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Comparison of two and three parameters

adsorption isotherm for Cr(VI) onto Kraft lignin
ARTICLE in CHEMICAL ENGINEERING JOURNAL FEBRUARY 2012
Impact Factor: 4.32 DOI: 10.1016/j.cej.2011.12.036

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Chemical Engineering Journal 183 (2012) 108111

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

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

Comparison of two and three parameters adsorption isotherm for Cr(VI) onto
Kraft lignin

Mirjana Brdar , Marina S ciban,

Aleksandar Takaci, Tatjana Dosenovic
Faculty of Technology, University of Novi Sad, Bul. Cara Lazara 1, 21000 Novi Sad, Serbia

a r t i c l e

i n f o

Article history:
Received 23 September 2011
Received in revised form 8 December 2011
Accepted 9 December 2011
Keywords:
Adsorption isotherm
Two- and three-parameter isotherm
Non-linear methods
Chromium
Lignin

a b s t r a c t
Equilibrium studies were carried out for the sorption of Cr(VI) onto Kraft lignin as an adsorbent. The experimental data were tted to the Freundlich, Langmuir, Temkin, DubininRadushkevich, RedlichPeterson,
Sips and Toth isotherms by non-linear method. We presented the comparison of two- and threeparameter isotherm. Only non-linear regression method was used in selecting the optimum isotherm
for the experimental data. The coefcient of correlation was used to select the best theoretical isotherm.
The best two-parameter isotherm is equally Langmuir and DubininRadushkevich isotherm. From threeparameter isotherms RedlichPeterson isotherm proved to be the best. Generally, RedlichPeterson
isotherm was found to be the best representative for Cr(VI) adsorption on the sorbent.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Extensive use of chromium, in e.g. electroplating, tanning, pigment manufacture, as a biocide and so on, results in discharges
of chromium-containing efuents into the nature. The soluble
hexavalent chromium is toxic and carcinogenic form, while the
less-soluble trivalent form has very low toxicity and is a required
nutrient. The two forms are inter-convertible in the environment
[1]. Since chromium is longstanding environmental contaminant, its discharging is limited, and accordingly, its removal from
wastewater prior to discharge into environment is necessary. There
are several techniques for chromium removal from wastewaters.
Recently, attention has been focused towards adsorption by alternative adsorbents which are mostly the biomaterials which are
byproducts or the wastes from large scale industrial operations
and agricultural waste materials [2]. Chromium adsorption onto
some biomaterials, under different conditions was studied [36] in
order to consider the adsorption phenomena, and get the data for
practical application. In this study, as adsorbent of Cr(VI) is applied
lignin, a residue that occurs in large quantities in cellulose production from wood. The utilization of lignin as potential adsorbent has
been increased in the latest years but it is still in the process of
development [7].

Corresponding author. Tel.: +381 21 4853631; fax: +381 21 4853631.

E-mail address: mbrdar@tf.uns.ac.rs (M. Brdar).
1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.12.036

The effectiveness of an adsorbent is estimated based on

its capacity, adsorption rate, its mechanical strength, possibility of regeneration and reuse and so on. The adsorbent
capacity is the most important parameter that mainly determines the rst. Adsorption capacity is determined on the base
of equilibrium experiments and some models of the adsorption isotherms. The different parameters and the underlying
thermodynamic assumption of these equilibrium models often
provide some insight into the adsorption mechanism, the surface properties and afnity of adsorbent. Several isotherm
equations can explain solidliquid adsorption systems, such
as: Langmuir, Freundlcih, Temkin, DubininRadushkevich, Sips,
Toth, RedlichPeterson [8]. Using the adsorption isotherms the
required amount of an adsorbent for the treatment of some
wastewater can be calculated. If some isotherm more precisely
describes adsorption, the calculated adsorbent dosage is more accurate.
The search for the best t adsorption isotherm using the method
of least squares is the most widely used technique by several
researchers [9,10]. Non-linear regression method is the best way
in selecting the optimum isotherm [9,1113]. Non-linear method
has an advantage that the error distribution does not get altered as
in linear technique, as all the isotherm parameters are xed in the
same axis.
In this study we analyzed the non-linear two-parameter equation of Freundlich, Langmuir, Temkin, DubininRadushkevich and
non-linear three-parameter equation of RedlichPeterson, Sips and
Toth isotherm model. The method of least squares was used to

M. Brdar et al. / Chemical Engineering Journal 183 (2012) 108111

109

predict the isotherm by a non-linear regression method. Mathematica 6, Wolfram Research software tool was used for calculation.

