Permanent hard water softening using carbon nanotube sheets

Maryam Ahmadzadeh Toghy, Toraj Mohammadi

Research Centre for Membrane Separation Processes, Faculty of Chemical Engineering, Iran University of Science and Technology (IUST), Narmak, Tehran, Iran
a b s t r a c t a r t i c l e i n f o
Article history:
Received 13 April 2010
Received in revised form 12 October 2010
Accepted 12 October 2010
Available online 10 November 2010
Keywords:
Carbon nanotube sheets
Permanent hard water softening
Adsorption
Isotherms
Kinetic models
Permanent hard water softening using oxidized carbon nanotube (CNT) sheets was performed. CNT sheets
were synthesized by chemical vapor deposition of cyclohexanol and ferrocene in nitrogen atmosphere at
750 C, and oxidized with concentrated nitric acid at room temperature and then employed as adsorbent for
permanent hard water softening. Various isotherms and kinetic models were applied to t the experimental
data. It was found out that the adsorption behavior of hard mineral ions by oxidized CNT sheets match well
with the Freundlich isotherm and the pseudo-second-order kinetic model. The results demonstrated that the
oxidized CNT sheets can be used as an effective adsorbent for hard water softening due to their high
adsorption capacity. Also, using the oxidized CNT sheets, hard water softening without CNT leakage into water
is economically feasible.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Hard water is water that has high mineral content mainly calcium
and magnesium ions. There are two types of water hardness:
temporary and permanent. Temporary hardness is caused by a
combination of calcium and bicarbonate ions in water. It can be
removed by addition of lime (calcium hydroxide) or by boiling in an
open container. Boiling promotes formation of carbonate from
bicarbonate and then calcium carbonate is precipitated, and conse-
quently the cooled leaving water is softer. Permanent hardness is
usually caused by the presence of calcium and magnesium sulfates in
water which become more soluble as temperature rises. Therefore,
permanent hardness cannot be removed by boiling. It can be removed
by using a water softener which works on the principle of ion
exchange in which calcium and magnesium ions are exchanged with
sodium or potassium ions, reducing the concentration of hardness
minerals to tolerable levels and thus making the water softer and
giving it a smoother feeling. Water softener gradually loses its
effectiveness and must be regenerated. This is accomplished by
passing a concentrated brine solution through it, causing the above
reaction to be reversed. Most of the salt employed in the regeneration
process gets ushed out of the system and is usually released into the
soil or drainage systems that can have damaging consequences to the
environment, especially in arid regions [1].
To avoid the addition of sodium or potassium ions from the
softener to the treated water and also the environmental problems of
water softeners, developing alternative methods and new materials
for hard water softening are important and essential.
Among many treatment processes that are currently used for
removal of ions from water such as chemical precipitation, evapora-
tion, ion exchange, adsorption, electrodialysis and reverse osmosis,
adsorption is a promising and widely applied method due to its cost
effectiveness [2].
Carbon materials are a class of signicant and widely used
engineering adsorbent. As a new member of the carbon family,
carbon nanotubes (CNTs) have exhibited great potentials as an
attractive adsorbent in water treatment and environmental protec-
tion [318]. This is due mainly to their extremely small size, uniform
pore distribution and large specic surface area. The metal ion
adsorption capacity of CNTs directly relates to their total surface
acidity including functional groups. Different acidic functional groups
such as carboxyls, lactones and phenols can be formed on CNT surface
after oxidation processes. Protons in the functional groups of the
oxidized CNTs are exchanged with the metal ions [2].
Recently, the powder of CNTs has been used as adsorbent in
adsorption processes very often. In industrial scale, when the powder
of CNTs is used as adsorbent, mixing of the CNTs with hard water with
ultrasonic agitation is not economically and technically possible. Also,
after adsorption process, it is difcult to completely remove the
powder of CNTs from treated water without centrifuging process.
Also, separation of the CNTs fromtreated water by ltration is difcult
because the lter may be quickly blocked by the CNTs. Also, the CNTs
may possess some degree of toxicity and as a result their safety is
controversial. Therefore, economical hard water softening without
CNT leakage into water is preferable [19,20].
In our previous studies [19,20], carbon nanotube sheets were
synthesized by chemical vapor deposition method and oxidized with
Desalination 268 (2011) 208213
Corresponding author. Tel.: +98 21 77240496; fax: +98 21 77240495.
