Desalination 272 (2011) 20–26

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Desalination
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 / d e s a l

Small-Sample Corrected Akaike Information Criterion: An appropriate statistical tool

for ranking of adsorption isotherm models
Onoja M. Akpa a, Emmanuel I. Unuabonah b,⁎
a
Department of Mathematical Sciences, Redeemer's University, Km 46, Lagos Ibadan Expressway, PMB 3005, Redemption City, Mowe, Nigeria
b
Department of Chemical Sciences, Redeemer's University, Km 46, Lagos Ibadan Expressway, PMB 3005, Redemption City, Mowe, Nigeria

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

Article history: Ranking of seven equilibrium isotherm models with various numbers of parameters (Langmuir, Freundlich,
Received 17 November 2010 Redlich–Peterson, Sip, Langmuir–Freundlich, Fritz–Schlunder-3 parameter and Fritz–Schlunder-4 parameter)
Received in revised form 21 December 2010 for the adsorption of Cu2+ and Cd2+ onto Bentonite and modified Bentonite clay was done using the small-
Accepted 22 December 2010
sample-corrected Akaike information criterion (AICc).
Available online 26 January 2011
It was observed that the Freundlich model ranked first among the adsorption isotherm models considered. In
Keywords:
most cases, using the AICc, the Langmuir model was ranked the second best isotherm model. Modification of
Adsorption Geothite, Humic acid, and Goethite + Humic acid with increase in temperature was observed to affect the
Corrected Akaike information criterion Relative Akaike Weight (RAW) which describes the performance of adsorption models relative to the
Isotherm model ranking adsorption model with the minimum AICc estimate. The AICc was found to rank adsorption isotherm models
Error functions better than error functions because it is more sensitive to model deviations and takes into consideration the
Bentonite number of parameters in an equilibrium isotherm model. AICc was found to be more reliable in resolving very
close performance of adsorption isotherms.
This study showed that the conventional isotherm model, Freundlich, is a better model for describing
experimental data from adsorption of Cu2+ and Cd2+ onto Bentonite and modified Bentonite adsorbents than
models derived from them and having a higher number of parameters.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction isotherm model. Nevertheless, the ability to test adsorption data on

Adsorption equilibria information is the most important piece of
information in understanding an adsorption process. Using a false
adsorption model can have significant implications on soil manage-
ment decisions especially in calculating Soil Saturation Index (SSI)
because an erroneous adsorption capacity can produce false SSI
estimates or predictions [1].
Consequently, several equilibrium isotherm models for adsorption
processes have been proposed at different times to describe
experimental data. In modeling adsorption data, more than one
candidate model is often fitted to the experimental data with the aim
to explore/study how close the experimental data are to the
theoretical (model) data obtained from these known isotherm models
with known background theories. The level of accuracy of estimating
isotherm parameter(s) is lost to estimation processes so that what is
finally assumed to be the estimates for the parameters in the model(s)
contains some level of inherent deviation from the model values.
However, a good fit to the data, does not necessarily mean that the
data can be explained by the theories that were used to formulate the
⁎ Corresponding author. Tel.: + 234 805 317 5971.
E-mail addresses: onojamatthew@yahoo.co.uk (O.M. Akpa), iyaemma@yahoo.com
(E.I. Unuabonah).
more sophisticated models can help in elucidating the underlying
mechanisms controlling the adsorption process and can lead to more
physically realistic parameter values.
Again, many error estimating functions (sum of absolute error,
average relative error, sum of square error, coefficient of determina-
tion, chi-squares etc.) have been used to assess the level of deviation
of the theoretical data from the experimental data [2–7]. Although,
they observed that experimental data gave better fit to isotherm
models with parameters greater than two, these error estimating
functions do not take into account the number of parameters in the
models. Hence, they cannot be used for model selection and to judge
which of the candidate model performs better and by what
magnitude.
The AIC [8] has been used for model selection and ranking of
models in a variety of modeling research in psychology [9], in
medicine and in physiology for gene expressions [10,11], in wildlife
management [12], in modeling fertility curves in demographic studies
[13], and in agriculture for flood frequency modeling, [14]. However, it
has not been applied extensively in ranking equilibrium isotherm
models for adsorption although Bolster and Hornberger [1] expressed
the usage of AIC for Linearized Langmuir Equations. Malesh and El-
Khaiary [15] used the AIC in judging the better adsorption model
between Langmuir and Freundlich isotherm models for experimental

