particle; (iii) it can be further generalized for the case of
adsorption of charged species on a charged surface, involving different
aspects of electrostatic interactions [156].
Other kinetic models (or equations) which can be used for
description of the sorption kinetics and which are not discussed
here in details are: a reversible second-order rate expression by
Dzombak and Morel [32], model by Gosset at al., describing the
kinetics of metal removal by peat [157], Langmuir–Hinshelwood
kinetic model [158,159], Freundlich kinetic equation [160], modified
pseudo-first order model [161] and the Ritchie equation, introduced
originally for the adsorption of gases on solids [162].
3. Concluding remarks
Predicting the rate at which pollutants (dyes, heavy meals, phenolic
compounds) are removed from aqueous solutions by using various types
of low-cost materials is one of the crucial factors which influences the
effectiveness of the sorption process. A great number of papers report the
experimental kinetic isotherms of sorption measured in many systems
12 W. Plazinski et al. / Advances in Colloid and Interface Science 152 (2009) 2–13

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