The adsorption potential of iron acetate coated activated alumina (IACAA) for removal of arsenic [As (III)] as arsenite by batch sorption technique is described. IACAA was characterized by XRD, FTIR, EDAX and SEM instruments. Percentage adsorption on IACAA was determined as a function of pH, contact time and adsorbent dose. The study revealed that the removal of As (III) was best achieved at pH =7.4. The initial As (III) concentration (0.45 mg/L) came down to less than 0.01 mg/L at contact time 90 min with adsorbent dose of 1 g/100 mL. The sorption was reasonably explained with Langmuir and Freundlich isotherms. The thermodynamic parameters such as ΔG0, ΔH0, ΔS0 and Ea were calculated in order to understand the nature of sorption process. The sorption process was found to be controlled by pseudo-second order and intraparticle diffusion models.
The adsorption potential of iron acetate coated activated alumina (IACAA) for removal of arsenic [As (III)] as arsenite by batch sorption technique is described. IACAA was characterized by XRD, FTIR, EDAX and SEM instruments. Percentage adsorption on IACAA was determined as a function of pH, contact time and adsorbent dose. The study revealed that the removal of As (III) was best achieved at pH =7.4. The initial As (III) concentration (0.45 mg/L) came down to less than 0.01 mg/L at contact time 90 min with adsorbent dose of 1 g/100 mL. The sorption was reasonably explained with Langmuir and Freundlich isotherms. The thermodynamic parameters such as ΔG0, ΔH0, ΔS0 and Ea were calculated in order to understand the nature of sorption process. The sorption process was found to be controlled by pseudo-second order and intraparticle diffusion models.
Arsenic contamination in natural water is the worldwide problem. There have been
widespread reports of arsenic poisoning, in the major parts of Ganga delta in West
Bengal [1], Brahmaputra basin [2], in northern eastern part of India, particularly Golaghat district of
Assam [3] and other low-lying areas in Bangladesh [4]. The provisional standard guideline for concentration of arsenic is fixed
at 10 ppb (0.01 mg/L) in the drinking water.In natural waterarsenic exists in inorganic forms with the oxidation [5] states −3, 0, +3 and +5. Arsenic is uniquely sensitive to
mobilization (at pH 6.5-8.5) under both oxidizing and reducing conditions [6]. Predominantly, the species arsenite [As (III)] and arsenate [As (V)]
exist in ground and surface water respectively. This is why trivalent arsenite
predominates in moderately reducing anaerobic environments such as groundwater [7] and pentavalent species are stable in oxygen rich aerobic environments.
It is reported that As (III) is more toxic to biological systems than As (V) [8]. Inorganic species of arsenic represents a potential threat to
environment, human and animal health due to their carcinogenic and other effects.
Long term drinking water exposure causes skin, lung, bladder and kidney cancer as
well as pigmentation changes, skin thickening (hyperkeratosis) neurological
disorders, muscular weakness, and loss of appetite [9]. It is very essential, therefore, to remove arsenic from water. Usually,
a removal technique of arsenic from aqueous system should be: (i) safe in operation
with respect to the maximum contaminant level, (ii) highly efficient, (iii) easy for
application and (iv) low cost [10]. Conventional water treatment processes remove toxic metal ions through
mechanism such as sorption and particle removal. Advanced water treatment
techniques, which can be used as either a primary treatment or post treatment,
involve ion exchange, reverse osmosis, adsorption, coagulation, precipitation,
adsorption-co precipitation with hydrolyzing metals [11] etc. Now a day, the adsorption process is getting the best preference
over other treatment processes. Available literature demonstrated that arsenic
removal can be achieved by adsorption process using activated alumina [12] iron oxide-coated sand [13] iron oxide-coated cement [14] and activated red mud [15]. There is also report of arsenic removal by coagulation method using
ferric chloride [16]. The removal of arsenic from drinking water using activated alumina (AA)
is found to be the best removal adsorbent as per reports [17]. However, for As (III) removal, both the rate of adsorption as well as
low adsorption capacity of As (III) limits the use of AA [18]. But most of the oxides of iron and manganese are available only as fine
powders or are generated in aqueous suspension like hydroxides or gels [19]. Adsorbents in powder form have practical limitations, including
difficulty in solid/liquid separation, low hydraulic conductivity and leaching of
the metal/metal oxide along with treated water [20].Present study was carried out to evaluate the performance of iron acetate coated
activated alumina (IACAA) for As (III) removal. The process parameters such as
effect of adsorbent dose, pH, initial concentration and contact time were
investigated. The Langmuir and Freundlich isotherm models were tested for their
applicability. Thermodynamic parameters for the process were also calculated to
complete the investigation for efficacy of IACAA in removal of arsenic from
contaminated water.
