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a r t i c l e i n f o a b s t r a c t
Article history: Hydrous Ce(IV)Zr(IV) oxide (Ce/Zr 1:1, mol/mol) (HCZMO) prepared by simple chemical precipita-
Received 13 January 2014 tion was nanoparticles (6070 nm) agglomerate with irregular surface morphology. The BET surface
Received in revised form 12 April 2014 area, pore volume and pHzpc were estimated to be 185.04 m2 g1 , 0.1219 cm3 g1 and 5.8 (0.2), respec-
Accepted 14 April 2014
tively. Investigation of uoride adsorption over HCZMO from its aqueous phase at an optimized pH 6.0
Available online 24 April 2014
showed that the adsorption kinetics and equilibrium data described, respectively, the pseudo-second
order equation (R2 = 0.980.99) and the Langmuir isotherm (R2 > 0.99) very well. Values of the com-
Keywords:
puted Arrhenius activation energy, Ea (1.16 kJ mol1 ), Langmuir monolayer capacity, (19.5 mg g1 ), DR
Adsorption
Fluoride
adsorption energy, EDR (15.05 kJ mol1 ) and isosteric heat of reaction, Hr (0.518 kJ mol1 ) suggested
Cerium(IV)zirconium(IV) mixed oxide that the uoride has high afnity for homogeneous HCZMO surface for adsorption. Evidences appeared
Removal from the equal distribution co-efcient values and too well Langmuir isotherm t. The uoride adsorp-
Thermodynamics tion reactions at 298313 K with HCZMO were spontaneous (G0 = negative) despite endothermic nature
Desorption (H0 , kJ mol1 = +3.53, +4.04), owing to the increase of entropy (S0 , J mol1 K1 = +12.4, 13.8). More than
95% uoride was released from F HCZMO (24.8 mg F g1 ) by 1.0 M NaOH, conrming the ion-exchange
adsorption mechanism inclining to chemisorption. 1 g HCZMO per liter of a groundwater (F : 4.40 mg L1 )
can reduce uoride level below 1.5 mg L1 in batch treatment.
2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2014.04.095
0169-4332/ 2014 Elsevier B.V. All rights reserved.
666 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676
process. In this respect, the effects of Ce to Zr mole proportions and 3. Results and discussion
also the calcined temperatures on HCZMO were investigated for u-
oride adsorption for the material optimization. Variable parameters 3.1. Material optimization for uoride adsorption
such as pH, contact time, inuence of uoride concentration and
effect of some groundwater occurring ion on uoride adsorption Some bimetallic hybrid oxides comprising of Ce, Zr, Mn and
over optimized HCZMO sample were carried out by batch method. Sn including single Ce and Zr oxides investigated only for uoride
Here, 50 mL uoride solution at a desired concentration level (Ci , adsorption from its aqueous solution at pH 7.0 have been shown in
mg L1 ) was mixed with 0.05 g of HCZMO (excepting dosage exper- supporting information (SI) section (Fig. SI-1). It shows that the
iment) inside the 100 mL polyethylene (PE) bottles and agitated hydrous Ce(IV)Zr(IV) mixed oxide (HCZMO) showed the high-
at 275 (5) rpm in a thermostated shaker for 2 h (excepting the est capacity of uoride adsorption supporting the pre-assumption
kinetic experiment). Since the pHzpc value of HCZMO was analyzed made.
to be 5.66.0, the batch adsorption experiments were conducted For the optimization, Ce/Zr mole ratio in HCZMO was also varied
with uoride solution at a pH 5.8 (0.2), excepting the pH inuence and investigated for the uoride adsorption. The results obtained
experiments. are presented in Fig. SI-2, which indicated the increase of uoride
Inuences of pH on the uoride adsorption over HCZMO adsorption amount (qe , mg g1 ) with increasing Ce/Zr (mol/mol)
were carried out separately at pH 3.0, 4.0, 5.0, 6.0, 7.0, 8.0 value from 1.0:0.2 to 1:1, and remained nearly constant up to the
and 9.0 loading three separate uoride solutions of initial Ce/Zr ratio 1:4. Thus, the HCZMO having Ce/Zr value 1:1 could
concentrations (Ci , mg L1 ) = 5.0, 10.0 and 20.0 mg g1 , maintain- be a novel material for uoride scavenging from the high uoride
ing other parameters for experiments as specied above kept waters.
