Effect of Silver Activation of Zirconium Phosphate on the Methylene

Journal of Applied Sciences Research 5(7): 893-904, 2009
© 2009, INSInet Publication
Effect of Silver Activation of Zirconium Phosphate on the Methylene
Blue Adsorption
1
Z. Barhon, 2 A. Albizane, 1 M. Azzi, 3 N. Saffaj, 3 J. Bennazha, 2 S.A. Yo Unssi
1
Laboratoire Interface Matériau et Environnement, Université Hassan II – Ain Chock,
Casablanca, Maroc
2
Laboratoire de Matériaux, Environnement et Catalyse, Université Hassan II - Mohammedia,
Maroc
3
Université Ibn Zohr. Faculté Polydisciplinaire de Ouarzazate - Maroc
Abstract: Batch sorption experiments were carried out using á -zirconium phosphate and silver activated
zirconium phosphate for the removal of methylene blue (MB) from aqueous solutions. Effects of process
parameters pH, contact time and temperature were studied. Equilibrium data are mathematically modeled
using the Freundlich and Langmuir adsorption models. Maximum dye uptake was found to be 38 mg/g
and 122 mg/g for á -zirconium phosphate and silver activated zirconium phosphate respectively. The
results indicate that zirconium phosphate can be used as a good adsorbent. Pseudo-first-order, pseudosecond order and intraparticle diffusion models were tested. From experimental data it was found that
adsorption of MB onto the both materials follow pseudo second order kinetics. External diffusion and
intraparticle diffusion play roles in adsorption process. Free energy of adsorption (ÄGE), enthalpy change
(ÄHE) and entropy change (ÄSE) were calculated to predict.
Key words: Methylene Blue; Zirconium phosphate; Silver nitrate; Adsorption kinetic
coagulation [6] , photodegradation [7], and adsorption [8].
Currently, adsorption processes are usually used
due to their economic, ecological and technological
advantages. Among many kinds of adsorbents has often
been used in the remove of organic pigments and dyes
due to its low cost, high surface area and high cation
exchange capacity [9].
Zirconium phosphate is an important class of
inorganic material that is widely studied in different
chemical fields including ion exchange, high
temperature stability, performance and high reactivity,
ion conduct and catalysis, and has received
considerable attention [10].
Sorption capacity of synthetic zirconium phosphates
is related to their relatively no negligible surface area,
swelling properties and high cation exchange capacity.
The assessment of applicability of this kind of material
should be based on a detailed description of structural
and chemical properties such as pore structure and
surface acidity. The chemical treatment of synthetic
zirconium phosphates has long been studied with the
intention of modifying their texture and acidity in order
to make them useful as adsorbents or catalysts
supports [11,12].
INTRODUCTION
Nowadays the preservation of water resources to
prevent their pollution by toxic elements is one of the
more important challenges for the human race because
the progress of textile, leather, surface treatment,
mining, motorcar and chemical industries generate
toxics such as dyes which are ejected into the
environment [1,2] . Methylene Blue is a basic (or
cationic) dye employed in several industrial fields, such
as textiles, paper, and cosmetics. Its presence in
discharged water represents a serious problem because
of its persistence and non-biodegradable characteristics.
Highly colored effluents containing Methylene Blue can
affect aquatic life present in natural water by
decreasing sunlight penetration and/or even leading to
direct poisoning of living organisms [3]. Although its
low toxicity, it can cause some specific harmful effects
in humans such as heartbeat increase, vomiting shocks,
cyanosis, jaundice and tissue necrosis [4].
Consequently, there is considerable need to treat
these effluents prior to their discharge into receiving
waters. There are many techniques for removing dyes
from waste water, such as, membrane process [5],
Corresponding Author:
Z. Barhon, Laboratoire Interface Matériau et Environnement, Université Hassan II – Ain Chock,
Casablanca, Maroc.
Tél + 212 6 63 27 31 96, Fax +212 5 22 66 53 04
E-mail address: [email protected]
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J. App. Sci. Res., 5(7): 893-904, 2009
Different metals such as Ag, Cu and Zn were used
in the modification of Zirconium phosphate [13,14]. The
silver loaded zirconium phosphate was recently
emerging as various commercial products due to its
high antibacterial activity [15], its catalytic activity [16]
and its good photochemical property [17,18].