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.12.057
 O.M. Akpa, E.I. Unuabonah / Desalination 272 (2011) 20–26
data yet there is the dearth of information on the extensive application
of the AIC in the ranking adsorption isotherm models.
This work applies extensively, a small-sample-corrected Akaike
information criterion (AICc), in ranking seven equilibrium isotherms
models using adsorption data obtained from the adsorption of Cd2+
and Cu2+ onto Goethite, Humic acid and Goethite–Humic acid
modified Bentonite clay. The use of the AICc is because of its strong
ability to operate with small data points and yet produce reliable
results.
Model data in this work were obtained using the solver technique
of the Solver add-on in the Microsoft Excel Software because of its
ability to minimize the sum of squares for the residual (SSR) and thus
provide very reliable model data.
The aim of this work is to show the efficacy of AICc in appropriately
ranking equilibrium models for better soil management practices and
for correct prediction of the mechanism of adsorption on surfaces.
2. Theories
2.1. The Akaike information criterion (AIC)
The AIC developed by Akaike [8] is a methodology for model
selection in a situation where more than one model has been fitted to
data and screening of the candidate models is crucial to the objectives
of the research work [13].
The general form for calculating the AIC is given as:
AIC = 2k − 2 lnðLÞ
where k is the number of parameters in the model, n is the number of
data points, ln is the natural logarithm and L is the maximum value of
the likelihood function for the model.
Let us assume that the model errors are normally and indepen-
dently distributed. Let n be the number of data points and the sum of
squares for the residual (SSR), then the AIC becomes [9]:


SSR
AIC = 2k − n ln
ðn − kÞ
where k, and ln are as defined in Eq. (1).
When the number of observation (n) is small, Burnham and
Anderson [14] defined a bias-adjustment or correction for the AIC as:
 
2kðk + 1Þ
AICc = AIC +
n−k−1
k and n as defined in Eq. (1). Since AICc converges to AIC as n tends to
infinity, Burnham and Anderson [16] recommended that AICc should be
used in place of AIC regardless of the number of observations (n).
To quantify the plausibility of each model as being the most
approximating, we need an estimate of the likelihood of our model,
given our data i.e. L (model/data).
Now, let
Δi = AICci − min AICc
where Δi is the difference between the AICc of the best fitting model
and that of model i, AICci is AICc for model i, min AICc is the minimum
 
AICcvalue of all models. Then, L (model/data) ∝ exp − 12 Δi where
exp − 2 Δi is the relative likelihood of the model given the data.
1
Normalizing the relative likelihood values gives:
 
exp − 12 Δi
λi =
R   Peterson's exponent, and Ce and qe are as obtained in Langmuir
∑ exp − 12 Δi
i=1
where wi is the Akaike weight for the ith model [16].
21
The model for which AICc is minimal is selected as the best model
that better describes the experimental data obtained. AICc is not a test
in any sense: no single hypothesis (model) is made to be “null”, there is
no arbitrary α level, and there is no arbitrary notion of “significance”.
Instead there are concepts of evidence and a “best” inference, given the
data and the set of a priori models representing the scientific
hypotheses of interest. Akaike's general approach not only allows
the best model to be identified, but also allows the ranking of the rest of
the models under consideration.
2.2. Freundlich model
The Freundlich model [17] is a very common model used in the
analysis of adsorption data. It is based on the relation between the
adsorbed quantity qe and the solute concentration in equilibrium
solution, Ce. It describes non-ideal and reversible adsorption and it is
not restricted to the formation of the monolayer. This empirical model
can be applied to multilayer adsorption, with a non-uniform
distribution of adsorption heat and affinities over the heterogeneous
surface [18].
The nonlinear mathematical expression for this model is
1= n
qe = KF Ce : ð6Þ
2.3. Langmuir model
ð1Þ
The Langmuir model is another very common model based on
reaction hypotheses [19]. Some basic assumptions of these models
include: the solid is assumed to have a limited adsorption capacity qm
and all the adsorption sites (i) are assumed to be identical, (ii) each
site retains one molecule of the given compound and (iii) all sites are
energetically and sterically independent of the adsorbed quantity. The
nonlinear mathematical expression for the model is:
ð2Þ qm bCe
qe = ð7Þ
1 + bCe
where qe is the amount of solute adsorbed per unit weight of adsorbent
(mg g− 1), Ce is the equilibrium concentration of solute in the bulk
solution (mg/L), qm is the monolayer adsorption capacity (mg g− 1) and
b is the constant related to the energy of adsorption (L g− 1). It is the
ð3Þ
value reciprocal of the concentration at which half the saturation of the
adsorbent is attained.
2.4. Redlich–Peterson model
Jossens and co-workers modified the three parameter isotherm
first proposed by Redlich and Peterson [20] to incorporate features of
both the Langmuir and Freundlich equations. The versatile model has
a linear relationship with concentration in the numerator and an
exponential function in the denominator to represent adsorption
ð4Þ
equilibria over a wide concentration range, that can be applied either
to both homogeneous and heterogeneous systems. Mathematically, it
can be described as follows:
ACe
qe = ð8Þ
1 + BCeβ
where A and B Redlich–Peterson's parameters, β is the Redlich–
ð5Þ
equation. At low concentrations the Redlich–Peterson isotherm
approximates to Henry's law and at high concentrations its behaviour
approaches that of the Freundlich isotherm.
22 O.M. Akpa, E.I. Unuabonah / Desalination 272 (2011) 20–26