xed. Inuence of the calcined temperature of HCZMO (Ce/Zr = 1:1)
Inuences of contact time (for kinetics) on the uoride adsorp- on uoride adsorption amount (qe , mg g1 ) was investigated using
tion reaction with HCZMO were investigated from the solute the calcined (5 h) material at 100 , 200 , 300 , 400 and 500 C sep-
solutions of Ci = 5.0, 10.0 and 20.0 mg L1 (ionic strength, I: 0.1 M arately. Results obtained show nearly same qe value up to a calcined
NaCl solution) and pH = 5.8 0.2. temperature of 300 C (Fig. SI-3). Thus, the material which was used
Isothermal equilibrium experiments were conducted separately calcining at 300 C showed highest capacity (qe = 9.8 1.0 mg g1 )
at 20 , 30 , 40 and 55 C using the uoride solution of C0 ranged of uoride adsorption from a solution of Ci = 10.0 mg L1 , but that
in (5.035.0) mg L1 at an I = 0.1 M NaCl and a pH 5.8 (0.2). Here, material when employed calcining above 300 C at identical exper-
50 mL portion of each uoride solution mixing with 0.05 g HCZMO imental conditions showed a substantial decline of the qe -value
was successively agitated taking in seven separate PE bottles up which is found to be similar with Wu et al. [33] and Liua et al.
to an equilibrium time (2.0 h). Thermodynamic parameters (S0 , [36]. Wu et al. [33] reported that the hydroxyl groups attached
H0 , and G0 ) were evaluated from the analysis of the equilibrium to the surface of metal oxide are primarily responsible for the
results. uoride binding. Thus, the elimination of surface (S) hydroxyl
For estimating the competitive inuences of some groundwa- groups (2S OH 2S O + H2 O) with increasing calcined tempera-
ter occurring ions on the present reaction, 50 mL uoride solution ture causes the depletion of qe value. The as-prepared HCZMO when
(Ci = 10.0 mg L1 ) in the presence of 1.0 mM of a competing ion at calcined at temperatures > 300 C eliminates surface OH groups
pH = 5.8 (0.2) was mixed with 0.05 g HCZMO in PE bottles and as water giving anhydrous material, and causes the depletion of
agitated for 2.0 h. The competing ions were derived from Na2 CO3 , qe value. Moreover, the decrease of surface area with increasing
Na2 HPO4 , NaCl, Na2 SO4 , and Na2 SiO3 . calcined temperature may also diminish the adsorption capacity
For the uoride desorption tests, 0.05 g of uoride-rich HCZMO [36]. Analyzed experimental results conrmed that the as-prepared
(24.8 mg F g1 ) was agitated (300 rpm) for 1.0 h with 50 mL NaOH HCZMO (Ce/Zr 1:1, mol/mol) calcined at 300 C is an optimized
solution (concentrations: 0.14.0 M) taking into PE bottles (capac- material for uoride adsorption. Thus, the HCZMO (Ce/Zr 1:1,
ity: 250 mL). mol/mol) calcined at 300 C was characterized properly by different
After each experiment, the HCZMO particles were separated physicochemical tools, and used for evaluating the uoride adsorp-
immediately after experiment by ltration through 0.45-m mem- tion behavior.
brane lter. Fluoride concentration of each ltrate (Cf , mg L1 ) was
analyzed by SPADANS method using UV-Vis spectrophotometer 3.2. Physicochemical characterization of HCZMO (Ce/Zr 1/1,
[45]. The capacity of HCZMO for uoride adsorption (qe , mg g1 ) mol:mol)
was calculated based on the following mass balance equation
(Eq. (1)): The changes of equilibrium solution pH (pHf ) with respect to
initial solution pH (pHi ) are shown in Fig. SI-4, indicating the pHzpc
of HCZMO analyzed to be 5.8 (0.2). This must have a signicant
role on the adsorption reactions as the material surface should be
(Ci Cf ) V
qe = (1) (i) positive at pH < 5.8 (0.2), (ii) neutral at pH = 5.8 (0.2) and (iii)
M negative at pH > 5.8 (0.2).