In the present study, aqueous solutions of MB
were used as model compound in an attempt to
evaluate sorption properties of á-zirconium phosphate
and silver activated zirconium phosphate. The
equilibrium, kinetic and thermodynamic data of the
adsorption process were also studied to understand the
adsorption mechanism of methylene blue molecules
onto zirconium phosphate samples.
2.3. Kinetic Procedure: Batch studies were conducted
in an automatic shaker using 100 cm 3 of adsorbate
solution and a fixed adsorbent dosage. The agitation
speed of the shaker was fixed at 300 rpm for all batch
experiments. The samples at different time intervals (0120 m in) were taken and centrifuged. T he
concentration of the supernatant at different time
intervals was analyzed as before.
2.4. Effect of Temperature: A 100 mg of synthetic
Ag-ZrP sample was added to each 500 cm 3 volume of
methylene blue aqueous solution having a known initial
concentration. The experiments were carried out at 27,
40, 60, 80 and 90º C in a constant temperature shaker
bath which controlled the temperature to within ±2 ºC.
In all cases, adsorption equilibrium was reached within
2h.
M ATERIALS AND M ETHODS
2.1. Preparation and Characterization of Zirconium
Phosphates: Amorphous zirconium phosphate a-ZrP
was prepared as described by Clearfield method [19]. áZirconium phosphate was prepared by refluxing
amorphous zirconium phosphate a-ZrP in phosphoric
acid H 3PO 4 for 24h. The resulting crystalline á- ZrP
was centrifuged, washed with deionised water and dried
at 80°C for 48h.
2.5. Thermodynamic Parameters: In order to fully
understand the nature of adsorption, the thermodynamic
studies play an important role to determine spontaneity
and heat change for the adsorption process. This paper
also presents the thermodynamics parameters related to
the adsorption of dyes such as free energy change
(ÄG º ), enthalpy change (ÄH º ) and entropy change (ÄS º),
which have been calculated using following equations:
On the other hand, silver activation was made by
adding 5g of amorphous zirconium phosphate a-ZrP to
solution of silver nitrate AgNO 3 (400 mg; 200 cm 3)
and agitated for 1h. Then, 18 cm 3 of phosphoric acid
H 3PO 4 was added and the mixture was refluxed for 2
days to yield precipitate denoted Ag-ZrP for the
simplicity. The sample was centrifuged, washed with
deionised water and dried at 80°C for 2 days. For all
samples, the phases X-ray powder diffraction (XRD)
patterns were obtained by Philips X'Pert PRO with Cu
Ká radiation and the FTIR measurements were
performed with 4 cm -1 resolution by VERTEX 70
spectrometer.
(1)
where R is gas constant and K is the equilibrium
constant and T is the temperature in Kelvin. According
to van’t Hoff equation:
(2)
and the free energy change can be obtained as:
(3)
ÄG o and ÄS o can be obtained from the slope and
intercept of a van’t Hoff plot of ln K versus 1/T.
2.2. Adsorption Experiments: All solutions were
prepared from reagent-grade purity chemicals without
further purifications. Aqueous methylene blue was
prepared from its chloride salt (Methylene blue
chloride, Merck, M = 319.86 g.mol-1).
In adsorption experiments, methylene blue
concentration was varied in 30–70 mg.dm -3 range. The
pH of the solutions, ranging from 4 to 10, was
adjusted using nitric acid and sodium hydroxide. At the
end of each adsorption period, the supernatant was
centrifuged. The concentration of MB remaining in the
supernatant after adsorption was determined using UVVIS spectrophotometer (Standard UNICAM) at ë max
of 663 nm.
RESULTS AND DISCUSSION
3.1. Characterization: The XRD patterns of á –ZrP
and Ag-ZrP is reported in Fig. 1. The spectra of both
materials exhibit the same main reflections with
different intensity and resolution. On the other hand,
the interlayer spacing for all materials was retained at
around 0.75nm. The X-ray diffraction patterns of á-ZrP
indicated that a well crystallized material was obtained,
in agreement with published data [20] whereas Ag-ZrP
presents broad ill-defined reflections indicating its low
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J. App. Sci. Res., 5(7): 893-904, 2009
Fig. 1: X-ray powder diffraction of (a) á-ZrP, and (b) Ag-ZrP
cristallinity. The different degrees of crystallinity can
be also associated with the modification of sample
morphology [21].