E-mail address: torajmohammadi@iust.ac.ir (T. Mohammadi).
0011-9164/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.10.028
Contents lists available at ScienceDirect
Desalination
j our nal homepage: www. el sevi er. com/ l ocat e/ desal
concentrated nitric acid and then employed as a practical adsorbent
for sodium chloride and some divalent heavy metal ions' removal
fromwater. In the present work, capability of the oxidized CNT sheets
for permanent hard water softening (calcium and magnesium sulfate
removal from water) was investigated. Also, various isotherms and
kinetic models were used to describe the adsorption behavior of hard
mineral ions onto the oxidized CNT sheets.
2. Experimental procedure
2.1. Synthesis of the CNT sheets
Details of the synthesis process of the CNTs sheets were presented
elsewhere [1921]. The as-synthesized CNT sheets were immersed in
concentrated nitric acid (65%, Merck) for 20 h and then washed using
deionized water several times until pH of the washing water showed
no change, then dried at 110 C for 24 h. These oxidized CNT sheets
were used as adsorbent for hard mineral ions removal from water.
Scanning electron microscope (SEM, Philips: XL30) was used for
analysis of the CNT sheets morphology, and nanostructure of the CNTs
was determined by transmission electron microscope (TEM, Philips:
CM200).
2.2. Adsorption procedure
Batch adsorption experiments were carried out using 100, 300, 600,
900 and 1200 mg/l solutions prepared fromanalytical grade calciumand
magnesium sulfates (Merck) in deionized water. All the experiments
were performed via soaking 50 mg of the CNT sheets in 25 ml of the
prepared solutions at room temperature (25 C). A conductometer
(CRISON, GLP 32) was used to measure the salt concentration of the
solutions. Water conductivity directly depends on salt concentration.
These dependencies (calibration curves of the conductometer for
calcium and magnesium sulfates) are shown in Fig. 1. The amount of
adsorbed salts can be obtained using the following equation:
q
e
=
C
0
C
e
V
w
1
where q
e
is the equilibrium adsorption uptake (mg/g), C
0
is the initial
salt concentration (mg/l), C
e
is the equilibrium salt concentration
(mg/l), V is the volume of the solution (l) and w is the mass of the
adsorbent (g).
3. Results and discussion
3.1. Characterization of oxidized CNT sheets
Fig. 2 shows the synthesized oxidized CNT sheets: (a) an overview
image, (b) a surface SEM image (inset: a TEM image of a typical CNT
with inner tube diameter of about 10 nm and outer tube diameter of
about 3040 nm) and (c) a high magnication SEM image. From the
SEM images, the CNT sheet is regarded as an entangled CNT network.
The CNT sheets have high exibility and are not easily broken during
oxidation, washing and drying processes.
Oxidation of the CNTs can offer not only a more hydrophilic surface
structure, but also a great number of acidic functional groups. As
mentioned, the metal ion adsorption capacity of CNTs directly relates to
their total surface acidity including functional groups. As reported in
literature, different acidic functional groups such as carboxyls, lactones
and phenols can be formed by nitric acid oxidation [13]. These functional
groups induce a negative charge on the CNT surface and oxygenatoms of
these functional groups donate their single pair of electrons to the metal
ions, and this consequently increases cation exchange capacity of the
CNTs [2,10]. Protons in the functional groups of the CNTs are exchanged
with the metal ions. The chemical interaction (bond) between the metal
ions and the surface acidic functional groups of the CNTs is mainly
responsible for adsorption [2,12,14]. The surface total acidity of the as-
synthesized and the oxidized CNT sheets were quantied by Boehm
method [13] and presented in Table 1.
The surface charge depends on pH of the surrounding electrolyte.
There is a pH value, called point of zero charge (PZC), at which the
net surface charge is zero. The pH
PZC
of the as-synthesized and the
oxidized CNT sheets were quantied by mass titration [14] and
presented in Table 1. As observed, the pH
PZC
shifts to lower pH values
after nitric acid oxidation. These results conrmed the data obtained
from Boehm's titration.
