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Langmuir 2008, 24, 5393-5399 5393

Kinetics of Solute Adsorption at Solid/Aqueous Interfaces: Searching


for the Theoretical Background of the Modified Pseudo-First-Order
Kinetic Equation
Wadysaw Rudzinski*,, and Wojciech Plazinski
Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek 8,
30-239 Cracow, Poland, and Department of Theoretical Chemistry, Faculty of Chemistry, Uniwersytet
Marii Curie-Skodowskiej, pl. M. Curie-Skodowskiej 3, 20-031 Lublin, Poland

ReceiVed January 7, 2008. ReVised Manuscript ReceiVed February 11, 2008

It is shown that the modified pseudo-first-order (MPFO) kinetic equation proposed recently by Yang and Al-Duri
simulates well the behavior of the kinetics governed by the rate of surface reaction and described by our general kinetic
equation, based on the statistical rate theory. The linear representation with respect to time, offered by the MPFO
equation seems to be a convenient tool for distinguishing between the surface reaction and the diffusional kinetics.
Also, a method of distinguishing between the surface reaction and the intraparticle diffusion model based on analyzing
the initial kinetic isotherms of sorption is proposed. The applicability of these procedures is demonstrated by the
analysis of adsorption kinetics of the reactive yellow dye onto an activated carbon.

Introduction of time. Such a simple linear representation was a convenient


Adsorption at solid/solution interfaces is of crucial importance and therefore very attractive tool to correlate the experimental
for life on our planet, a large variety of industrial processes, and kinetic isotherms.
a variety of processes in environmental protection. In the case Common use of the Lagergren equation also led to discovery
of the environmental processes, adsorption is an efficient and of various discrepancies between predicted and observed
economically feasible process for the treatment of wastewater behaviors of the kinetic adsorption isotherms. Typical observa-
containing chemically stable pollutants such as dyes or poisoning tions were follows:
ions, for instance. Here the solution and the sorbent are brought The Lagergren kinetic equation was not able to correlate the
into contact for a limited period of time, so not only the equilibrium whole kinetic isotherm, i.e., the kinetic data monitored at both
features of such solid/solution systems but also their evolution short and long adsorption times.
in time are of fundamental importance for the sorption technique The linear Lagergren plot could commonly correlate well
to be an effective process for wastewater treatment. So it is no adsorption data monitored at longer adsorption times when a
surprise that so many papers were published on the kinetics of system was not far from equilibrium but failed to describe the
sorption at solid/solution interfaces. It is very impressive to note initial region corresponding to short adsorption times.
that the first ever theoretical paper on adsorption was that The following three hypotheses have been considered to explain
proposing a theoretical expression to describe the kinetics of these typical deviations:
adsorption at the solid/solution interface. This was the paper by (1) Monitored kinetics is a multistep process in which switching
Lagergren, published in 1898 in which the kinetic equation, takes place from one kinetic mechanism to another.
commonly called the pseudo-first-order equation was proposed.1
However, even more impressive is the fact that, after more than (2) The monitored kinetic isotherm corresponds to various
one century, this equation is still one of the most popular and processes occurring simultaneously and one of them dominates
widely used equations to correlate the experimentally monitored in a certain region of times.
kinetic isotherms of adsorption. At the same time, this kinetic (3) The applied Lagergren equation is a lumped form of a
equation has remained an essentially empirical one until very more adequate but also sophisticated equation which eventually
recently. It was Azizian2 who proposed its first derivation based might correlate kinetic data better.
on the classical fundamental TAAD approach (theory of activated The scientists accepting the first of the above-mentioned
adsorption/desorption), whereas Rudzinski and Plazinski3 derived hypotheses applied different Lagergren plots to correlate different
it for the first time by applying the new fundamental SRT approach parts of the monitored kinetic isotherm. While following the
to the kinetics of interfacial transport (statistical rate theory). second hypothesis, the scientists considered the whole kinetic
The Lagergren pseudo-first-order equation leads to the conclusions process as composed of kinetic processes occurring on different
that the logarithm of the difference between the equilibrium parts of a solid surface. In response to the third hypothesis, a
and the monitored adsorbed amount should be a linear function variety of other kinetic equations was proposed to correlate
experimental data. Some of them were purely empirical and
* Corresponding author, rudzinsk@hermes.umcs.lublin.pl. intuitively related to the kinetic mechanism when the adsorption

Institute of Catalysis and Surface Chemistry, Polish Academy of kinetics is governed by the rate of surface reaction. These have
Sciences.