Method and methodology
Arsenic trioxide, iron acetate, hydrochloric acid and sodium chloride of analytical
reagent grade were procured from E. Merck (India) Ltd and used as received.
Activated alumina was obtained from Loba Chemie Pvt., India with size between 70 and
230 μm. Double distilled (DD) water was used throughout for preparing solution.
All the instruments used for the experimental purpose were calibrated as per
recommended procedure. The initial pH of the arsenic solutions was adjusted using
NaOH (0.1 M) and/or HCl (0.1 M) solutions as and when necessary and measured by
Cyberscan pH 510 (Eutech) instrument. The determination of concentration of arsenic
was done using AAnalyst 200 Atomic Absorption Spectrophotometer (Perkin Elmer). All
the measurements were based on integrated absorbance and performed at 193.7 nm by
using a quartz tube analyser (Perkin Elmer) followed by the atomization temperature
2000 K. Scanning Electron Microscope (JEOL 6390LV) was used to study the morphology
of the samples. The Energy Dispersive X-rays Analysis (EDAX) attached to the SEM was
used to analyze the elemental constituents of the adsorbents. Mineral phases of
activated alumina, iron acetate coated activated alumina and arsenic adsorbed iron
acetate coated activated alumina were characterized by powder X-ray diffraction
(Bruker D8). The measurement conditions were taken as follows: anode material = Cu;
K-alpha, ג = a 1.5406 Ǻ. Fourier Transform Infrared Spectrophotometer
(FTIR) spectrum, (NICOLET Impact I-410) was used to scan the elements.Preparation of IACAA was carried out in two steps. In first step, 25 g of
activated alumina was impregnated with 25 mL of 1.5 M
(CH3COO)2Fe in a heat resistant dish and the mixture was
heated to 110°C after thorough mixing, until it became dry. In the second step,
the same mixture was calcined at 400°C for 3 hours, cooled to room
temperature and washed with DDwater until the washed water became clear. The washed
samples were dried at 110°C for 8 hours and stored in air tight containers
for further use.Batch sorption experiments were conducted to obtain rate and equilibrium data. The
reaction mixture consisting 100 mL of known concentration of As (III) solution
and known quantity of IACAA was shaken in a temperature controlled orbital shaker at
three different temperatures of 301 K, 306 K and 311 K. Spiked waterarsenic concentration was fixed at 0.45 mg/L. The effect of adsorbent dose was
studied by varying the adsorbent dose from 0.1 g/100 mL to
2.5 g/100 mL and maintaining pH of the solution at 7.4 with a constant
contact time of 90 min. The study of the effect of initial pH of the solutions
on arsenic uptake by the adsorbent was done by using fix dose of the adsorbent at
varying pH of the solutions. The effect of contact time was studied with varying
contact time from 30 to 180 min keeping pH of the solutions and dose of the
adsorbent constant. The sorption isotherm was also performed by mixing 1 g of
IACAA with 100 mL spiked arsenic concentration at different initial
concentrations of arsenic. The kinetics and thermodynamic parameters were
established by conducting the experiments at different reaction times and at three
different temperatures respectively.
Desorption experiments
To determine the reusability of the IACAA samples adsorption/desorption cycles
were repeated using the adsorbent sample. 100 mL solution of both NaOH and
HCl (0.1, 0.3 and 0.5 M) and 1 g of the adsorbed adsorbent was used
separately and agitated for about 2 hours at shaken speed of 165 rpm.
The aqueous phase was then separated and concentration of arsenic in that phase
was determined.