This equation is characterized by two tting parameters KF and nF

represented by:

2. Materials and methods

q = KF C 1/nF

2.1. Materials
Water solution of K2 Cr2 O7 , of different concentrations, was prepared by dilution of 0.25 mol/l stock solutions by distilled water,
just before experiments. All chemicals used were of analytical
reagent grade.
Kraft lignin was obtained from the sulfate pulping process of
poplar and beech wood (70:30) conducted in a pulp mill. Lignin
was precipitated from black liquor with sulfuric acid and washed
by distilled water. After ltering and drying at room temperature,
the lignin was obtained as a ne black-brown powder (particle
size < 0.25 mm). The BET surface area of Kraft lignin was measured
and it was found to be 0.77 m2 /g. The average pore diameter was
4.3 nm. This indicates that lignin did not have a well-developed
surface, and therefore, could not be characterized as an excellent
adsorbent.
2.2. Batch adsorption studies
The batch experiments were carried out by shaking 5 g (m)
of Kraft lignin in 1 l of aqueous solution of Cr(VI) at pH 2. The
adsorption experiments were done for this pH value in accordance
with results of previous investigations [2,14]. The suspension was
shaken by agitation speed of 110 rpm, at 20 C, up to 3 h, which
is sufcient contact time [14]. The adsorbent was then ltered
through the Gooch G4 crucible, and residual heavy metal ions in
the ltrate were determined. The concentration of heavy metal
ions in the aqueous solution before (C0 ) and after adsorption (C)
was determined by oxi-reduction titration [15]. Experiments were
duplicated and the results were averaged.
The amount of heavy metal ions adsorbed per specied amount
of adsorbent (q) was calculated as follows:
q=

C0 C
m

The magnitude of the Freundlich adsorption capacity nF gives

an indication of favorability of adsorption. The value of nF ranges
from 2 to 10 indicating good adsorption capacity, 12 moderate
adsorption capacity and less than one indicate poor adsorption
capacity.
The Langmuir isotherm [17] applies to localized adsorption of
monolayer surface coverage assuming that each adsorbed molecule
occupies one adsorption site. The derivation of the Langmuir
isotherm was obtained by considering both the rates of adsorption and desorption, integrating the net rate of surface coverage
and, at equilibrium, the isotherm equation reduces to the simple
two-parameter equation:
q=

qL KL C
1 + KL C

where qL is the maximum monolayer adsorption capacity, and KL is

the equilibrium constant which is related to the enthalpy of adsorption through the Vant Hoff equation.
The Temkin isotherm [18] is a two-parameter isotherm, too.
Temkin and Pyzhev are considered to have the effect of some
indirect adsorbate/adsorbate interaction on adsorption isotherms
and suggested that because of the interaction the heat of adsorption of all the molecules in the layer would decrease linearly with
coverage. The Temkin isotherm has generally been applied in the
following form:
q = BT ln(AT C)
where AT is the Temkin isotherm constant and BT is the Temkin
isotherm energy constant.
The DubininRadushkevich is also two-parameter isotherm.
This isotherm is expressed as follows [19]:

 

q = qD exp AD ln 1 +

1
C

2 

where m is a mass adsorbent per liter of solution.

2.3. Adsorption isotherms
Batch equilibrium adsorption experiments were used for adsorbent assessment through plots of adsorption isotherms. Adsorption
isotherms can also be mathematically expressed. This was done
already in the early 1900s in the work of Freundlich [16] and
Langmuir [17]. Later, other adsorption isotherm relationships have
been developed, mainly based on the two mentioned. Their success
undoubtedly reects their ability to t a wide variety of adsorption
data quite well, but it may also partly reect the appealing simplicity of the isotherm equations and the ease with which their
adjustable parameters can be estimated. Both isotherm equations
can be transformed to a linear form and so their two adjustable
parameters are easily estimated either by graphical means or by
linear regression. This ease of tting may have led to the Langmuir and Freundlich isotherms enjoying rather more success than
they deserve since closer examination of the data often reveals systematic deviations from the tted isotherms. For many isotherms,
including those with three or more adjustable parameters, it is no
longer possible to estimate the adjustable parameters by ordinary
linear regression or by any reliable graphical means, and so it is
necessary to use nonlinear regression.
The Freundlich equation [16] is an empirical model that considers heterogenous adsorptive energies on the adsorbent surface.