Department of Theoretical Chemistry, Faculty of Chemistry, Uni- been the Elovich and the pseudo-second-order kinetic isotherms,
wersytet Marii Curie-Skodowskiej. for instance. Also, there have been proposed equations corre-
(1) Lagergren, S. Kungliga SVenska Vetenskapsakademiens. Handlingar 1898, sponding to the kinetic mechanism when the adsorption kinetics
24, 1.
(2) Azizian, S. J. Colloid Interface Sci. 2004, 276, 47. is governed by the rate of intraparticle diffusion. The square-root
(3) Rudzinski, W.; Plazinski, W J. Phys. Chem. B 2006, 110, 16514. dependence of the adsorbed amount on time generally has been
10.1021/la8000448 CCC: $40.75 2008 American Chemical Society
Published on Web 04/22/2008
5394 Langmuir, Vol. 24, No. 10, 2008 Rudzinski and Plazinski

believed to be a solid check that the adsorption kinetics is in the bulk phase (b) and the phase adsorbed on the surface (a).
controlled by the intraparticle diffusion. Further, k and T denote the Boltzmann constant and absolute
Meanwhile, recently it has been shown by Rudzinski and temperature, as usual. For the bulk phase the following expression
Plazinski that such a square-root dependence in the initial region is accepted
of adsorption times may also be typical of kinetics controlled by
the rate of surface reaction. They arrived at this conclusion by b ) b + kT ln c (3)
accepting the popular Langmuir model of adsorption and applying
the new fundamental SRT approach to adsorption kinetics.4 While where c is the concentration of the solute in the bulk phase. The
applying that new SRT approach, Rudzinski and Plazinski5 have expression for a is derived from the equilibrium adsorption
also shown that the Lagergren equation is the limiting form of isotherm. This is because one fundamental assumption of the
the kinetic isotherm corresponding to the Langmuir model of SRT approach is that the adsorbed phase is in a quasi-equilibrium.
adsorption, when the system is not far from equilibrium. It means that all the correlation functions are the same as they
Therefore, we may summarize the present situation as follows. would be at equilibrium at the same surface coverage.
Using the new fundamental SRT approach to adsorption kinetics, So let us consider the popular Langmuir model of adsorption
we have arrived at much more adequate and accurate kinetic and its corresponding adsorption isotherm:
equations to represent the kinetics which is governed by the rate of KLce
surface reactions. That more adequate but also more complicated e ) (4)
equation reduces to the square-root dependence on time for short 1 + KLce
adsorption times and to the Lagergren equation for long times. These In eq 4 KL is the temperature-dependent Langmuir constant
simple equations are very attractive for being used to correlate whereas the subscript e refers to the equilibrium conditions.
experimental data, but their use is limited to short and long adsorption Assuming also that the bulk/surface exchange rate is proportional
times, respectively. Here we are going to show that the new modified to the frequency of the collisions of the solute molecules with
pseudo-first-order kinetic equation proposed recently on an empirical the available fraction of surface, one arrives at the following rate
basis by Yang and Al-Duri6 reproduces very well the exact solution equation
of our kinetic equation in the whole region of adsorption times. It
means that this empirical equation reproduces well the behavior of
our theoretical kinetic isotherm in the whole region: from short
initial times to long times when the system is close to equilibrium.
d
dt
) Klsce(1 - e) KLc
[
1-

-
1
KLc 1 - ] (5)