Figs. 3 and 4 show the adsorption behavior of hard mineral ions
(Ca
2+
and Mg
2+
) onto the oxidized CNT sheets at different initial salt
concentrations as a function of adsorption time. As can be observed,
adsorption uptake of hard mineral ions increases with time and then
reaches to equilibrium. As can be observed, increasing initial
adsorbate concentration increases signicantly the equilibrium
adsorption uptake of hard mineral ions onto the oxidized CNT sheets.
It can be explained that the impetus of initially high concentration is
larger than that of initially lowconcentration, and as a result, sorption
onto the CNT sheets is a diffusion based process [22]. Also, it can be
observed that the equilibrium is reached faster at initially lower salt
concentration, probably because the sorption sites adsorb available
metal ions more rapidly at lower salt concentration [2,23].
The equilibrium adsorption uptake is an important factor because it
determines how much adsorbent is required quantitatively for enrich-
ment of an analyte from a given solution. Fig. 5 shows the equilibrium
adsorption uptake (nal adsorption capacity) of the oxidized CNT sheets
at different initial adsorbate (Ca
2+
and Mg
2
) concentrations. As can be
observed, the nal adsorption capacities of Ca
2+
and Mg
2+
reach 5.4679
and 7.1521 mg/g for C
0
=100 ppm, 17.3253 and 21.5626 mg/g for
Fig. 1. Calibration curves of conductometer for (a) calcium sulfate and (b) magnesium
sulfate solutions.
209 M.A. Toghy, T. Mohammadi / Desalination 268 (2011) 208213
C
0
=300 ppm, 34.1258 and 42.2658 mg/g for C
0
=600 ppm, 60 and
81.2564 mg/g for C
0
=900 ppm and 77.4598 and 101.4590 mg/g for
C
0
=1200 ppm. It is obvious that the nal adsorption capacity of Mg
2+
is
larger than that of Ca
2+
, especially at higher initial adsorbate
concentration. Electrostatic interactions as one basic type of the
adsorbateadsorbent interactions involve the attractions by electrical
charges differences between the adsorbent and the adsorbate. Electro-
static interactions are proportional to charges of ions and inversely
proportional to distance between centers of interacting ions (van der
Waals radii). Since the ionic radius determines the van der Waals radii, it
has a strong effect onthe electrostatic interactions. For a givenadsorbent,
its electrostatic interaction potential with adsorbate ions increases with
decreasing ionic radius of the adsorbate. Ionic radius increases with
increasing atomic weight for elements in the same family of the periodic
table [24]. The ionic radius of Mg
2+
is smaller than that of Ca
2+
and as a
result its nal adsorption capacity (as a result of electrostatic interac-
tions) onto the oxidized CNT sheets is larger, especially at higher initial
adsorbate concentration.
3.2. Adsorption kinetics
For a successful scale-up of hard water softening using the
oxidized CNT sheets, kinetic studies are essential since they describe
the adsorbate uptake rate, which in turn controls the residence time in
the adsorbentsolution interface.
In order to analyze the adsorption kinetics of hard mineral ions,
two kinetic models including the pseudo-rst-order [25] and the
pseudo-second-order [26] models were applied to t the experimen-
tal data. The effect of the initial adsorbate concentration was
investigated to nd the best kinetic model.
The pseudo-rst-order kinetic model can be expressed by:
dq
t
dt
= k
1
q
e
q
t
: 2
The equation decision (2) can be expressed in linear form:
log q
e
q
t
= log q
e

k
1
2:303
t: 3
Fig. 2. Synthesized oxidized CNT sheets, (a) an overview image, (b) a surface SEM
image (inset: TEM image of a typical CNT) and (c) a high magnication SEM image.
Table 1
Surface acidity and pH
PZC
of the as-synthesized and the oxidized CNT sheets.
Surface acidity (mmol/g) pH
PZC
As-synthesized CNT sheets 1.6 6.8
Oxidized CNT sheets 3.6 3.9
Fig. 3. (a) Effect of initial salt concentration on (a) conductivity and (b) adsorption
uptake of the calcium sulfate solution for the oxidized CNT sheets.
210 M.A. Toghy, T. Mohammadi / Desalination 268 (2011) 208213
The pseudo-second-order kinetic model is expressed by:
dq
t
dt
= k
2
q
e
q
t

2
: 4
The equation decision (4) can be expressed in linear form:
t
q
t
=
1
k
2
q
2
e
+
1
q
e
t 5
where k
1
and k
2
is the adsorption rate constants of rst and second
order kinetic models, in min
1
and l/mg.min respectively; q
e
and q
t
, in
mg/g, are equilibrium adsorption uptake (at time t =) and
adsorption uptake (at time t), respectively.