Radushkevich and Dubinin have reported that the characteristic

sorption curve is related to the porous structure of the sorbent. The
constant BD , where AD = BD R2 T2 , is related to the mean free energy
of sorption per mole of the sorbate as it is transferred to the surface
of the solid from innite distance in the solution and this energy
can be computed using the following relationship [20]:
E=

2BD

where R is the universal gas constant, T is the temperature and qD

is the DubininRadushkevich isotherm constant.
The RedlichPeterson isotherm [21], contains three parameters,
ARP , BRP and g, and the form of the equation includes features of
the Langmuir and Freundlich isotherms. It may be used to represent adsorption equilibrium over a wide concentration range of
adsorbate. The exponent, g, lies between 0 and 1. When g = 1, the
RedlichPeterson equation becomes the Langmuir equation, and
when g = 0, it becomes the Henrys law. This isotherm is represented
by:
q=

ARP C
1 + BRP C g

The Sips isotherm [22] is a combination of the Langmuir and

Freundlich isotherms, which represent systems for which one

110

M. Brdar et al. / Chemical Engineering Journal 183 (2012) 108111

Table 1
Isotherm parameters for Cr(VI) onto Kraft lignin obtained by non-linear method
(two-parameter isotherms).
Langmuir

Temkin

DubininRadushkevich

KF = 0.13535
nF = 2.51719

KL = 2.16159
qL = 0.22744

AT = 76.6341
BT = 0.36635

qD = 0.19622
AD = 0.36635

adsorbed molecule could occupy more than one adsorption site

represented by the variable n in the isotherm equation given by:

It has three parameters, qs , Ks and ns , that could be expressed

as a function of temperature which allows easy interpolation and
extrapolation of the experimental isotherms to other temperatures
and compositions.
The Toth isotherm [23] is another isotherm that has three
parameters qt , Kt and t and that could be written as a function of
temperature. It is given by:
qt Kt C
(1 + (Kt C)t )

Freundlich
Langmuir

0.10

Tempkin
0.05

qs (Ks C)1/ns
.
q=
1 + (Ks C)1/ns

q=

0.15

q (mmol/g)

Freundlich

0.20

1/t

0.00
0.0

0.5

1.0

1.5

2.0

2.5

3.0

C (mmol/l)
Fig. 1. Two-parameters isotherms obtained using the non-linear method for the
sorption of Cr(VI) onto lignin.
Table 3
Coefcient of determination for various adsorption isotherms using experimental
data.
Two-parameters isotherm equation

r2

The Toth isotherm exponent is related to surface heterogeneity, usually less than or equal to unity. If t is equal to the unit this
suggests that the process occurs on a homogenous surface.

Freundlich
Langmuir
Temkin
DubininRadushkevich

0.899250
0.980539
0.876324
0.988620

3. Results

Three-parameters isotherm equation

r2

RedlichPeterson
Sips
Toth

0.994380
0.991305
0.987378

p

r2 =

p
i=1

i=1

(qmeas qcalc )
2

(qmeas qcalc ) +

p

i=1

(qmeas qcalc )2

where qcalc is the calculated equilibrium solid phase concentration,

qmeas is the measured equilibrium solid phase concentration and
q calc is the average of qcalc . If r2 = 1 then the goodness of t is perfect.
Unfortunately, due to the unavoidable errors in measurement, r2 is
always less than unity [24].
Fig. 1 shows the experimental and the predicted two parameter isotherms by non-linear method for the sorption of Cr(VI) onto
Kraft lignin. The Langmuir and DubininRadushkevich isotherm
have almost the same and high coefcient of determination when
compared to Freundlich and Temkin isotherm (Table 1). Thus, we
chose Langmuir isotherm. It is simpler than DubininRadushkevich
one.
The isotherm of adsorption indicates how the quantities of
molecules are distributed between the liquid and solid phase when
the adsorption processes reach balance. It is employed to establish the maximum capacity of adsorption of metals on adsorbents,
which is expressed in terms of quantity of metal adsorbed per