At the same time the simplicity of that empirical equation makes where Kls ) Klsce(1 - e). One can also take into account the
it a very attractive and convenient tool to correlate experimental set of technical parameters which characterize the conditions
data. The theoretical background of this modified pseudo-first-order under which the kinetic experiment is carried out, i.e., the volume
equation will be discussed, and its applicability will be presented of solution (V), the solute initial concentration (cin), and the
by an appropriate analysis of some experimental data reported in monolayer capacity (Nm) which is connected with the applied
the literature. mass of adsorbent. Using the notation

Theory
The famous Lagergren kinetic equation is usually written as
{ ) cinV Nm
) K lst ) Klsce(1 - e)t
(6)

follows1 and accepting relation 4 we can transform eq 5 to the following


form
d
) k1(e - )
d e( - )(1 - ) ( - e)(1 - e)
(1)
dt ) - (7)
where (t) is the monitored fractional surface coverage, e is that
d ( - e)(1 - e) e( - )(1 - )
surface coverage at equilibrium, i.e. Now, let us write for comparison the rate equation offered by
the classical TAAD approach
e ) lim (t)
tf
d
) Kac(1 - ) - Kd (8)
whereas k1 is a constant. The physical meaning of that constant dt
remained unexplained for more than one century because the in which Ka and Kd are the temperature-dependent constants
Lagergren equation has remained essentially an empirical one such that KL ) Ka/Kd Further, let us consider the limiting features
until very recently. Its first theoretical background was given by of these equations when t f and t f 0, respectively. For the
Azizian2 in 2004 and was based on the classical TAAD approach case t f , we expand the derivatives d/dt (or d/d) into their
to adsorption kinetics. Two years later Rudzinski and Plazinski Taylor series around ) e. Then from the TAAD equation (8)
proposed its theoretical derivation based on the new fundamental we obtain
SRT approach.3 Following that approach7

[ ( ) ( )]
d
d b - a a - b lim ) (Kace + Kd)(e - ) (9)
) Kls exp - exp (2) fe dt
dt kT kT
whereas the SRT equation 7 leads to the following expression:
where Kls is the rate of adsorption/desorption at equilibrium,
whereas b and a are the chemical potentials of adsorbate (solute) d 2( - e2)
lim ) ( - ) + O[e - ]2 (10)
fe d e( - e)(1 - e) e
(4) Rudzinski, W.; Panczyk, T.; Plazinski, W. J. Phys. Chem. B 2005, 109,
21868. Integration of both eqs 9 and 10 with the boundary condition
(5) Rudzinski, W.; Plazinski, W. J. Phys. Chem. C 2007, 111, 15100.
(6) Yang, X.; Al-Duri, B. J. Colloid Interface Sci. 2005, 287, 25. (t ) 0) ) 0 yields the following integral form of the Lagergren
(7) Ward, C. A.; Findlay, R. D.; Rizk, M. J. Chem. Phys. 1982, 76, 5599. equation
The Modified Pseudo-First-Order Kinetic Equation Langmuir, Vol. 24, No. 10, 2008 5395

ln(e - ) ) ln e - k1t (11) (t) ) Kact ) Kacint (20)


The constant k1 is defined in the case of eq 9 as It means that the plot vs t should, at t f 0, become linear with
tangent being a linear function of the initial solute concentration.
k1 ) Kace + Kd (12) One arrives at a dramatically different conclusion when the new
whereas in the case of eq 10: SRT approach is applied to represent the adsorption kinetics
governed by the rate of surface reactions.4
2Klsce( - e2) Let us remark that then, in the limit t f 0, both the diffusional
k1 ) (13) kinetic model and the surface reaction kinetic model predict the
e( - e)
same square-root dependence on time of the surface coverage.
Now let us note that also the popular intraparticle diffusion In the case of the surface reaction kinetic model, from eqs 4 and
model leads to the Lagergren equation in the limit f e Let 5 we obtain:
us consider for that purpose the most widely used mathematical
expression corresponding to this model8 d 1
lim ) Klsce(1 - e)KLcin (21)
tf0 dt

( )