Fig. 1 shows the AFM images of HCZMO surface at 2D and 3D
topographic views. A small portion of the 2D image was further
where V is the volume (L) of the solute solution and M is the mass extracted to note the surface prole, particle size approximation
of the adsorbent (g) for conducting experiments. The signicance and their distribution pattern. The surface appeared to be irregular
of Ci and Cf are noted previously. and undulatory in nature. The 3D topographical AFM image indi-
The zero point surface charge pH (pHzpc ) of optimized HCZMO cated porous nature of the sample and absence of any conspicuous
material was analyzed by the procedure as described by Babic structural feature, which is found to be similar with the result as
et al. [46]. Here 0.1 g of HCZMO was mixed to 50 mL 0.1 M reported by Debnath et al. [47]. From the particle size distribution
NaCl solution at an adjusted pH and agitated (300 rpm) for curve, it is evident that the average size of HCZMO particles was
48 h, and pH of each reaction mixture was analyzed. The nal ranged in 5060 nm indicating majority of 50 nm.
pH (pHf ) with respect to its pHi of each reaction mixture was Fig. 2 shows the XRD pattern of HCZMO sample between start
recorded. and end angles (2) of 10 and 70 . The moderate peaks at 28.7 ,
668 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676
Fig. 1. Atomic force microscopic images of HCZMO surface in (a) 3D view (b) 2D view, (c) an extracted prole from the 2D image and (d) the particle size distribution of
HZCMO.
33.1 , 47.6 and 56.4 indicated the presence of crystalline CeO2 adsorbed water, and that at = 1641 cm1 is attributed to the bend-
[48]. The XRD peak patterns also indicated the presence of tetrago- ing vibration of OH group [34,50]. The FTIR band at = 1623 cm1
nal ZrO2 phase [49]. Approximate size of particles calculated from showed the presence of Zr O bond, while that at = 2361 cm1
XRD peak data (inset of Fig. 2) using Scherers formula (a standard and 1380 cm1 were the characteristic peaks of Ce O vibration,
equation of solid-state physics) was ranged in 5565 nm. The par- suggesting the presence of Ce O and Zr O bonds in HCZMO
ticle size as-calculated by the Scherers equation using XRD peak [50].
data agreed well to the inference drawn from the AFM image. Fig. 4 shows the SEM micrograph (image-A) of HCZMO including
Fig. 3 shows the FTIR spectrum of HCZMO sample compar- EDAX analysis (spectrum-B). It has been found from the image-
ing with HZO and HCO. It is seen that the bands appeared for A that the material showed an irregular surface morphology with
HCZMO were at wave number () values 1051, 1133, 1389, 1623, agglomerized particles and porous structure. The surface composi-
2361 and 3325 cm1 . The broad band at = 3466 cm1 in the spec- tion of that material analyzed from the EDAX spectrum showed to
trum of HCZMO can be assigned to the stretching vibration of be nonstoichiometry with empirical formula CeZr1.729 O7.257 .
Fig. 2. XRD analysis of HCZMO with particle size calculation from XRD peak in inset.
A. Ghosh et al. / Applied Surface Science 307 (2014) 665676 669
3.3. Effect of pH
Fig. 4. (A) The scanning electron micrograph of HCZMO, and (B) EDX spectrum with atomic percentages and empirical composition of HCZMO in inset.
670 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676
Table 1
Kinetic parameters for the uoride adsorption reaction with HCZMO (pH 5.8 0.2)
in the presence of 0.1 M NaCl at three different uoride concentrations and temper-
ature 303(2) K.
5 10 20
kinetic parameters estimated relating to each analyzed equation Kinetic models Parameters 288 K 303 K 318 K
was calculated from the slope and the intercept are presented
Pseudo-second order k2 (g mg1 min1 ) 0.012 0.0204 0.026
in Table 2. The values of regression co-efcients (R2 ) and chi qe (mg g1 ) 4.230 5.410 5.740
squared (2 ) have indicated that the pseudo-second order equation R2 0.985 0.994 0.995
described the temperature dependent kinetic data somewhat bet- 2 0.034 0.016 0.015
ter (R2 = 0.9850.995, 2 = 0.0150.034) than the pseudo-rst order Pseudo-rst order k1 (min1 ) 0.051 0.086 0.074
equation (R2 = 0.970.98, 2 = 0.0210.044). The experimental qt qe (mg g1 ) 3.520 4.690 5.020
values were found too close to the modeled qt from pseudo-second R2 0.971 0.984 0.980
2 0.044 0.021 0.022
order kinetics at any given time and temperature. Increase of the
672 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676
Fig. 8. The plot of equilibrium adsorption capacity versus equilibrium concentration of uoride on HCZMO in the presence of 0.1 M NaCl at 303 (2) K and 293 (2) K at pH
5.8 (0.2) and the non-linear data ts with the Langmuir and Freundlich isotherm models.