2.5. Sip model 2.8.2. Average relative error (ARE)

Sip's isotherm [21] is a combination of both Langmuir and Freundlich
expressions and is used for predicting heterogeneous adsorption
systems. It is believed to circumvent the limitation of the increasing
adsorbate concentration associated with the Freundlich isotherm
model. The nonlinear mathematical representation of the isotherm is:
The ARE model [24] which indicates a tendency to under or
overestimate the experimental data, attempts to minimize the
fractional error distribution across the entire studied concentration
range [25].

q −q
p

ns ∑
e; exp e; calc q
ð14Þ
qm ðbs Ce Þ e; exp i
qe = ð9Þ i=1
1 + ðbs Ce Þns

where qm, bs, Ce, qe and ns are the same as those in Langmuir and
Freundlich isotherms.
Or, as in the Langmuir–Freundlich form:
This is an isotherm that also fuses both Langmuir and Freudlich
isotherms together. It is expected to describe heterogeneous
surfaces much better. The nonlinear form of the isotherm can be
written as
2.8.3. Marquardt's percent standard deviation (MPSD)
Marquardt's percent standard deviation (MPSD) error function
[26] has been previously used by a number of researchers in
adsorption isotherm studies [27–29]. According to the number of
degrees of freedom in the system, it is similar in some respects to the
modified geometric mean error distribution [30].
 2
qe; exp −qe; calc
p
kLF CenLF
qe = ð10Þ ∑ qe; exp
ð15Þ
1 + ðbLF Ce ÞnLF i=1 i

where kLF, nLF, Ce, qe and aLF are the same as those in Langmuir and
Freundlich isotherms. 2.8.4. Sum of absolute errors (EABS)
The approach is similar to the sum square error function, with an
2.6. Fritz–Schlunder three parameter model increase in errors which will provide a better fit at high concentration
data [27].
The Fritz–Schlunder is a three parameter equation [22] having the
following form p

∑
qe; exp −qe; calc
ð16Þ
qmFS KFS Ce i=1 i
qe = ð11Þ
1 + qmFS CemFS
3. Materials and methods
where qe is the adsorbed amount at equilibrium (mg g− 1), Ce the
equilibrium concentration of the adsorbate (mg/L), qmFS the Fritz–
Analar grade (Aldrich) Bentonite and Humic acid were purchased
Schlunder maximum adsorption capacity (mg g− 1), KFS the Fritz–
while Goethite was synthesised in the laboratory with method
Schlunder equilibrium constant (L mg− 1), and mFS is the Fritz–
described by Olu-Owolabi et al., 2010. Analar grade (Aldrich) of
Schlunder model exponent.
cadmium nitrate (Cd(NO 3 ) 2 ·4H 2 O) and copper nitrate (Cu
(NO3)·3H2O) were used. Analytical grade reagents and chemicals
2.7. Fritz–Schlunder four parameter model
were used throughout the investigation. The various Modification of
Bentonite was carried by methods described by Olu-Owolabi et al.
Another four-parameter equation of the Langmuir–Freundlich
[31].
type was developed empirically by Fritz and Schlunder [22]. It is
expressed by the equation:
3.1. Premodification with Goethite and Humic acid
ACeα
qe = with α and β ≤ 1 ð12Þ Five percent Goethite, Humic acid and Goethite–Humic acid
1 + BCeβ modified Bentonite clay samples were prepared by adding 5%
Goethite and Humic acid in 95% Bentonite and 5% each of Geothite
where qe is the adsorbed amount at equilibrium (mg g− 1), Ce the
and Humic acid in 95% Bentonite.
equilibrium concentration of the adsorbate (mg/L), A and B are the
Each sample was suspended in 50 mL 0.01 M NaNO3 in different
Fritz–Schlunder parameters, and α and β are the Fritz–Schlunder
plastic containers respectively. This was tightly covered and agitated
equation exponents.
at room temperature (28 ± 2 °C) for 5 days. Thereafter, samples
were dried at 50 °C, pulverised and sieved through 0.5 mm mesh size
2.8. Error estimating functions
sieve.

2.8.1. Hybrid fractional error function (HYBRD)

3.2. Initial metal ion concentration
This is a composite error function developed to improve on the sum
square error fit at low concentrations. Thus, each sum square error value
A range of concentration from 50 to 700 mg/L at pH 5.00 and 6.00
is divided by the experimental solid-phase concentration with a divisor
for Cu2+ and Cd2+ respectively was used. The pH used in this study
included in the system as a term for the number of degrees of freedom
were based on the results obtained from previous studies [31]. All
(the number of data points minus the number of parameters within the
Cu2+ samples were agitated for 4 h and all Cd2+ samples were
isotherm equation) [23].
agitated for 8 h. 0.001 M NaNO3 was used as electrolyte based on
" # data obtained in the initial experiments on the effect of electrolyte.
p  0.01 M NaOH and 0.1 M HCl were used to adjust the pH of adsorbate
∑ ðqe; exp −qe; calc Þ2 ð13Þ solutions. The solution was filtered and the filtrate was analysed
i=1 qe; exp i using flame AAS.
 O.M. Akpa, E.I. Unuabonah / Desalination 272 (2011) 20–26 23