Dn22 Its integration with the boundary condition (t ) 0) ) 0 yields

e
6
)1- 2
1
n)1 n2

exp -
r2
t (14)
) 2Klsce(1 - e)KLcint ) 2Klscinet (22)
where D is the intraparticle diffusivity and r is the particle radius.
Thus, at t f 0, tangent of this linear plot is always a linear
At long times, when f e, eq 14 reduces to the Lagergren-like
function of the expression (cine)1/2. It also means that the square
expression
root dependence on time of the monitored surface coverage
(t1/2) cannot be treated as a proof that the kinetics of sorption
D2 6
ln(e - ) ) - t + ln e + ln 2 (15) is governed by the rate of intraparticle diffusion.
r2 One should, however, remember that eq 21 does not apply at
which suggests that adjusting properly the value of e should extremely low times and surface concentrations when the
make the experimentally determined ln(e - ) data a linear predicted rate of adsorption is higher than the flux of solute
function of time. The tangent of such a linear plot will be equal molecules to the surface. For such extreme low times and surface
to -D2/r2 and its abscissa to (ln e + ln (6/2)). For the purpose concentrations a more complicated procedure is to be applied.9
of our further consideration, it is essential to emphasize that the Nevertheless, drawing such double-logarithmic plots may be a
value of e parameter determined from the abscissa should be source of interesting information concerning the first kinetic
equal to that making the plot ln(e - ) a linear function of time. process. Provided that it could be governed by the rate of
The important difference lies in the theoretical interpretation of intraparticle diffusion, as follows from eq 18, the tangent should
the abscissas in eq 15 (D) be a linearly increasing function of e. Thus, while considering
the first region of small adsorption times and surface coverages,
6 we face a similar situation to that when the system is close to
D ) ln e + ln (16) equilibrium. Namely, both the diffusional and the surface reaction
2
kinetics are represented by the same kind of theoretical expression,
and in eq 11 (L) and the difference lies only in the interpretation of their kinetic
coefficients. In the case of the diffusional kinetics the tangent
L ) ln e (17)
of the linear plot vs t1/2 will be a linear function of the equilibrium
It has been frequently emphasized in literature that for short surface coverage e, whereas in the case of the surface reaction
times, when the fractional uptake f e is less than around 0.3, model, it will be a more complicated function suggested by eq
eq 14 reduces practically to the following one 22.
Therefore, we may summarize the results of our considerations

 Dt
6e as follows:
) (18) In the initial region of short adsorption times the square-root
r
dependence of the adsorbed amount on time is the lumped
As we have already stated, the Lagergren equation is the expression valid for both the surface reaction and the diffusional
limiting form of both diffusional and the surface reaction kinetic kinetic models.
equations at long adsorption times when the system approaches For both kinetic models, the Lagergren expression is the
equilibrium. In the case of the surface reaction kinetic model, lumped form of appropriate, more adequate, and sophisticated
this conclusion was drawn by applying both the classical TAAD expressions, describing the rate of adsorption when the system
approach and the new fundamental SRT approach to adsorption approaches equilibrium.
kinetics. A somewhat different situation is faced when these two Distinguishing between these two kinetic models needs a
approaches are applied to predict the limiting form of the kinetic careful analysis of the behavior of the coefficients in these lumped
equations for short adsorption times, i.e., when t f 0. expressions.
While applying the classical TAAD approach to adsorption The square-root dependence on time or the Lagergren plots
kinetics, from eq 8, one arrives at the following limiting form have been frequently used to correlate experimental kinetic
of the surface reaction kinetic equation: isotherms. However, as the theoretical background of these
lumped relations has remained unclear until recently, both their
d
lim ) Kac (19) successful applications and the observed deviations could not
tf0 dt receive solid interpretation. It seems that the main source of their
Its integration with the boundary condition (t ) 0) ) 0 yields popularity and common use were the simple correlations of