Adsorption isotherm
Langmuir isotherm
The Langmuir isotherm is based on the assumption that, (i) maximum adsorption
corresponds to a saturated monolayer of adsorbate molecules on the adsorbent
surface, (ii) the energy of adsorption is constant and (iii) there is no
transmigration of adsorbate molecules in the plane of adsorbent surface. The
Langmuir isotherm [21] is expressed as:Where, q
is the equilibrium quantity adsorbed (mg/g), C
is the equilibrium concentration (mg/L), q
is the maximum adsorption capacity (mg/g) and b is the
Langmuir constant.
Freundlich isotherm
The linear form of the Freundlich isotherm [22] equation is expressed as:Where, q
is adsorbed amount (mg/g), C
is equilibrium arsenic concentration (mg/L), k
(mg/g) is the Freundlich constant related to adsorption capacity and
n is constant related to energy of intensity of adsorption.
Dimensionless equilibrium parameter (R
)
In order to predict the adsorption efficiency of the isotherms process the
Langmuir isotherm can be determined in terms of dimensionless equilibrium
parameter or Langmuir isotherm constant parameter (R
) which can be related with Langmuir isotherm constant by the following
equation [23].Where, b is the Langmuir isotherm constant and C
is the initial arsenic ion concentration (mg/L). The value of R
indicates the shape of the isotherms. If the value
0 < R
< 1 then the Langmuir isotherm is favourable, if
R
= 0 it is irreversible, if R
= 1 it is linear and if R
> 1 the isotherm is unfavourable.
χ2 (Chi-square) analysis
To recognize a suitable isotherm model for the sorption process,
χ2 analysis is to be generally carried out. The
χ2 test statistic is basically the sum of the squares of the
differences between the experimental data and the data obtained by calculating
from models, with each squared difference divided by the corresponding data
obtained by calculating from models. The equivalent mathematical statement
isWhere, q
is equilibrium capacity obtained by calculating from the model (mg/g) and
q
is the experimental data of the equilibrium capacity (mg/g). If the data
from the models are similar to the experimental data, χ2 will be a small number, but if they differ then χ2 will be a bigger number [24].
Thermodynamic investigations
Thermodynamic parameters associated with adsorption viz. standard free energy
change (ΔG
), standard enthalpy change (ΔH
), standard entropy change (ΔS
), activation energy (E
), were calculated as follows:The free energy of sorption process, considering the sorption distribution
coefficient Ko, is given by the equation:Where, ΔG
is the standard free energy change (kJ/mol), T is the
temperature in Kelvin and R is the universal gas constant
(8.314 J/mol/ K). The sorption distribution coefficient Ko for sorption reaction was determined from the slope of the plot against C
at different temperatures and extrapolating to zero C
according to the method suggested by Khan and Singh [25].The sorption distribution coefficient may be expressed in terms of
ΔH
and ΔS
as a function of temperature.Where, ∆H0 is the standard enthalpy change (kJ/mol) and ∆S0 is the standard entropy change (kJ/mol/K). The values of
∆H0 and ∆S0 can be obtained from the slope and intercept of a plot of 1n
K0 against respectively.A modified Arrhenius-type equation related to the surface coverage
(θ) is expression for sticking probability, S*. This is a function of the adsorbate/adsorbent system, which is the
measure of the potential of an adsorbate to remain on the adsorbent indefinitely [26] and it can be expressed as:Where, θ is surface coverage,Where, C0 and C
are the initial and equilibrium arsenic concentrations respectively. The
plot of ln(1–θ) against will give a linear plot with intercept of lnS* and
slope of .
Adsorption kinetics
In order to investigate the sorption mechanism for removal process, pseudo first
and second-order kinetic models are used at different experimental conditions. A
simple pseudo-first-order kinetic model [27], is represented as:Where q
is the amount of adsorbate on the surface of the adsorbent at time
t (mg/g) and K
is the equilibrium rate constant of pseudo-first-order sorption
(min-1).In addition, pseudo-second-order model is also widely used. Though there are four
types of linear pseudo-second-order kinetic models [28], the most popular linear form used has the equation:Where, , the amount of adsorbate on the surface of the adsorbent at
any time, t amount (mg/g), k being pseudo-second-order rate
constant (g/mg min), q
is the amount of adsorbate sorbed at equilibrium (mg/g)and the initial
sorption rate, h = (mg/g min). The value of q
(1/slope), k (slope2/intercept) and h
(1/intercept) of the pseudo-second-order equation were obtained experimentally
by plotting against t for arsenic sorption at different
temperatures.