Table 3
Non-linear and linear isotherm parameters of uoride adsorption equilibrium data on HCZMO at 303 (2) K and pH = 5.8 (0.2) in the presence of 0.1 M NaCl.
mg g1 (Table 3). The performance on uoride adsorption by 3.7. Heat of the reaction
HCZMO was assessed comparing with some literature available
materials (Table 4). It can be said that the present material has good The isosteric heat of adsorption is mainly a function of
prospect for ltration of high uoride groundwater. adsorption density. It can also provide further evidence for site
An essential feature of the Langmuir isotherm can be expressed homogeneity and indicates the reaction nature as endothermic or
by the separation factor (KL ), the dimensionless constant which is exothermic. The isosteric heat of adsorption can be calculated from
expressed by the relation (Eq. (7)). adsorption isotherms at two or more temperatures taking two dif-
ferent adsorbent dose using ClausiousClapeyron Eq. (8) [52].
1
KL = (7)
1 + b Ci R ln(C2 /C1 )
Hr = (8)
1/T1 1/T2
The signicance of each term of equation (7) has already been
given elsewhere. An adsorption reaction should be (i) favorable if KL where Hr is the isosteric heat (kJ mol1 ) of adsorption at a given
ranged in 0 < KL < 1.0, (ii) unfavorable if KL > 1.0, and (iii) irreversible adsorption density, R is the gas constant in SI unit; C1 and C2 are
if KL = 1.0 [61]. Values of the KL for the present adsorption reaction equilibrium concentrations of the adsorbate at temperatures T1
calculated to be ranged in 01.0 even for the Ci of uoride lesser and T2 , respectively. At the reaction temperatures 293 and 303 K,
than 1.0 mg L1 . Thus, the uoride adsorption over HZCMO is a the value of Hr was calculated for any two adsorption densi-
favorable process even at the level of uoride concentration that ties to be 0.518 kJ mol1 (Table 5). Thus, the Hr is independent
occurs commonly in groundwater [62,63]. of adsorption density, which signies the homogeneous nature of
Table 4
Comparative assessment of uoride adsorption capacity of HCZMO with some reported materials.
Table 5
Thermodynamic parameters for the uoride adsorption reaction with HCZMO at pH = 5.8 (0.2) in the presence of 0.1 M NaCl.
Initial uoride concentration (C0 , mg L1 ) H0 (kJ mol1 ) S0 (J mol1 K1 ) G0 (kJ mol1 ) at various temperature (K) Hr (kJ mol1 )
From these Eqs. (9) and (10), the Eq. (11) can be obtained.
S 0 H 0 1 Fig. 9. The plot of log (qe /Ce ) against 1/T (K) 103 for thermodynamic parameters.
log Kc = (11)
2.303R 2.303R T
The thermodynamic equilibrium constant, Kc was calculated by dened as the change of free energy when 1 mol of a solute is trans-
using Eq. (12), ferred to the surface of an adsorbent from innity i.e. from solution
[67] and can be calculated by the relation (Eq. (14)).
qe
Kc = (12)
Ce 1
EDR = (14)
1/2
where qe /Ce is called the adsorption afnity (L g1 ).
Here, qe (2)
(mg g1 ) signies the adsorption capacity and Ce (mg L1 ) is the
where is a DubininRadushkevich (DR) isotherm constant. It
remaining/equilibrium uoride concentration in the solution. So
can be evaluated by tting of the equilibrium data (Fig. 8) with the
the above relation (Eq. (11)) can be written as (Eq. (13))
DubininRadushkevich (DR) isotherm (Eq. (15)) [67]. It is a more
q generalize isotherm than the Langmuir as there is no assumption
e S 0 H 0 1
log = (13) of homogeneity and constancy of adsorption potential [68].
Ce 2.303R 2.303R T
ln Qe = ln Qm 2 (15)
Assuming S0 and H0 to be constant within the range of tem-
perature studied, the values of H0 and S0 can be computed from where Qe and Qm are the equilibrium and saturation capacities
the slope and intercept of the straight line plot of log(qe /Ce ) versus (mol kg1 ) of uoride adsorption a uoride by HCZMO, respec-
1/T, and G0 , the free energy change for the reaction, at various tively. Again, the is related with the equilibrium concentration
temperatures can also be calculated from Eq. (9). (Ce / , mol L1 ) by Eq. (16),
Taking the values of qe (mg g1 ) and Ce (mg L1 ) over a range of
temperature for uoride solution of Ci = 15.0 and 20.0 mg L1 , the 1
= RT ln 1+ (16)
values of log(qe /Ce ) are plotted against 1/T (Fig. 9) which shows /
Ce
a straight line with good regression coefcient value (R2 = 0.99).