(8) Suzuki, M. Adsorption Engineering; Kodansha: Tokyo, 1990. (9) Panczyk, T. Phys. Chem. Chem. Phys. 2006, 8, 3782.
5396 Langmuir, Vol. 24, No. 10, 2008 Rudzinski and Plazinski

experimental data offered by these lumped expressions. They


made their use very attractive for many researchers. So no surprise
that various attempts were made to modify these expressions to
increase the range of their applicability. Here we would like to
draw the readers attention to some very reasonable modification
proposed by Yang and Al-Duri6 on an empirical basis. Very
recently these authors proposed the following modification of
the Lagergren equation

d e
) KM (e - ) (23)
dt
where KM is a constant. We will call it the MPFO (modified
pseudo-first-order) equation. Its integration with the boundary
condition (t ) 0) ) 0 yields

ln(e - ) + ) ln e - KMt (24)
e
Let us remark that eq 23 is a hybrid between the square-root
dependence when f 0 and the Lagergren dependence when
f e. This is because
d 1
lim ) KMe2 (25)
tf0 dt
Figure 1. The comparison of the theoretical kinetic adsorption
When compared to eq 21 this would imply that in the limit isotherms calculated from the SRT equation (7) for three different
f 0 the coefficient KM has the following interpretation values of the equilibrium surface coverage: e ) 0.25 ()), e ) 0.5 (0),
and e ) 0.75 (O) with their approximate values calculated from the
Klscin MPFO equation (24) (s). In the case of panel (B) the linear representation,
KM ) (26) suggested by eq 24, was used. All calculations were performed for
e ) 1.1e.
Then in the limit f e, from eq 23 we obtain
d
lim ) KM(e - ) + O[e - ]2 (27)
fe dt
By comparison with eq 10 in the limit f e, the interpretation
of KM is identical with that of k1 coefficient given by eq 13.
The MPFO kinetic equation offers a very attractive simple
way of correlating experimental data. Now we are going to show
that this hybrid between the square-root and the Lagergren
dependence simulates fairly well the behavior of the fully exact
function (t) in eq 7 also in the mediate region between short
and long adsorption times. We performed some simple model
investigations, plotting kinetic isotherms calculated from eqs 7
and 24 as functions of the reduced time /0.9, where 0.9 is the
time when the surface coverage reaches the value ) 0.9e.
The dimensionless time for the MPFO equation is defined as )
KMt. The results are shown in Figures 1 and 2.
Looking through Figures 1 and 2, we can see a quite good
agreement between the theoretical kinetics isotherms predicted
by the MPFO equation (24) and the SRT expression (7). The
accuracy of MPFO equation (24) (treated as an approximation
of the exact equation (7)) is increasing while the parameter is
increasing. Then we have also found that when the value of
Figure 2. The comparison of the theoretical kinetic adsorption isotherms
is very high in comparison to e, one can observe the reverse calculated from the SRT equation (7) and from the MPFO equation (24)
behavior, i.e., a decreasing accuracy of approximation (24). (s). All calculations were performed for ) 2e. All the notations are
However, the situation that . e is highly nontypical when the same as in Figure 1.
considering the real kinetic experiments. This is because such
high values of parameters mean that no significant changes in drawn that the MPFO equation reproduces the SRT expression
the solute concentration will be observed in the course of (7) best for the low values of e.
experiment. From the point of view of a successful application Then, we also decided to compare the behavior of theoretical
of an adsorption process, the highly desirable situation is that kinetic isotherms calculated from the full form of the IDM
e, i.e., when almost all the sorbate is removed from the equation (14) with those calculated from the MPFO equation
solution. An inspection into literature seems to suggest that the (24). Now, the dimensionless time for the IDM equation is defined
most typical cases are these when lies between these two values as ) D2t/r2. The results are shown in Figure 3. One can see
) 1.1e and ) 2e, accepted in our model calculations there a somewhat systematically worse agreement than that in
presented in Figures 1 and 2. A general conclusion can also be Figure 2. It seems, however, that the MPFO empirical equation
The Modified Pseudo-First-Order Kinetic Equation Langmuir, Vol. 24, No. 10, 2008 5397

Figure 4. The experimental kinetic isotherms for the RY/F-400 system


reported by Yang and Al-Duri, measured at the four initial solute
concentrations: 35.4 mg/L (O), 60.3 mg/L (0), 87.2 mg/L (4), and 131
mg/L ()). The solid lines (s) are the linear fits with abscissa values set
as zero.