Intraparticle diffusion model
The contact time experimental results can be used to study the rate-limiting step
in the adsorption process, [29] and its equation can be expressed as:Where, k
is the intraparticle rate constant (mg/g min 0.5). The
slope of plot of q
0versus t1/2 gives the value of the intraparticle rate constant.
Results and discussion
Effect of adsorbent dose
The effect of adsorbent dose on arsenic removal at fixed initial arsenic
concentration is shown in Figure 1. It was observed
that the adsorption efficiency increases rapidly with increase in adsorbent dose
from 0.1 – 1 g/100 mL; a marginal increase is observed on
further increase in the adsorbent dose. The removal efficiency was observed to
increase sharply up to 1 g/100 mL of As (III) solution thereafter
removal becomes almost constant. Thus, 1 g/100 mL was taken for other
studies. The increase in the efficiency of removal may be attributed to the fact
that with the increase in adsorbent dose, more adsorbent surface is available
for the solute to be adsorbed [30].
Figure 1
Effect of adsorbent dose on As (III) adsorption at As(III)
concentration = 0.45 mg/L, pH = 7.4 and
contact time = 90 min.
Effect of adsorbent dose on As (III) adsorption at As(III)
concentration = 0.45 mg/L, pH = 7.4 and
contact time = 90 min.
Effect of pH
The effect of pH on the adsorption of As (III) onto IACAA was studied in the pH
range of 4.2 to 9.2. Figure 2 reveals that the
efficiency of As (III) removal increases with increasing pH from 4.2 to 7.4. In
the present study best arsenic removal of 98.5% has been achieved at
pH = 7.4. The removal efficiency of IACAA is found to decrease both
at lower and higher pH from 7.4. The highly protonated surface of IACAA is not
favourable for As (III) removal resulting almost no change in the extent of
adsorption within the pH range 4.2 to 6.1. With increase in pH of the system,
the degree of protonation of the surface reduces gradually and approaches to
zero near zero point charge (ZPC) of the adsorbent. The species like
H2AsO4 - and
HAsO4 2- which may be formed during the
adsorption process may play a role in the molecule surface interaction or
occlusion phenomena and may also affect the arsenic adsorption mechanism [31].
Figure 2
Effect of pH on As (III) adsorption at As(III)
concentration = 0.45 mg/L, adsorbent
dose = 1 g/100 ml and contact
time = 90 min.
Effect of pH on As (III) adsorption at As(III)
concentration = 0.45 mg/L, adsorbent
dose = 1 g/100 ml and contact
time = 90 min.
Effect of contact time
Figure 3 demonstrates the effect of contact time on
the adsorption of As (III) onto IACAA. From the figure it is clear that
adsorption efficiency increases with increasing contact time, reaching a maximum
removal at contact time of 90 minutes; thereafter removal becomes linearly
constant. This may be due to the overlapping of active sites with arsenic
species as the contact time increases and also due to decrease in the effective
surface area resulting in the conglomeration of exchange particle [32].
Figure 3
Effect of contact time on As (III) adsorption at As(III)
concentration = 0.45 mg/L, adsorbent
dose = 1 g/100 L and pH = 7.4.
Effect of contact time on As (III) adsorption at As(III)
concentration = 0.45 mg/L, adsorbent
dose = 1 g/100 L and pH = 7.4.
Effect of initial concentration
Effect of initial concentration on the percentage removal of As (III) was studied
by varying different initial arsenic concentration. The effect of initial
concentration on removal of As (III) was shown in Figure 4 which reveals that removal efficiency is higher with lower initial
arsenic concentration (0.40 mg/L); a gradual decrease in As (III) uptake by
IACAA was observed with increasing feed concentration of As (III). The reason
for the decrease in As (III) adsorption efficiency at higher initial
concentration may be due to fact that the active sites ultimately becomes
saturated with adsorbed arsenic and further addition of arsenic to the solution
would not be expected to increase the amount to be adsorbed significantly [33].