The slope and the intercept of each linear plot in Figs. 6 and 7 are
used to calculate the adsorption rate constants (k
1
and k
2
) and the
amount of adsorption in equilibrium (q
e
). The calculated kinetic
parameters for adsorption of hard mineral ions onto the oxidized CNT
sheets under different initial hard mineral ion concentrations are
listed in Table 2. As can be observed, the correlation coefcients (R
2
)
of the pseudo-second-order kinetic model are higher than those of the
pseudo-rst-order kinetic model. Also, the experimental q
e
values are
closer to q
e
values calculated from the pseudo-second-order kinetic
model especially at lower adsorbate concentration. With increasing
adsorbate concentration, the deviation of the q
e
values calculated
from the pseudo-second-order kinetic model from the experimental
q
e
values increases. Accordance of the experimental data with the
pseudo-second-order kinetic model indicates that the adsorption of
hard mineral ions onto the oxidized CNT sheets is controlled by
chemical adsorption [27]. Chemical adsorption as one basic type of the
adsorbateadsorbent interactions involves valence forces through
sharing or exchanging electrons between adsorbent and adsorbate. In
chemical adsorption, it is assumed that the adsorption capacity is
proportional to the number of active sites occupied on the adsorbent.
Generally, the adsorption process can be either electrostatic or
chemical in nature, and frequently involves both [24]. The results
demonstrated that the adsorption process of hard mineral ions onto the
Fig. 4. (a) Effect of initial salt concentration on (a) conductivity and (b) adsorption
uptake of the magnesium sulfate solution for the oxidized CNT sheets.
Fig. 5. Effect of initial hard mineral ions (Ca
2+
and Mg
2+
) concentration on the
equilibrium adsorption uptake.
Fig. 6. Pseudo-rst-order kinetic models for adsorption of (a) Ca
2+
and (b) Mg
2+
onto
the oxidized CNT sheets at different adsorbate concentrations.
211 M.A. Toghy, T. Mohammadi / Desalination 268 (2011) 208213
oxidized CNT sheets involves both electrostatic and chemical interac-
tions. At higher initial adsorbate concentration, adsorption is controlled
by electrostatic interactions, while at lower initial adsorbate concentra-
tion, adsorption is controlled by chemical interactions.
3.3. Adsorption isotherms
The experimental data for hard mineral ion adsorption onto the
CNT sheets were analyzed using Langmuir and Freundlich adsorption
isotherm models. The Langmuir isotherm was used successfully to
characterize the monolayer adsorption process. It can be represented
by the following equation:
q
e
=
q
m
K
L
C
e
1 + K
L
C
e
: 6
The equation decision (6) can be expressed in linear form:
C
e
q
e
=
1
K
L
q
m
+
C
e
q
m
7
where q
e
is the equilibriumadsorption uptake of hard mineral ions, in
mg/g, C
e
is the equilibriumconcentration of hard mineral ions, in mg/l,
q
m
is the maximum adsorption capacity corresponding to the
complete monolayer coverage, in mg/g and K
L
is the Langmuir
constant which is related to the energy of adsorption.
An essential characteristic of Langmuir isotherm can be expressed
by a dimensionless constant called equilibrium parameter:
R
L
=
1
1 + K
L
C
0
8
where K
L
is the Langmuir constant and C
0
is the highest initial heavy
metal ions concentration, in mg/l. The value of R
L
indicates the type of
the isotherm to be either unfavorable (R
L
N1), linear (R
L
=1),
favorable (0bR
L
b1) or irreversible (R
L
=0).
The Freundlich isothermmodel is a semi-empirical equation based
on the adsorption occurred on heterogeneous surface. It can be
presented by the following form:
q
e
= K
F
C
n
e
: 9
The equation decision (9) can be expressed in linear form:
log q
e
= n log C
e
+ log K
F
10
where q
e
is the equilibrium adsorption uptake of hard mineral ions, in
mg/g, C
e
is theequilibriumconcentrationof hardmineral ions inmg/l and
K
F
andnare the Freundlichparameters relatedtoadsorptioncapacityand
adsorption intensity, respectively.