unit of mass of adsorbent used. It can be seen that the adsorption isotherm of chromium exhibited Langmuir behavior, which
indicates that the uptake occurs on a homogenous surface by monolayer adsorption and can be described in terms of chemisorptions
as the formation of an ionic or covalent bonds between adsorbent
and adsorbate.
All three-parameter equation types give a very high coefcient
of determination (Table 3). Fig. 2 shows experimental data and the
predicted equilibrium curve using non-linear method for the threeparameter isotherm RedlichPeterson, Sips and Toth, respectively.
The highest coefcient of determination for RedlichPeterson
isotherm suggests that it is the best curve model of experimental data. The Toth isotherm exponent t is nearly unity. It tells us
that this is the process occurs on a homogenous surface. All three
three-parameter isotherm suggests that the sorption capacity of
Kraft lignin to uptake Cr(VI) to be 0.180.19 mmol/g.
0.20

0.15

q (mmol/g)

We used nonlinear regression methods for determining the

parameters of various isotherm models for the experimental data.
The parameters of isotherm are presented in Tables 1 and 2.
Despite the undeveloped adsorption surface, the lignin proved
to be a very good adsorbent for the adsorption of Cr (VI) ions from
water, in the range of other biomaterials [2,7].
In this paper, the coefcient of determination r2 , was used to
test the best-tting isotherm to the experimental data:

0.10
Redlich Peterson
Sips

0.05
Table 2
Isotherm parameters for Cr(VI) onto Kraft lignin obtained by non-linear method
(three-parameter isotherms).
RedlichPeterson

Sips

Toth

ARP = 0.33449
BRP = 0.98618
g = 0.99987

Ks = 2.85631
qs = 0.19863
ns = 0.66653

Kt = 0.84740
qt = 0.28981
t = 1.28614

0.00
0.0

Toth

0.5

1.0

1.5

2.0

2.5

3.0

C (mmol/l)
Fig. 2. Three-parameters isotherms obtained using the non-linear method for the
sorption of Cr(VI) onto lignin.

M. Brdar et al. / Chemical Engineering Journal 183 (2012) 108111

Since the RedlichPeterson parameter g is nearly 1, this means

that the equilibrium isotherm behaves as Langmuir, not as Freundlich isotherm. It can be concluded that surface of Kraft lignin
is homogenous for dichromate ions adsorption i.e. all adsorption
sites are equal. This is conrmed by coefcient of determination.
The obtained results show that three parameter isotherms better
reect the adsorption of copper(VI) on lignin than two parameter
isotherms.

4. Conclusions
The equilibrium sorption of Cr(VI) by Kraft lignin was
explained using the two- and three-parameters isotherm equations. For two-parameter isotherms, both, the Langmuir and
the DubininRadushkevich isotherm were found to be the best
choice. This is indicated by a higher coefcient of determination
obtained for Langmuir (r2 = 0.980539) and DubininRadushkevich
(r2 = 0.988620) isotherms compared to Temkin (r2 = 0.876324) and
Freundlich (r2 = 0.899250) isotherms. For RedlichPeterson, Sips
and Toth isotherms coefcient of determination is greater than
0.987, so we conclude that all three of the three-parametric equations show very good agreement with experimental data. The
presented research showed that for three-parameters isotherm
equation is the best RedlichPeterson isotherm model. Also, the
study shows the non-linear regression method including threeparameter isotherm to be the best way to obtain the isotherm
parameters. Finally, the lignin proved to be a very good adsorbent
for the adsorption of Cr(VI) ions from water, in the range of other
biomaterials.

Acknowledgements
The work presented here was supported by the Serbian Ministry
of Education and Science (project III44006) and Serbian Ministry of
Science, Technology and Environmental Protection Project (project
174009).
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