Clearfield and co-workers have shown that the unit
cell dimensions of á –ZrP vary with the degree of
crystallinity [22] . The ratio of intensities of the 002 and
204 is known to vary; samples exhibiting preferred
orientation of the particles have an intense reflection
corresponding to hkl = 002, where with as low
crystallinity materials such as Ag-ZrP have the 204
reflection as the more intense [20]. This low crystallinity
for Ag-ZrP can be due to the exchange of Hydrogen
ions by silver ions.
These results were assessed by FTIR data (Fig. 2)
from which it was shown that there is no drastic
change observed in band position in the FTIR spectrum
of Ag-ZrP as compared to á-ZrP. However, the
intensities of some peaks (Table 1) concerning the OH
bands were slightly reduced after activation of
Zirconium phosphate by silver nitrate confirming
probably the substitution of hydrogen by silver ions.
adsorbent was more protonated and competitive
adsorption occurred between H + protons and free dye
ions and their hydroxides toward the fixation sites [23].
Therefore, H + ions react with anionic functional groups
on the surface of the adsorbent and result in restriction
of the number of binding sites favourable for the
adsorption of MB ions. However, a favourable increase
in adsorption for all materials was observed above pH
8.0. The reason of this behaviour is that the surface is
predominantly negative due to dissociation of weakly
acidic oxygen-containing groups takes place. Thus, the
adsorbent surface is able to attract and exchange
cations in solution. Coulombic forces favour the
interaction of cationic dyes. At pH > 8, a decrease in
adsorption of MB ions was observed due to the
formation of soluble hydroxyl complexes [24]. All
further experiments were carried out at pH 8.0.
3.2.2. Effect of Contact Time: Fig. 4. shows the
removal of methylene blue on different samples as a
function of contact time. It is apparent that removal of
MB ions is dependent on the contact time. Indeed, the
adsorption is rapid in the early stages and then attains
an asymptotic value for larger adsorption time when
equilibrium is reached. This is due to the high
concentration gradient in the beginning of adsorption
which represents a high driving force for the transfer
of MB from solution to the surface of supports [7]. On
the other hand, silver activation of samples leads to an
increase in the adsorption capacity of methylene blue.
This is indicative of the high number of exchangeable
sites and specific surface area produced after silver
activation of the studied material.
3.2. Adsorption Study:
3.2.1 Ph Effect: The effect of pH on adsorption of
MB ions on á-ZrP and Ag-ZrP was studied at a
temperature of 27±2°C by varying the initial pH and
the results are shown in Fig. 3. They have revealed
that pH is the dominant parameter controlling the
adsorption.
The dye ions uptake increased with increasing pH
because the anionic groups are more available to retain
adsorbate ions. At lower pH, the amount adsorbed was
found to decrease because the surface area of the
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J. App. Sci. Res., 5(7): 893-904, 2009
Fig. 2: Infrared spectra of (a) á-ZrP, and (b) Ag-ZrP
Table 1: Assignment of features observed in optical vibrational
Peaks (cm-1 )
Assignment
970
ã (POH) stretching vibration
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------1619
(í2 ) ‘scissors’ mode of crystal water
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------3170
(í3 ) antisymmetric or (í1 ) symmetric stretches of the crystal/interlayer water
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------3509
(í1 ) symmetric stretches of the crystal/interlayer water
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------3598
(í3 ) antisymmetric stretches of the crystal/interlayer water
Fig. 3: Effect of pH on MB adsorption onto (a) á-ZrP and (b) Ag-ZrP, Conditions : Adsorbent dosage 200
mg.dm -3, t = 2h, MB concentration 40 mg.dm -3
suitable model that can be used for design purposes [25].
The salient features of isotherms are needed before the
kinetics of the adsorption process is interpreted. The
dynamic adsorptive separation of solute from solution
onto an adsorbent depends upon a good description of
the equilibrium separation between the two phases.