3.3. Adsorption of metal ions on modified Bentonite Table 1

Comparison of equilibrium isotherm models at various temperature for the of Cu2+ and
Cd2+ onto Bentonite clay.
0.2 g Bentonite clay was weighed into four different 60 mL plastic
bottles. Initial metal ion concentrations in the range of 50 to 700 mg/L L F Re Si Lafr FrSc FrSc2
were prepared from their stock solutions using 0.001 M NaNO3 as Cu2+ 30 °C
electrolyte. 20 mL of the metal ion solution to be investigated was K 2 2 3 3 3 3 4
added to the different sample bottles. The pH was adjusted with either SSR 4.27 2.56 2.28 2.23 2.29 2.29 2.30
2
χ 0.43(4.85) 0.17(0.42) 0.09 0.08 0.10 0.10 0.10
0.1 M NaOH or 0.1 M HCl to 5.07 for Cu2+ and 6.02 for Cd2+ and
HYBRD 1.01 0.42 0.34 0.33 0.35 0.34 0.34
sample solutions were agitated at room temperature 28 ± 2 °C for 4 MPSD 0.39 0.11 0.06 0.06 0.07 0.06 0.06
and 8 h for Cu2+ and Cd2+ respectively. The solutions were filtered ARE 1.14 0.74 0.57 0.49 0.58 0.55 0.52
and the filtrates analysed using flame AAS. The experiment was EABS 4.29 3.63 3.16 2.98 3.23 3.14 3.14
repeated at 50 °C. The same procedure was followed for adsorption of AICc 8.40 5.32 16.36 16.22 16.38 16.37 48.84
λi 4.65 1.00 249.48 232.81 251.70 250.54 2.81 × 109
metal ions onto Goethite, Humic-acid, Goethite–Humic acid modified
Bentonite using 0.2 g of 5% modified Bentonite. At the pHs of the Cu2+ 50 °C
adsorbate solutions, it is known that Humic acid adsorbed on the SSR 15.69 2.81 2.88 3.02 3.17 2.82 2.81
surface of Bentonite will not be desorbed [32]. χ2 3.60(6.72) 0.30(0.47) 0.32 0.32 0.33 0.31 0.30
HYBRD 4.80 0.53 0.55 0.56 0.58 0.26 0.53
All experiments were carried out in duplicate and the amount
MPSD 1.91 0.13 0.14 0.13 0.14 0.13 0.13
adsorbed by adsorbent after FAAS reading of equilibrium solution was ARE 2.46 0.60 0.64 0.64 0.66 0.61 0.60
calculated by difference. The averages of both values were used for EABS 8.34 3.06 3.14 3.23 3.38 3.07 3.06
data analysis. Six data points were used for statistical analysis. AICc 16.20 5.87 17.76 18.03 18.33 17.64 50.03
Different lamps for each metal ion were used during the analysis at λi 174.82 1.00 381.27 437.33 507.92 358.31 3.88 × 109