The thermodynamic parameters estimated are shown in Table 5, where R is the molar gas constant (8.314 J mol1 K1 ) and T is the
which indicated the spontaneous nature (G0 = negative) of the absolute temperature.
reaction despite the uoride adsorption over HCZMO surface was Like other authors [65,66], the equilibrium data were ana-
an endothermic (H0 = positive) process. Thus, the uoride adsorp- lyzed with the DR isotherm (Eq. (15)) for evaluating the average
tion over HCZMO occurs spontaneously, because the entropy (S0 , energy of adsorption. Here, the values of Qm (mol kg1 ) and
J mol1 K1 = +12.8 and +13.4) increased at the solidliquid inter- (mol2 kJ2 ) were evaluated from the intercepts and the slopes
face when uoride adsorbed over HCZMO from the Ci = 15.0 and of the linear plot of ln qe versus 2 (Fig. SI-9, R2 = 0.976), which
20.0 mg L1 and also the gain of energy from the surroundings were 2.11 and 2.20 103 , respectively. Inserting the value of
[65,66]. The signicant increase of entropy is due to the release of in Eq. (14), the value of EDR obtained was 15.07 kJ mol1 . It is
H2 O molecules at the solidliquid interface with F (aq) adsorption known that an adsorption reaction will occur by (i) physisorption if
by the solid surface. EDR = 8.0 kJ mol1 , (ii) ion-exchange if EDR = 8.016.0 kJ mol1 and
(iii) chemisorptions if EDR > 16.0 kJ mol1 [6567]. As the value of
3.9. Energy of adsorption EDR estimated for the present reaction is 15.07 kJ mol1 and closer
to 16 kJ mol1 , the uoride adsorption reaction with HCZMO will
The mean free energy of adsorption (EDR ) is important for dis- be predicted to be an ion-exchange [65] process with inclination to
tinguishing physical and chemical adsorption process, which is the chemisorptions.
674 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676
3.10. Activation parameters and, the uoride adsorption is too low in alkaline pH range. Based on
this observation, the uoride desorption from F-HCZMO was con-
The activation energy of a reaction can be evaluated from the ducted separately by the batch process varying 0.14.0 M NaOH
Arrhenius equation (Eq. (17)) [52] solution. The results obtained are presented in Fig. SI-13. It has
E been found that the desorption percentage increased with increas-
a
k2 = A exp (17) ing alkali concentration and more than 95% desorption took place
RT
with 1.0 M NaOH solution. The present result has been found to be
where k2 is the rate constant (g mg1 min1 ), A is the temperature- better than the results that reported by Patel et al. [40].
independent factor (g mg1 min1 ), Ea is the activation energy
(kJ mol1 ) of a reaction. The signicances of R and T are known 4. Field validation
well and given earlier.
Taking logarithm of Eq. (17), the following Arrhenius type linear Groundwater sample was collected from a tube well (Location:
relationship (Eq. (18)) can be obtained. Pitidiri village, 23 02.867 N, 86 35.123 E,) of district Purulia in
E 1 West Bengal (India) and analyzed for some water quality param-
a
ln k2 = ln A + (18)
R T eters before treatment with HCZMO. The parameters estimated
(mg L1 except pH) were pH (7.1), total hardness (as CaCO3 ) (620),
Taking the pseudo-second order rate constant value (best t
total alkalinity (385), Ca2+ (86.17), Mg2+ (98.42), Fetotal (0.09),
model), when the value of ln k2 was plotted against 1/T showed
TDS (871), Turbidity (1.8), Na+ (28.9), K+ (4.7), Cl (234.93), F
a straight-line plot (Fig. SI-10) with good regression coefcient
(2.45), PO4 3 (0.05), NO3 (48.82), SO4 2 (286.17) and electrical
value (R2 = 0.99). The values for A and Ea calculated from intercept
conductivity (1340). This groundwater sample was spiked with u-
and slope of the plot were 7.2 104 g mg1 s1 and 1.16 kJ mol1 ,
oride to increase its concentration to 4.4 mg L1 . The solid material
respectively. Very low value of each parameter suggested that the
(HCZMO) of a denite amount ranged in 0.21.0 g was mixed per
uoride has high combining afnity with HCZMO surface.