Figure 3. The comparison of the theoretical kinetic adsorption isotherms


calculated from the IDM equation (14) and from the MPFO equation
(24) (s). All the notations are the same as in Figure 1.

may simulate also the behavior of the kinetics governed by


intraparticle diffusion. The general conclusion, therefore, is that
distinguishing between these two kinetic mechanisms will be a
difficult problem. Figure 5. The tangents of the linear plots presented in Figure 4, plotted
in the coordinates suggested by the IDM equation (18) (b) or by the
Analysis of Experimental Data SRT equation (22) (9) to describe adsorption kinetics in the initial
region of surface coverages.
In this section we introduce the following additional notation:
N(t) denotes the amount adsorbed as a function of time, while Both the SRT approach and the IDM equation (18) predict
Ne is the amount adsorbed at equilibrium. As an example we that at the initial short times the linear dependence of amount
present here the analysis of the experimental data published in adsorbed on the square root of time is to be observed. Thus, in
2001 by Yang and Al-Duri10 on sorption of reactive dyes onto the first step of analysis, we fitted the initial part of measured
Filtrasorb-400 activated carbon. All details related to the kinetic data by the linear through origin function which
experimental procedures and the adsorption system description corresponds to the SRT equation (22) and the IDM simplified
can be found in their original paper. We have chosen the reactive equation (18). We took into account only those data points for
yellow/activated carbon (RY/F-400) adsorption system for our which the relation N(t) e Ne/3 was fulfilled, as, according to the
further analysis. The adsorption kinetics for this system was simple model investigation, this is the limit of the applicability
studied at four initial solute concentrations, as can bee seen in of eq 18. The results are shown in Figure 4.
Figure 5 in the original paper. The kinetic experiments were Let us denote the tangents of these linear fits, presented in
accompanied by the measurements of the equilibrium adsorption Figure 4, as R. According to the theories presented in the previous
isotherm. Also, the value of monolayer capacity was determined, section, the values of these tangents should be (1) either a linear
which allows presentation of Ne values as e. Yang and Al-Duri function of Ne, suggested by the IDM and eq 18 or (2) a linear
found that the empirical Fritz-Schluender isotherm equation function of (cinNe)1/2, suggested by the SRT equation (22).
correlates best the equilibrium adsorption data. The determined
In both cases the values of the abscissas of these linear fits
parameters of this equation as well as the description of the
should be again set as zero, which is due to the physical meaning
technical conditions of the investigated system at which the
and the mathematical form of eqs 18 and 22. Figure 5 shows the
experiments was carried out (mass of sorbent, volume of solution
results of our investigation.
and initial sorbate concentrations) allow us to (1) calculate the
Ne value corresponding to a given initial solute concentration As one can see in Figure 5, the proposed analysis can hardly
and (2) transform the measured data into the N(t) vs t form. answer the question whether the SRT approach or IDM is more
Then it is to be emphasized that the kinetic and the equilibrium appropriate to represent the initial sorption kinetics.
adsorption isotherms were measured for different ranges of surface Therefore, in the next step we used full forms of both the IDM
coverage. The Fritz-Schluender empirical equation was used to equation (14) and the SRT equation (5) to fit all the experimental
generate the values of the equilibrium adsorption isotherm in the data points, by adjusting the parameters D2/r2 and Kls,
region of the surface coverage at which the kinetics was respectively. The Langmuir isotherm equation (4) was used to
experimentally monitored. But then we assumed, of course, that calculate the values of KL for each pair of (ce, e). The values
the Langmuir model can be accepted in the range of surface of these best-fit parameters are collected in Table 1, and the
coverages where the sorption kinetics were measured. goodness of the fits is presented in Figure 6.
Looking into Figure 6 one may conclude that both IDM and
(10) Yang, X.; Al-Duri, B. Chem. Eng. J. 2001, 83, 15. SRT kinetic models offer a similar fit of experimental data. But
5398 Langmuir, Vol. 24, No. 10, 2008 Rudzinski and Plazinski