3.2.3. Isotherm Studies: The adsorption isotherm
indicates how the adsorbate molecules distribute
between the liquid phase and the solid phase when the
adsorption process reaches an equilibrium state. The
analysis of the isotherm data by fitting them to
different isotherm models is an important step and the
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J. App. Sci. Res., 5(7): 893-904, 2009
Fig. 4: Effect of time on removal of MB ions on (a) á-ZrP, and (b) Ag-ZrP Conditions : Adsorbent dosage 200
mg.dm -3, temperature 27±2°C, pH 8.0.
Many models have been proposed to explain adsorption
equilibrium, but the most important factor is to have
applicability over the entire range of process
conditions. The most widely used isotherm models for
solid-liquid adsorption are the Freundlich and Langmuir
isotherms.
(5)
where q m is the maximum amount of adsorption
(mg.g-1 ), K L is the affinity constant (dm 3.mg -1) and C e
is the solution concentration at equilibrium (mg.dm-3).
The Langmuir isotherms are plotted in Fig. 5.2. The
adsorption capacities predicted by the two isotherms
are compared and the corresponding Freundlich and
Langmuir isotherm parameters, along with the
regression coefficients are listed in Table 2.
3.2.3.1. Freundlich Isotherm: The Freundlich model
assumes that the sorption takes place on heterogeneous
surfaces and adsorption capacity depends on the
concentration of dye at equilibrium. The well-known
logarithmic form of Freundlich model is given by the
following equation [26, 27]:
Examination of the data shows that the Langmuir
model parameters describe the adsorption of MB ions
onto different samples better than that of Freundlich
model. The linear R² coefficients for the linearized
Langmuir plots are all above 0.99 revealing good
correlation of experimental data to the Langmuir
model.
(4)
where K F and n are the Freundlich constants
related to adsorption capacity and adsorption intensity,
respectively. So, the plot of ln qe against ln Ce of Eq.
(4) should give a linear relationship, from which 1/n
and K F can be determined from the slope and the
intercept respectively. The theoretical Freundlich
isotherms are shown in Fig. 5.1.
3.2.4 Kinetic Studies: The kinetics of adsorption
describes the rate of dye uptake on zirconium
phosphate materials (ZrP) and this rate controls the
equilibrium time. The kinetics of adsorbate uptake is
required for selecting optimum operating conditions for
the full-scale batch process [29]. The kinetic parameter,
which is helpful or the prediction of adsorption rate,
gives important information for designing and
modelling the processes. The kinetics of the sorption
data was analyzed using different kinetic models such
as pseudo-first-order and pseudo-second-order models.
3.2.3.2. Langmuir Isotherm: The Langmuir theory
assumes that sorption takes place at specific sites
within the adsorbent, which means that once a dye
molecule occupies a site, no further adsorption can take
place at that site. Therefore, at equilibrium, a saturation
point is reached beyond which no further adsorption
can occur and the saturation monolayer can be then
represented by the following expression [28]:
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J. App. Sci. Res., 5(7): 893-904, 2009
Fig. 5: Adsorption isotherms predicted by (1) Freundlich and (2) Langmuir models of MB on (a) á-ZrP, and (b)
Ag-ZrP Conditions: Adsorbent dosage 200 mg.dm -3, pH 8.0., temperature 27±2°C
Table 2: Freundlich and Langmuir parameters for adsorption of MB dye onto studied samples
Langmuir parameters
Freundlich parameters
--------------------------------------------------------------------------------------------------------------------------------------------------KL (dm3 .mg-1 )
qm (mg/g)
R2
KF (mg/g)
1/n
R2
á-ZrP
0,090
51,89
0,99
19,70
0,194
0,93
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Ag-ZrP
0,432
135,31
0,99
72,76
0,159
0,92
at time t (min) and equilibrium time, respectively. The
first order constants can be obtained by plotting log (q e
- q t) versus time, as shown in Fig. 6.