Figure 4
Effect of initial concentration on As (III) adsorption at
pH = 7.4, adsorbent
dose = 1 g/100 ml and contact
time = 90 min.
Effect of initial concentration on As (III) adsorption at
pH = 7.4, adsorbent
dose = 1 g/100 ml and contact
time = 90 min.
Analysis studies
The surface morphology of iron acetate coated activated alumina (IACAA) adsorbent
before and after treatment with arsenic samples were examined by scanning
electron microscope (SEM). SEM photographs before and after treatment with
arsenic are given in Figures 5(a) and (b)
respectively. It is clear that the surface morphology of these two samples is
different which confirms the arsenic sorption onto the IACAA adsorbents. X-ray
diffraction patterns of activated alumina, IACAA and arsenic adsorbed IACAA are
given in Figures 6(a), (b) and (c) respectively.
Crystalline phases were identified by software database published by the Joint
Committee on Powder Diffraction Standards (JCPDS). The main mineral phases of
alumina, iron and arsenic sorption on IACAA respectively were identified as
Al2O3 (JCPDS-79-1557), AlFeO3
(JCPDS-84-2154) and FeAsO4 (JCPDS-78-1545). The FTIR spectra of IACAA
before and after adsorbing As (III) in aqueous solution are shown in
Figures 7(a) and (b). In the Figure 7(a) IR spectrum of IACAA shows distinct bands at 1748,
1638, 1459 and 1383 cm-1. As described elsewhere [34], these bands arise from Fe-OH stretching and banding vibration from
part of hydroxyl groups, which are converted from the iron oxide in the forms of
transient complex species such as Fe-OH, Fe(OH)2 or FeO(OH) on the
surface of IACAA. The As (III) adsorption leads to promote intensity of the
spectrum by an order of magnitude without many changes in the individual
positions of bands. But the IR band in Figure 7(a)
that shifts from 698 cm-1 in case of IACAA to 782 cm-1
upon As (III) adsorption is attributed to the As-O stretching band following
partial substitution of Fe3+ by As3+. These results are in
reasonable agreement with the earlier studies of As (III) sorption to Fe and Al
oxide [35]. EDAX analysis of adsorbents after adsorption of arsenic showed the
presence of oxygen, arsenic, alumina and iron. The graphical representation is
depicted in Figure 8.
Figure 5
SEM image of IACAA. SEM of coated activated (a) before
sorption of arsenic &(b) after sorption of arsenic.
Figure 6
X-Ray spectra of Activated Alumina and IACAA.
(a) Activated Alumina (b) IACAA before As (III) adsorption
(c) IACAA after As (III) adsorption.
Figure 7
FTIR spectra of IACAA.
(a) IACAA before As (III) adsorption (b) IACAA after As
(III) adsorption.
Figure 8
% Elemental of IACAA adsorbents after adsorption of arsenic analyzed
by EDAX.
SEM image of IACAA. SEM of coated activated (a) before
sorption of arsenic &(b) after sorption of arsenic.X-Ray spectra of Activated Alumina and IACAA.(a) Activated Alumina (b) IACAA before As (III) adsorption
(c) IACAA after As (III) adsorption.FTIR spectra of IACAA.(a) IACAA before As (III) adsorption (b) IACAA after As
(III) adsorption.% Elemental of IACAA adsorbents after adsorption of arsenic analyzed
by EDAX.
Adsorption studies
The linear plot of 1/C
versus 1/q
of Langmuir isotherm Figure 9(a) with higher
R2 value indicates the monolayer adsorption on IACAA. The values
of q
and b were calculated from the slope and intercept respectively
are presented in Table 1.
Figure 9
Adsorption isotherm models of IACAA. (a): Langmuir isotherm of
IACAA. (b): Freundlich isotherm of IACAA.
Table 1
A comparison of Langmuir and Freundlich isotherm parameters obtained
at different temperatures
Temp (K)
Langmuir isotherm parameters
Freundlich isotherm parameters
qm(mg/g)
b(L/mg)
R2
SD
1/n
n
kf(mg1-1/nL1/ng-1)
R2
SD
301
0.0897
0.1035
0.9918
0.3776
0.4899
2.04
0.8374
0.9877
0.0212
306
0.0903
0.1038
0.9844
0.5053
0.4888
2.05
0.8332
0.9776
0.0274
311
0.0909
0.1041
0.9823
0.5336
0.4928
2.03
0.8128
0.9754
0.0288
Temp: Temperature.