their respective wavelengths (copper 324.8 nm and cadmium

Cd2+ 30 °C
228.9 nm). SSR 4.19 2.46 2.11 2.40 2.40 2.11 1.87
χ2 0.15(1.28) 0.32(0.75) 0.14 0.21 0.19 0.15 0.14
4. Results and discussions HYBRD 0.63 0.64 0.39 0.50 0.49 0.40 0.34
MPSD 0.15 0.26 0.10 0.17 0.16 0.11 0.08
ARE 1.14 0.74 0.57 0.49 0.58 0.55 0.52
The error estimating functions (HYBRD, MPSD, ARE, and EABS) tend EABS 4.29 3.63 3.16 2.98 3.23 3.14 3.14
to favour the models with more than two parameters (Tables 1–4). To AICc 8.28 5.07 15.88 16.66 16.66 15.90 47.59
draw conclusions based on results obtained from error measurements λi 4.97 1.00 222.34 327.93 328.66 224.20 1.71 × 109
might lead to erroneous interpretation of adsorption data obtained
Cd2+ 50 °C
empirically. In ranking adsorption isotherm models error estimating
SSR 11.85 3.07 3.01 3.14 3.15 2.98 3.07
functions do not take into consideration the number of fitted parameters χ2 3.00(2.24) 0.25(0.59) 0.22 0.23 0.23 0.20 0.25
in computing the deviation of the theoretical data from the empirical HYBRD 3.70 0.57 0.53 0.54 0.53 0.49 0.57
data. MPSD 1.54 0.20 0.17 0.16 0.15 0.14 0.20
ARE 2.06 0.88 0.84 0.85 0.84 0.80 0.88
Tables 1–4 show that the AICc for the Freundlich model has the
EABS 6.90 3.93 3.90 4.00 4.00 3.89 3.93
minimum AICc value except for the adsorption of Cd2+ onto Goethite AICc 12.77 4.77 16.49 16.50 16.76 16.50 50.89
modified Bentonite at 30 °C. This implies that the theoretical data λi 54.71 1.00 351.88 352.44 402.49 353.08 1.04 × 1010
obtained from the Freundlich model fits the experimental data better
Note: Data in bracket were obtained from [31] without the use of solver add-on.
than other equilibrium isotherm models. From the theory of the
Freundlich isotherm model the adsorbents used in this work are
heterogeneous in nature and they might not be very efficient in
removing Cd2+ and Cu2+ from aqueous solutions at low concentra- predicts a monolayer adsorption capacity characteristic of the
tion ranges. A similar result has been obtained by El-Khaiary and Langmuir isotherm.
Malash, [33] when they observed that experimental data gave better It is observed in Tables 1–4 that the error estimating functions
fitting to Langmuir than to Redlich–Peterson using AIC to rank them. show values for the various models that are not significantly different.
Statistically, it is expected that the higher the number of This makes it very difficult to arrive at the best isotherm model
parameters in a model equation, the closer the theoretical estimates suitable for the adsorption. However, an estimate of the AICc for the
should be to the empirical data. However, the results of this study models and the Relative Akaike Weight (RAW), λi (number of times
shows the contrary due to the fact that apart from the fundamental the best model is more likely to be the correct model than the another
parameters used in the conventional adsorption isotherm models model), computed as a normalized relative likelihood values (Eq. (5))
(Freundlich and Langmuir models), all other equilibrium isotherm for the candidate models gave values that clearly distinguished the
models used in this study listed other parameters whose values are models and thus better ranked the models. For instance, in Table 1, for
basically constants limited by certain variables rather than para- the adsorption of Cu2+ onto Bentonite clay at 30 °C, the error
meters that represent the inherent mechanism(s) of the adsorption estimated values for the HYBRD error function are 1.01, 0.42, 0.34, and
process. These parameters were added to the conventional adsorption 0.34 for Langmuir, Freundlich, Redlich–Peterson and Fritz–Schlunder-
isotherm models with the intent of improving the performance of the 4 parameter adsorption isotherm models. However, it was observed
models, but in doing so the number of unknown parameters increases from the λi values that the Freundlich model is 4.65 times better than
making it difficult to find good parameter values, which in turn hurts the Langmuir model, 249.48 times better than the Redlich–Peterson
the performance of the model. As such there is a strong probability model and 2.81 × 109 times better than the Fritz–Schlunder-4
that results obtained from these models would not intrinsically fit the parameter model. A similar trend was observed in results from the
experimental data well compared to the conventional model other tables (Tables 2–4), except for data for Cd2+ at 30 °C in Table 2
(Freundlich). For example, at low concentrations the Redlich- where the Langmuir model appears to perform better than the
Peterson isotherm approximates to Henry’s law and at high Freundlich model which may be due to experimental biases. In most
concentrations its behaviour approaches that of the Freundlich cases, using the AICc, the Langmuir isotherm model was the second
isotherm [31]. At low adsorbate concentrations, the Sip isotherm best isotherm model (Tables 1–4). These results further show that the
reduces to the Freundlich isotherm; while at high concentrations, it conventional adsorption isotherm models (Langmuir and Freundlich
24 O.M. Akpa, E.I. Unuabonah / Desalination 272 (2011) 20–26

Table 2 Table 3
Comparison of equilibrium isotherm models at various temperature for the of Cu2+ and Comparison of equilibrium isotherm models at various temperature for the of Cu2+ and
Cd2+ onto Goethite modified Bentonite clay. Cd2+ onto Humic acid modified Bentonite clay.

L F Re Si Lafr FrSc FrSc2 L F Re Si LaFr FrSc FrSc2

Cu2+ 30 °C Cu2+ 30 °C
K 2 2 3 3 3 3 4 K 2 2 3 3 3 3 4
SSR 7.81 5.95 5.25 5.22 5.22 5.25 5.25 SSR 5.21 1.81 0.78 0.70 0.67 0.67 0.68
2 2
χ 0.38(13.9) 0.41(1.01) 0.18 0.17 0.17 0.18 0.18 χ 1.34(10.3) 0.54(0.66) 0.23 0.26 0.26 0.23 0.27
HYBRD 1.37 0.97 0.71 0.73 0.73 0.71 0.73 HYBRD 1.54 0.85 0.29 0.33 0.33 0.29 0.34
MPSD 0.36 0.29 0.12 0.13 0.13 0.12 0.12 MPSD 0.59 0.54 0.15 0.18 0.18 0.15 0.20
ARE 0.61 0.53 0.14 0.19 0.19 0.14 0.14 ARE 1.27 0.89 0.60 0.61 0.61 0.60 0.62
EABS 1.35 0.37 0.02 0.04 0.04 0.02 0.02 EABS 4.73 2.57 1.67 1.39 1.39 1.67 1.44
AICc 12.01 10.38 21.36 21.33 21.33 21.36 53.79 AICc 9.59 3.23 9.98 9.25 8.99 8.99 41.54
λi 2.26 1.00 242.12 237.96 237.96 242.12 2.67 × 109 λi 23.99 1.00 27.85 20.22 17.79 17.79 2.08 × 108