The adsorption kinetics were best described by
Lagergren model for the first 20 min and thereafter the
data deviate from theory for all the samples. Thus, the
model represents the initial stages where rapid
adsorption occurs well but cannot be applied for entire
adsorption processes [31]. This confirms that it is not
appropriate to use the Lagergren model to predict the
adsorption kinetics for MB ions onto studied samples
for the entire sorption period. The regression
coefficients (R ²) were in the range of 0.85-0.86, which
3.2.4.1. Pseudo-first-order M odel: Sorption kinetic
data were treated with the Lagergren first-order rate
model [30],
(6)
Integrating Eq. (6), the kinetic rate expression
becomes
(7)
where K 1 (min-1) is the first-order rate constant, q t
and q e,1 (mg.g -1) represent the amount of dye adsorbed
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Fig. 6: Pseudo-first-order adsorption kinetics of MB on (a) á-ZrP, and (b) Ag-ZrP Conditions: Adsorbent dosage
200 mg.dm-3 , MB concentration 40 mg.dm-3 , pH 8.0., temperature 27±2°C
shows that the model can be applied but it is not
appropriate to describe the entire process. The
experimental data and model predicted data are
represented in Table 3.
3.2.5. Adsorption M echanism: For a solid-liquid
sorption process, the solute transfer is usually
characterized by external mass transfer (boundary layer
diffusion), or intraparticle diffusion, or both [32]. The
three steps analyze the mechanisms of adsorption as
follows:
1. Migration of the solute from bulk of the solution
to the surface of the adsorbent
2. Diffusion of the adsorbate through the boundary
layer to the surface of the adsorbent
3. Adsorption of the adsorbate at an active site on
the surface of the adsorbent
4. Intra-particle diffusion of adsorbate into the
interior pores of the adsorbent.
Generally, the last step is the equilibrium reaction
and it is very rapid; the resistance is hence assumed to
be negligible. The slowest step determines the ratecontrolling parameter in the adsorption system.
However, the rate-controlling parameter might be
distributed between intraparticle and film diffusion
mechanisms. In order to see whether the intra-particle
diffusion is a rate limiting step in the adsorption
process, a study is undertaken by using the model of
intra-particle diffusion.
According to W eber and Morris [33], the
intraparticle diffusion varies with square root of time
and a characteristic coefficient K id is given by the
equation
3.2.4.2. Pseudo-second-order M odel: The sorption
data was also analyzed in terms of pseudo-second-order
mechanism [31] , described by in linear form:
(8)
W here q e,2 (mg.g -1), is the maximum adsorption
capacity and K 2 (g.mg-1.min-1) is the rate constant of
pseudo-second-order adsorption.
If initial adsorption rate is
(9)
then Eq. (8) becomes
(10)
If pseudo-second-order model is applicable, the
plot of t/q t versus t of Eq. (10) should give a linear
relationship from which the constants q e,2, h and K 2 can
be determined. The results of the linear correlation of
t/q t according to t (Fig. 7) are noted in Table 4.
The predicted values of q e,2 agree very well with
experimental values and regression coefficients of
above 0.99 shows that the adsorption phenomena
followed second-order kinetics for the entire adsorption
process.
(11)
where K id (mg.g-1.min -1/2) and C are the
intraparticle diffusion rate constant related to the extent
of boundary layer thickness.
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Table 3: First-order kinetic parameters of MB
qe,1 (mg.g-1 )
K1 (min-1 )
R2
á-ZrP
4,96
0,058
0,85
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Ag-ZrP
12,47
0,102
0,86
Fig. 7: Pseudo-second-order adsorption kinetics of MB on (a) á-ZrP, and (b) Ag-ZrP Conditions: Adsorbent
dosage 200 mg.dm -3, pH 8.0., temperature 27±2°C
Table 4: Second-order kinetic parameters of MB
K2 (g.mg-1 .min-1 )
qe,2 (mg.g-1 )
R2
á-ZrP
0,033
38,31
0,99
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Ag-ZrP
0,008
123,91
0,99
In the M orris–W eber model, if a straight line
passing through the origin is obtained when plotting t1/2
against q t, an intraparticle diffusion process can be
assumed as the rate controlling step of the adsorption
process [34] . W hen the plot does not pass through origin
it is possible to conclude that a boundary layer effect
occurs at a given degree and thus the intraparticle
diffusion process is not the unique rate controlling
step [35].