Table 1. The Values of the Best-Fit Parameters Used to Fit the


Kinetic Isotherms Measured by Yang and Al-Duria
cin (mg/L) Ne (mg) Kls (L/(min/mg)) D2/r2 (1/min) Nmax/Ne
35.4 83.9 3.70 10-5 2.55 10-3 0.99
60.3 145.2 3.08 10-5 1.57 10-3 0.98
87.2 211.6 2.51 10-5 9.40 10-3 0.89
131 319.3 2.59 10-5 7.89 10-3 0.86
a
The obtained agreement between theory and experiment is shown in
Figure 6. Nmax is the maximum value of N(t) monitored during the experiment.

Figure 7. The MPFO linear representation (24) of the experimental


kinetic data and their SRT approximation shown in Figure 6 and obtained
by using the Kls parameters collected in Table 1. All notations as in
Figure 4.

Figure 6. The agreement between the experimental kinetic isotherms


and the theoretical isotherms calculated from the IDM equation (14) and
the SRT equation (5) by using the best-fit parameters collected in Table
1. All notations as in Figure 4.

then the inspection of Table 1 seems to advocate for the SRT


kinetic model. Namely, the Kls parameter values are less dependent Figure 8. (A) The MPFO linear representation (24) of those experimental
on cin than those of the D2/r2 parameter. Strong changes in the data points for which the condition N(t) < 0.66 Ne is fulfilled and (B)
the Lagergren plots (15) for the second parts of kinetic isotherms for
values of the parameters which should be constant do not speak which N(t) > 0.66 Ne. All notations as in Figure 4.
in favor of an underlying physical model. In particular, very
close to each other are the two values Kls ) 2.51 10-5 L/(mg/ into Figure 6, it is difficult to judge whether or when switching
min) and Kls ) 2.59 10-5 L/(mg/min), corresponding to the takes place from one kinetic mechanism to another.
two highest initial concentrations: cin ) 87.2 mg/L and cin ) 131 A different picture emerges on the MPFO linear plot ln(Ne -
mg/L. So, it seems important to notice that these two kinetic N(t)) + N(t)/Ne vs t, as shown in Figure 7. However, there is also
isotherms lie in a region which is further from equilibrium than another important fact relating to the presented MPFO linear
the two others. This is depicted by the values of Nmax/Ne collected representations of experimental data. Namely, these representa-
in Table 1. Therefore, one may conclude that the two kinetic tions, presented in Figure 7 were obtained by using the
isotherms corresponding to the two highest initial concentrations experimentally determined (i.e., by using the parameters of
lie in the kinetic region where the SRT model applies better. The Fritz-Schluender isotherm) Ne values. A much better linearity
other two kinetic isotherms lie in a region which is closer to than those presented in Figure 7 can be obtained when treating
equilibrium, so they may be also influenced by another kinetic Ne as the best-fit parameter. Nevertheless, accepting such a
mechanism which is typical of the systems which are close to procedure in the case of the adsorption system investigated here
equilibrium. That kinetic mechanism has been identified in our leads us to higher Ne values than those obtained from the
previous paper as the one controlled by the rate of intraparticle equilibrium adsorption isotherm. These higher Ne values were
diffusion.5 Thus, also in the case of the adsorption system next used by us to calculate the corresponding ce values. It
investigated here by us, we arrive at the same picture of adsorption appeared that this procedure led us to unphysical values of
kinetics. equilibrium solute concentration: ce < 0. Thus, the conclusion
In the initial region, far from equilibrium, the kinetics is can be drawn that only experimentally determined values of Ne
governed by the rate of surface reactions. should be used when the data transformation N(t) f ln(Ne -
When the system approaches equilibrium, switching takes place N(t)) + N(t)/Ne is applied.
from the surface reaction kinetics to that governed by the Looking into Figure 7 one can observe a highly linear trend
intraparticle diffusion. in the behavior of the experimental data from very short times,
Now we are going to show that the MPFO linear representation up to those corresponding to roughly two-thirds of the equilibrium
(24) may serve as a test more sensitive to the changing kinetic surface coverage. This would mean that this is the coverage at
mechanism than the usual N(t) vs t representation. Indeed, looking which switching takes place from the surface reaction to the
The Modified Pseudo-First-Order Kinetic Equation Langmuir, Vol. 24, No. 10, 2008 5399