liter of water sample for estimating the efciency of the material as
uoride scavenger by batch procedure. Here, the reaction mixture
3.11. Adsorption mechanism
was stirred by a digital mechanical stirrer (speed: 1000 rpm) for
2.0 h and ltered. The ltrate of each experiment was analyzed for
Fig. SI-11 shows the FTIR spectra of HCZMO and F adsorbed
uoride. The results obtained are shown in Fig. SI-14. It has been
HCZMO. It is seen that the bands at = 1051 and 1133 cm1 of
seen that 1.0 g HCZMO per liter of water can reduce the uoride
HCZMO shifted to 1089 cm1 , respectively, indicating the forma-
level from 4.4 mg L1 to below 1.50 mg L1 , which is below the per-
tion of M F linkage [50]. It is exciting that the three new peaks
missible level of uoride in drinking water for the countries of cold
at = 1744, 2851 and 2926 cm1 appeared in the spectrum of
climate. Increase of HCZMO dose from 1.0 g to 1.5 g per liter of water
uoride-rich HCZMO, which might be for the formation of Ce F
reduced to uoride level to below 1.0 mg L1 , which is below the
and Zr F bonds those arose owing to uoride adsorption. In addi-
permissible level for the countries of hot climate.
tion, the estimated pH-effect (Section 3.3), binding constant and
the EDR (15.07 kJ mol1 ) values suggested previously that the pos-
sible adsorption mechanism of uoride by HCZMO can be expressed 5. Conclusion
by the reactions (R4 ) and (R5 ) presented in effect of pH sub-section.
This agrees well with (i) the small change of the solution pH and (ii) In the present study, HCZMO was prepared by low tempera-
the existence of S F bond in the FTIR spectrum of uoride adsorbed ture and green method; and characterized as a microcrystalline
HCZMO. The mechanism proposed is similar with other researchers nanostructured material with irregular surface morphology. The
[33,68] for uoride adsorption over metal oxide surface. pHzpc (5.8 0.2) and BET surface area (185.04 m2 g1 ) has indicated
good possibility to be used as an adsorbent for water treatment.
3.12. Competitive effect of some ground water occurring ions This material when used for uoride adsorption showed highest
capacity at pH 5.56.0. The kinetic of uoride adsorption over
Common ground water occurring anions are phosphate, chlo- HCZMO occurred according to the pseudo-second order kinetic
ride, sulphate, carbonate, and silicate which may inuence model. The Langmuir isotherm which described the equilibrium
uoride adsorption over HCZMO. Fig. SI-12 displays the result well showed the monolayer adsorption capacity 19.5 mg g1 .
of uoride adsorption over HCZMO in the presence of ions Low activation energy (1.16 kJ mol1 ) and high adsorption energy
specied above. It is found that the sequence of adverse inu- (15.05 kJ mol1 ) indicated high afnity of uoride for HCZMO sur-
ence on uoride adsorption over HCZMO can be given as face. Surface homogeneity and endothermicity indicated from
HPO4 2 > Cl > SO4 2 > HCO3 > SiO3 2 . It has been seen that the isosteric heat of reaction (Hr ) had been conrmed from the
phosphate ion has stronger adverse effect comparing to others on Langmuir isotherm t and positive H0 , respectively. The spon-
uoride adsorption over HCZMO. It appears also that the chloride taneity of uoride adsorption over HCZMO (G0 = negative) despite
might compete well with uoride to get adsorbed on HCZMO sur- endothermic (H0 = positive) is owing to the increase of entropy
face. The signicantly strong adverse inuence of phosphate on (S0 = positive) of this reaction. 50 mL of 1.0 M NaOH solution is
uoride adsorption was also reported for the case of adsorbents regenerated the 0.1 g uoride-rich material up to >95%. Batch treat-
such as chitosan beads [63], granular ferric hydroxide [69], and ment of 1.0 L eld sample with 1.0 g of HCZMO reduced the uoride
CeAl mixed metal oxide [70]. Fortunately, the phosphate concen- level from 4.4 mg L1 to well below of 1.5 mg L1 , indicating good
tration in groundwater is very low [70]; hence its effect on uoride application possibility of HCZMO for the treatment of high uoride
adsorption by HCZMO could hardly be a limiting factor. ground water.
According to the pHzpc of HCZMO and initial pH-effect on the Authors wish to extend their sincerest thanks to the Depart-
uoride adsorption by HCZMO, it was found that the uoride ment of Science and Technology, Govt. of India, New Delhi for
adsorption by HCZMO decreased signicantly with increasing pH awarding JRF to Abir Ghosh. Authors are also grateful to the Head,
A. Ghosh et al. / Applied Surface Science 307 (2014) 665676 675
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