Cu2+ 50 °C Cu2+ 50 °C
SSR 15.08 2.73 2.75 2.75 3.11 2.74 2.73 SSR 12.25 0.52 0.52 0.52 0.92 0.52 0.52
χ2 3.53(33.2) 0.29(0.45) 0.25 0.30 0.34 0.30 0.29 χ2 3.35(19.5) 0.14(0.19) 0.14 0.14 0.20 0.14 0.14
HYBRD 4.67 0.51 0.48 0.52 0.59 0.25 0.51 HYBRD 4.10 0.16 0.16 0.16 0.23 0.16 0.16
MPSD 1.87 0.12 0.11 0.12 0.14 0.12 0.12 MPSD 1.74 0.06 0.06 0.06 0.07 0.06 0.06
ARE 1.94 0.23 0.15 0.25 0.28 0.25 0.23 ARE 2.24 0.40 0.40 0.40 0.38 0.40 0.40
EABS 4.56 0.45 0.20 0.49 0.53 0.48 0.45 EABS 7.55 1.39 1.39 1.40 1.78 1.40 1.40
AICc 15.96 5.70 17.48 17.48 18.23 17.47 49.86 AICc 14.72 − 4.30 7.43 7.53 10.93 7.49 39.86
λi 168.87 1.00 359.74 360.92 523.32 357.87 3.88 × 109 λi 13,458 1.00 352.74 370.58 2029.77 363.02 3.89 × 109

Cd2+ 30 °C Cd2+ 30 °C
SSR 2.00 2.32 1.44 1.30 1.30 1.44 1.78 SSR 6.62 1.53 0.78 0.85 0.85 0.78 0.83
χ2 0.23(4.66) 0.27(0.41) 0.10 0.08 0.08 0.11 0.16 χ2 1.41(10.2) 0.53(0.61) 0.27 0.31 0.31 0.27 0.30
HYBRD 0.52 0.45 0.25 0.22 0.22 0.04 0.30 HYBRD 1.76 0.80 0.35 0.42 0.42 0.20 0.40
MPSD 0.22 0.16 0.07 0.05 0.05 0.07 0.08 MPSD 0.63 0.52 0.19 0.24 0.24 0.19 0.23
ARE 0.50 0.42 0.06 0.04 0.04 0.04 0.25 ARE 1.42 0.91 0.65 0.71 0.71 0.65 0.70
EABS 0.78 0.37 0.02 0.06 0.07 0.10 0.35 EABS 5.69 2.46 1.74 1.74 1.74 1.74 1.75
AICc 3.86 4.74 13.58 12.99 12.99 13.61 47.29 AICc 11.02 2.25 9.88 10.43 10.43 9.89 42.75
λi 1.00 1.56 129.28 96.39 96.44 131.54 2.70 × 109 λi 80.25 1.00 45.46 59.67 59.67 45.46 6.23 × 108

Cd2+ 50 °C Cd2+ 50 °C
SSR 2.15 1.38 0.58 0.74 0.74 0.58 0.58 SSR 12.92 1.25 1.25 1.29 1.49 1.27 1.25
χ2 0.28(0.66) 0.27(0.41) 0.08 0.06 0.06 0.08 0.07 χ2 3.40(13.0) 0.19(0.27) 0.18 0.20 0.23 0.19 0.19
HYBRD 0.54 0.42 0.12 0.12 0.12 0.02 0.12 HYBRD 4.28 0.27 0.26 0.28 0.32 0.18 0.27
MPSD 0.27 0.19 0.04 0.03 0.03 0.04 0.04 MPSD 1.79 0.07 0.07 0.07 0.09 0.07 0.07
ARE 0.56 0.41 0.02 0.08 0.08 0.02 0.02 ARE 2.31 0.41 0.41 0.43 0.50 0.42 0.41
EABS 0.79 0.29 0.03 0.06 0.06 0.03 0.03 EABS 7.62 2.07 2.11 2.14 2.39 2.12 2.07
AICc 4.27 1.60 8.17 9.56 9.56 8.16 40.62 AICc 15.04 1.01 12.75 12.92 13.81 12.82 45.17
λi 3.80 1.00 26.71 53.65 53.65 26.71 2.98 × 108 λi 1112 1.00 353.66 386.25 602.58 367.1 3.88 × 109

Note: Data in bracket were obtained from [31] without the use of solver add-on. Note: Data in bracket were obtained from [31] without the use of solver add-on.