Table 2. The Values of the Tangents (KM, D2/r2) and of the Abscissas of Their Linear Plots (Data Regressions) Presented in Figure 8
MPFO plot Lagergren plot
cin (mg/L) ln Ne (SRT) ln Ne + ln(6/ ) (IDM)
2
KM (1/min) abscissa (exptl) 2 2
D /r (1/min) abscissa (exptl)
35.4 4.43 3.93 1.81 10-3 4.45 2.78 10-3 3.87
60.3 4.98 4.48 9.40 10-3 4.99 2.23 10-3 4.97
87.2 5.35 4.86 6.15 10-3 5.36 1.10 10-3 5.00
131 5.84 5.34 5.30 10-3 5.78 9.54 10-3 5.49
diffusional kinetic mechanism. We have faced a similar situation be combined yet with a kind of a film resistance equation. Such
in our previous works, where such switching occurred at about still complicated model of adsorption kinetics seems to be
80% of the equilibrium surface coverage in the systems suggested by the data presented in Figure 4. There, best linear
investigated by us.5 Then, as the remaining parts of the kinetic regressions will not originate at zero. Combining the SRT equation
isotherms are closer to equilibrium, they should be well correlated with a film resistance model would result into a system of two
by the Lagergren plots (15). Thus, assuming that switching in differential equations. We will present a more complicated model
our present system occurs at 66% of the equilibrium surface in a future publication.
coverage, we decided to construct the following graphical
illustration. Conclusions
Every kinetic isotherm was divided into two parts: the first
part containing N(t) values smaller than 0.66Ne and the second The MPFO equation can reproduce very well the behavior of
part the values N(t) > 0.66Ne. the kinetic eqs 5, 7, 11, and 22 based on the SRT approach by
The first part was correlated by using the linear MPFO assuming the Langmuir model of adsorption and a homogeneous
representation (24) whereas the second part was correlated by solid surface. The accuracy of this approximation is the highest
the linear Lagergren plot (15). for the values of parameter, corresponding to the most common
Looking into Figure 8, we can see fairly good linear experimental conditions. Thus, the empirical MPFO equation
correlations, predicted by the assumption of switching from the can be treated as an approximation of our exact SRT equation.
surface reaction to the diffusional sorption kinetics. So, it seems The linear representation of the MPFO equation (24) can be
interesting to analyze the values of the coefficients (tangents, applied only when the true experimental values of Ne are known.
abscissas) of their linear regressions. They are collected in This is because treating Ne as the best-fit parameter, leading to
Table 2. the best linearity of ln(Ne - N(t)) + N(t)/Ne vs t plots, enables
One can see when looking into Table 2 that the values of obtaining unphysical values of Ne as well as ce when the mass
abscissas in the MPFO plots are in very good agreement with balance relation is used.
their theoretically predicted values, i.e., with ln Ne. However, in One can propose a simple method, based on the analysis of
the case of the Lagergren plots, their abscissas are generally not kinetic adsorption isotherms measured at very short, initial times
equal to ln Ne as suggested by eq 11. Moreover, their values are of experiment, to distinguish between the SRT and the IDM
not equal to ln Ne + ln (6/2) as predicted by the diffusional kinetic models. This, however, would require measurements
Lagergren-like expression (15). This is more evidence for the carried out with an exceptionally high accuracy.
fact that switching takes place from one kinetic mechanism to
Such possibility is offered by applying the linear MPFO
another.
representation (24). This has led us to discover switching from
An explanation as to why such switching takes place may not
the surface reaction to diffusional kinetics when the surface
be a trivial problem. At present we may launch the following
coverage reaches about two-thirds of the equilibrium surface
hypothesis.
coverage.
There may exist a gradient of concentration at the entrance
to pores of the adsorbent. So, in general the SRT equations should LA8000448