In the plot of q t versus t1/2 (Fig. 8), the same
general trend was obtained with first curved shape
followed by a linear relationship and finally a plateau
region. The plot shows two parts, the initial curved
portion can be attributed to the effect of the diffusion
layer and the second linear portion that can be related
to the intra-particle diffusion [36] and plateau to the
equilibrium. In this stage, the intraparticle diffusion
starts to slowdown, probably due to the low
concentration of solute in the liquid phase [3]. The
slope of the linear part of the plot is considered as a
kinetic parameter (K id) characteristic of the kinetic of
adsorption in the domain where the intraparticle
diffusion is a limiting step and the intercept C
representative of the thickness of the interface solutionadsorbent; i.e. the larger of the intercept, the greater is
the boundary layer effect. The calculated intraparticle
diffusion parameters are given in Table 5. The
intraparticle diffusion process is controlled by the
diffusion of ions within the adsorbent.
3.2.6. Effect of Temperature: In order to assess the
effect of temperature on A g-ZrP adsorption
performance, Fig. 9 was drawn and showed that an
increase in temperature (from 27 to 95 ºC) leads to
increase in MB uptake. The adsorption isotherms
present a linear increase of adsorption capacities at low
dye concentrations indicating great affinity of MB
molecules towards material layers [37].
3.2.7. Thermodynamic Parameters: A typical ln K vs.
1/T plot is shown in Fig. 10. The thermodynamic
quantities calculated are given in Table 6. The values
demonstrate a spontaneous and favourable adsorption
process in all the temperature range (ÄG º < 0). The
negative values of standard Gibbs energy change (ÄG º)
in all the cases are indicative of the spontaneous nature
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J. App. Sci. Res., 5(7): 893-904, 2009
Fig. 8: Intraparticle diffusion plot for the adsorption of MB on (a) á-ZrP, and (b) Ag-ZrP Conditions: Adsorbent
dosage 200 mg.dm-3 , MB concentration 40 mg.dm -3 , pH 8.0., temperature 27±2°C
Table 5: Intraparticle diffusion rate parameters and diffusion coefficients
Kid /(mg.g-1 .min1 /2 )
C
á-ZrP
0,084
37,17
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Ag-ZrP
0,201
120,69
Fig. 9: Adsorption isotherms of MB retention onto Ag-ZrP as function of temperature
Table 6: Thermodynamic parameters for adsorption of methylene blue on studied sample
T /(K)
ÄGo /(kJ.mol-1 )
ÄHo /(kJ.mol-1 )
ÄSo /(J.K-1 .mol-1 )
R2
300
-1,036
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------313
-1,172
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------333
-2,439
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------353
-3,289
11,72
42,52
0,99
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------363
-3,714
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------353
-5,579
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------368
-6,672
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J. App. Sci. Res., 5(7): 893-904, 2009
Fig. 10: ln K vs. 1/T for MB adsorption onto Ag-ZrP
of the interaction without requiring large activation
energies of adsorption. As can be seen from the Table
6, the adsorption process of MB is more and more
favourable at highest temperatures; ÄGº was found to
decrease with increasing adsorption temperature.
The positive value of entropy change reflects the
affinity of the Ag-ZrP for MB and increased
randomness at the solid/solution interface with some
structural changes in the adsorbate and adsorbent. Also,
positive (ÄSº ) value corresponds to an increase in the
degree of freedom of the adsorbed species [37].
2.
3.
4.
Conclusion: Silver activated Zirconium phosphate (AgZrP) shows better adsorption of MB ions than á-ZrP.
Initial 20 min was sufficient to exchange most of MB
ions from their aqueous solutions. The optimum pH for
the adsorption of MB was around 8.
Equilibrium removal by zirconium phosphates
samples followed typical adsorption isotherms such as
Langmuir isotherms. On the other hand, MB ions
adsorption was found to obey a pseudo-second-order
model. The adsorption process was found to be
controlled by both film diffusion as well as pore
diffusion.
This study indicates viability of modified zirconium
phosphates in pollution monitoring of warm industrial
effluents. Hence the studied samples can be suggested
as an alternative to adsorb MB dye from aqueous
pollutants in standard conditions.
5.
6.
7.
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