Results from Tables 1–4 suggest that temperature negatively

models) are still better models for describing adsorption data from
any adsorption system.
If we consider the error estimating functions in ranking the
isotherm models, then conventional isotherm models (Langmuir and
Freundlich) will not be favoured to best describe the experimental
data obtained and besides there will be no significant difference
between models that show better fits, making it difficult to judge the
isotherm that gives the best fit to experimental data as seen from
Tables 1–4 and Figs. 1–4 in supplementary data 2. In addition, as
mentioned earlier, error estimating functions do not take into
consideration the number of parameters in an equilibrium isotherm
model equation in ranking models, their results cannot be relied on.
Thus, the AICc is favoured in ranking these isotherm models.
Furthermore, the AICc is a better criterion for ranking models instead
of the error functions because it is sensitive to very small differences
between AICc values obtained for the various models via its Relative
Akaike Weight (RAW), λi (Tables 1–4).
Theoretical data were observed to be closer to the experimental
data when the Microsoft Excel® Solver Add-in Technique was used for
fitting. This is evident in the estimate of the error model using Chi-
square model (results shown in parenthesis in Tables 1–4) which
shows that the error function gave higher values compared with those
obtained by the Solver technique. This is because the Solver technique
has reduced the error inherent in estimating theoretical data using the
error function mode.
affected the performance of candidate models with respect to the
Freundlich model. It was observed that results from the candidate
models at higher temperature produced higher Akaike Weights relative
to the Freundlich models (Tables 1–4). For example, in Table 3, using
the Langmuir, Redlich–Peterson, Sip, Langmuir–Freundlich, Fritz–
Schlunder and Fritz–Schlunder 2 models, the RAW (λi) for the
adsorption of Cu2+ onto Bentonite clay was 4.65, 249.48, 232.81,
251.70, 250.54, 2.81 × 109 at 30 °C and 174.82, 381.27, 437.33, 507.92,
358.31, 3.88 × 109 at 50 °C (Fig. 1). For the adsorption of Cd2+ onto
Humic acid modified Bentonite at 30 °C and 50 °C it was 80.25, 45.46,
59.67, 59.67, 46.46 and 6.23 × 108 and 1112, 353.66, 386.25, 602.58,
367.10 and 3.88 × 109 respectively (Fig. 2). These results suggest that
other candidate isotherm models become less able to appropriately fit
experimental data as temperature increased from 30 °C to 50 °C relative
to the Freundlich isotherm model. This implies that temperature has an
influence on the performance of isotherm models when they are used to
fit adsorption data. As a general rule, the equation parameters are
governed mainly by the operating conditions such as the alteration of
pH, temperature and concentration of adsorbate [34].
At 30 °C, modification of Bentonite with Humic acid and Geothite +
Humic acid mixture was found to have an impact on the performance of
isotherm models. Modification of Bentonite clay with Goethite
improved the fitting performance of experimental data (obtained at
30 °C) to isotherm models as compared with data from other adsorbents
at same temperature while Humic acid modification further improved
 O.M. Akpa, E.I. Unuabonah / Desalination 272 (2011) 20–26 25

the appropriate model compared with other models

Table 4

Number of times Freundlich model is more likely

1200
Comparison of equilibrium isotherm models at various temperature for the of Cu2+ and
Cd2+ onto Goethite+Humic acid modified Bentonite Clay.
La
L F Re Si Lafr FrSc FrSc2 1000
Re
Si
Cu2+ 30 °C
LaFr
K 2 2 3 3 3 3 4 800
FrSc
SSR 6.20 2.08 0.80 1.11 1.11 0.80 1.06
2
χ 1.20(4.82) 0.66(8.35) 0.26 0.32 0.32 0.26 0.30
HYBRD 1.47 1.04 0.34 0.46 0.46 0.34 0.42 600
MPSD 0.51 0.66 0.19 0.27 0.27 0.19 0.23
ARE 1.24 0.97 0.65 0.76 0.76 0.65 0.73
EABS 5.39 2.49 1.88 2.29 2.29 1.88 2.25 400
AICc 10.62 4.08 10.06 12.05 12.05 10.06 44.21
λi 26.46 1.00 19.91 53.99 53.99 19.91 5.19 × 108
200
Cu2+ 50 °C
SSR 6.98 1.15 1.15 1.12 0.96 1.13 0.89
χ2 1.13(4.26) 0.14(0.30) 0.14 0.14 0.03 0.14 0.03 0
30°C 50°C
HYBRD 1.72 0.28 0.28 0.26 0.12 0.30 0.10
MPSD 0.76 0.12 0.12 0.12 0.03 0.12 0.02
temperature (°C)
ARE 1.54 0.62 0.62 0.61 0.35 0.61 0.33
EABS 6.17 2.49 2.49 2.47 2.07 2.47 1.97 Fig. 2. Effect of temperature on the performance of adsorption isotherms as against
AICc 11.34 0.50 12.22 12.11 11.17 12.15 43.17 Freundlich Isotherm in the adsorption of Cd2+ onto Humic acid modified Bentonite
λi 225.71 1.00 351.51 332.60 207.71 338.17 1.85 × 109 clay.