The slope and the intercept of each linear plot in Fig. 8 are used to
calculate Langmuir and Freundlich parameters. The calculated
Langmuir and Freundlich parameters are listed in Table 3. As can be
observed, the Freundlich model agrees well with the experimental
data, with a correlation coefcient value being close to one
(R
2
=0.9962 for Ca
2+
and R
2
=0.9895 for Mg
2+
). The values of K
F
calculated using the Freundlich model are large indicating that the
oxidized CNT sheets have high afnity toward hard mineral ions
(K
F
=44.6952 for Ca
2+
and K
F
=61.2787 for Mg
2+
). The constant
value of K
F
is higher for adsorption of Mg
2+
onto the oxidized CNT
sheets which is consistent with the experimental observation (Fig. 5).
Derivation of the n values fromunity indicates a non linear adsorption
Fig. 7. Pseudo-second-order kinetic models for adsorption of (a) Ca
2+
and (b) Mg
2+
onto the oxidized CNT sheets at different adsorbate concentrations.
Table 2
Parameters of kinetic models for adsorption of hard mineral ions onto the oxidized CNT sheets.
Ions Cons. (ppm) q
e, exp
Pseudo-rst-order kinetic model Pseudo-second-order kinetic model
q
e
k
1
R
2
q
e
k
2
10
5
R
2
Ca
2+
100 5.4679 2.9833 0.0248 0.9523 5.7241 29.8457 0.9993
300 17.3253 7.2594 0.0415 0.8427 17.7619 20.2165 0.9994
600 34.1258 30.0123 0.0253 0.9901 39.2156 1.4321 0.9949
900 60.0000 55.2586 0.0175 0.9687 89.2857 0.1921 0.9743
1200 77.4598 104.5682 0.0248 0.9254 111.1111 0.1617 0.9863
Mg
2+
100 7.1521 2.7842 0.0156 0.7913 7.3529 31.2945 0.9978
300 21.5626 9.6449 0.0424 0.9080 22.2222 17.5214 0.9992
600 42.2658 41.0487 0.0354 0.9817 50.0000 1.4153 0.9940
900 81.2564 106.2674 0.0396 0.9886 106.3829 0.2809 0.9677
1200 101.459 122.2081 0.0327 0.9837 131.5789 0.2362 0.9786
212 M.A. Toghy, T. Mohammadi / Desalination 268 (2011) 208213
takes place on heterogeneous surfaces. Also, not much difference
among the adsorption intensities (n) of hard mineral ions is observed.
Following the results, to avoid the addition of sodiumor potassium
ions from water softeners to the treated water and also the
environmental problems of the water softeners, the oxidized CNT
sheets with high practical potential can be recommended as an
economical and effective adsorbent for hard water softening in
industrial scale. Using the oxidized CNT sheets as adsorbent
eliminates problems of agitating and removing of the CNTs with and
from water before and after adsorption process, respectively.
4. Conclusion
Chemical vapor deposition was used for synthesis of CNT sheets.
The CNT sheets were oxidized with concentrated nitric acid at room
temperature and then employed as a practical adsorbent for
permanent hard water softening (calcium and magnesium sulfates
removal from water). The adsorption behaviors of hard mineral ions
by the oxidized CNT sheets match well with the Freundlich isotherm
model and the pseudo-second-order kinetic model. Using the
oxidized CNT sheets as adsorbent, economical permanent hard
water softening without CNT leakage into water is feasible.
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Fig. 8. (a) Langmuir and (b) Freundlich isotherms for the adsorption of hard mineral
ions (Ca
2+
and Mg
2+
) onto the oxidized CNT sheets.
Table 3
Parameters of Langmuir and Freundlich isotherms for adsorption of hard mineral ions
onto the oxidized CNT sheets.
Ions Langmuir isotherm Freundlich isotherm
q
m
K
L
10
3
R
L
R
2
n K
F
R
2
Mg
2+
94.3396 0.5769 0.00138 0.7821 1.2727 61.2787 0.9895
Ca
2+
79.6446 0.6019 0.00144 0.9136 1.1692 44.6952 0.9962
213 M.A. Toghy, T. Mohammadi / Desalination 268 (2011) 208213