Cd2+ 30 °C
SSR 8.68 1.22 0.82 1.07 1.07 0.82 0.95 + Humic acid modified Bentonite, RAW gave 4.65, 2.26, 23.99 and 26.46
χ2 1.48(12.5) 0.44(1.37) 0.25 0.33 0.33 0.25 0.28 respectively. A similar trend was observed for Cd2+. This indicates that
HYBRD 2.00 0.67 0.35 0.49 0.49 0.35 0.41 modification of the Bentonite clay surface may also play a role in the
MPSD 0.68 0.43 0.20 0.29 0.29 0.20 0.23
performance of an isotherm model when they are used in fitting
ARE 1.56 0.84 0.68 0.77 0.77 0.68 0.73
EABS 6.83 1.98 1.99 2.14 2.15 1.99 2.15
experimental data from adsorption studies.
AICc 12.65 0.90 10.20 11.80 11.81 10.20 43.51
λi 355.84 1.00 104.46 233.62 233.66 104.46 1.79 × 108
5. Conclusion
Cd2+ 50 °C
SSR 8.86 2.33 2.33 2.34 2.33 2.34 3.24
χ2 0.98(13.0) 0.37(0.48) 0.37 0.37 0.37 0.37 1.01 The ranking of adsorption models by small-sample corrected
HYBRD 2.07 0.54 0.54 0.54 0.56 0.54 1.60 Akaike information criterion (AICc) was carried out on adsorption
MPSD 0.97 0.15 0.15 0.15 0.18 0.16 1.01 data obtained for the adsorption of Cu2+ and Cd2+ onto Bentonite and
ARE 1.58 0.70 0.70 0.71 0.80 0.71 1.22
modified Bentonite clays. The following observations were
EABS 6.74 3.19 3.20 3.20 3.36 3.21 3.43
AICc 12.77 4.77 16.49 16.50 16.76 16.50 50.89
λi 54.71 1.00 351.88 352.44 402.49 353.08 1.04 × 1010 • The AICc is an appropriate statistical tool for ranking isotherm
models than the error estimating functions currently in use because
Note: Data in bracket were obtained from [31] without the use of solver add-on.
it is more sensitive to model deviations even at very close
performance of adsorption isotherm models and account for the
fitting performance (Fig. 3). Although, with the Goethite–Humic Acid number of parameter in each model in ranking them.
modified Bentonite clay fitting performance was better than for the • Modification and increased temperature could vary the fitting
unmodified yet it was slightly reduced when compared with those pattern of experimental data.
obtained from Goethite modified clay. For instance, adsorption of Cu2+
onto Bentonite, Goethite modified, Humic acid modified and Goethite 300
the appropriate model compared with other models
Number of times Freundlich model is more likely

La
the appropriate model compared with other models

Re
Number of times Freundlich model is more likely

250
600 Si
LaFr

La FrSC
500 200
Re
Si
400 LaFr
150
FrSc

300
100

200

50
100

0 0
30°C 50°C Bentonite Goethite Humic GH
temperature (°C) Type of adsorbents

Fig. 1. Effect of temperature on the performance of adsorption isotherms as against Fig. 3. Effect of modification of Bentonite on the performance of adsorption isotherms
Freundlich isotherm in the adsorption of Cu2+ onto Bentonite clay. against Freundlich isotherm.
26 O.M. Akpa, E.I. Unuabonah / Desalination 272 (2011) 20–26
• In most cases the conventional isotherm models (Freundlich and
Langmuir) were more favored to describe equilibrium data than the
other isotherm models with three or more parameters.
Appendix A. Supplementary data
Supplementary data to this article can be found online at doi:10.
1016/j.desal.2010.12.057.
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Glossary
qe: amount of adsorbate on adsorbent at equilibrium (mg g− 1)
Ce: amount of adsorbate in equilibrium solution (mg g− 1)
Qo: adsorption capacity of adsorbent (mg g− 1)
b: langmuir constant related to energy (L g− 1)
A: Redlich Peterson and Fritz–Schlunder constant (L g− 1)
B: Redlich Peterson and Fritz–Schlunder constant (L mg− 1)
β: Redlich Peterson and Fritz–Schlunder exponent
KFS: Fritz–Schlunder equilibrium constant (L mg− 1)
α: Fritz–Schlunder exponent
mFS: Fritz–Schlunder model exponent
qmFS: Fritz–Schlunder maximum adsorption capacity (mg g− 1)
1/n: Freundlich constant indicative of the intensity of the adsorption.
KF: Freundlich constant indicative of relative adsorption capacity of the adsorbent
(mg g− 1)
ns: Sips constant
as: Sips constant
nLF: Langmuir–Freundlich constant which is equivalent to the Freundlich constant, n
aLF: Langmuir–Freundlich constant which is equivalent to the Langmuir constant, b
KLF: Langmuir–Freundlich variable which is equivalent to the Langmuir adsorption
Capacity, Qo (mg g− 1)
L: Langmuir model
F: Freundlich model
Re: Redlich–Peterson model
S: Sip model
Lafr: Langmuir–Freundlich model
FrSc: Fritz–Schlunder three parameter model
FrSc 2: Fritz–Schlunder four parameter model