Adsorption isotherm models of IACAA. (a): Langmuir isotherm of
IACAA. (b): Freundlich isotherm of IACAA.A comparison of Langmuir and Freundlich isotherm parameters obtained
at different temperaturesTemp: Temperature.In case of Freundlich isotherm, the value of k
and n (Table 1) are obtained from the
linear plot of ln q
vs ln C
Figure 9(b). Value of n lying between
1 and 10 also indicates the favourable conditions for adsorption isotherms as
well.Langmuir isotherm constant parameter, R
values at different temperatures studied were calculated and are given in
Table 2.
Table 2
The
and Chi-square values of IACAA
Temp
RLvalues
χ2values for isotherms
(K)
0.40 mg/L
0.42 mg/L
0.45 mg/L
0.50 mg/L
0.52 mg/L
Langmuir
Freundlich
301 K
0.0236
0.0225
0.0210
0.0189
0.0182
5.01E-05
7.93E-01
306 K
0.0235
0.0224
0.0209
0.0188
0.0181
8.04E-05/
7.84E-01
311 K
0.0234
0.0223
0.0208
0.0187
0.0180
9.02E-05
7.32E-01
The
and Chi-square values of IACAAR2 values for Langmuir isotherm (0.991, 0.984 and 0.982) at different
temperatures 301 K, 306 K and 311 K are presented in
Table 1. It was found out that Langmuir
adsorption model is better fitted than Freundlich model. The χ2 values calculated using equation (4) is given in Table 2. In case of Langmuir isotherm, the χ2 values are found to be much lower than that of Freundlich isotherm
and hence the adsorption of arsenic on IACAA follows preferably Langmuir
isotherm.
Thermodynamic studies
The thermodynamic parameter viz. ∆G0, ∆H0, ∆S0 and E
were calculated with the help of equations (5, 6, 7, 8) and are presented
in Table 3. The negative value of standard free
energy and positive value of entropy change indicate the spontaneity of sorption
of arsenic. The value of enthalpy change was positive, indicating that the
sorption process is endothermic [36]. The positive value of ∆S0 shows the increasing randomness during the sorption of arsenic on
IACAA. The value of S* is found to be 0.011 which is very close to zero indicating that
adsorption mechanism follows chemisorptions [37].
Table 3
Thermodynamic parameters obtained at three different temperatures
during arsenic sorption on IACAA
Thermodynamic parameters
Temp. (K)
ΔGo(KJ/mol)
ΔHo(kJ/mol)
ΔSo(kJ /mol/K)
Ea(kJ/mol)
S*
301
−9.84
2.0
0.0390
1.66
0.0110
306
−10.04
311
−10.23
Thermodynamic parameters obtained at three different temperatures
during arsenic sorption on IACAA
Kinetics studies
The Lagergren plots of log(q
–q
) versus t obtained from the equation (9) for various
temperatures viz. 301, 306 and 311 K are given in Figures 10(a), (b) and (c). The values of K
at three different temperatures were calculated from slopes of the
respective linear plots and also the correlation coefficient (R2)
were computed and the values are given in Table 4.
Figure 10
Lagergren plot of IACAA at three different temperatures. (a):
Lagergren plot of IACAA at 301 K. (b): Lagergren plot of
IACAA at 306 K. (c): Lagergren plot of IACAA at 311K.
Table 4
Lagergren constants for sorption of arsenic on IACAA at different
temperature
C0
Mass
301 K
306 K
311 K
(mg/L)
(g)
Kad
R2
Kad
R2
Kad
R2
(min-1)
(min-1)
(min-1)
0.40
1.0
0.0333
0.9914
0.0583
0.8531
0.0434
0.9355
0.42
1.0
0.0464
0.9411
0.0952
0.8703
0.0473
0.9612
0.45
1.0
0.0672
0.9755
0.0495
0.9972
0.0811
0.9311
0.50
1.0
0.0733
0.9330
0.0622
0.8530
0.0862
0.9463
0.52
1.0
0.0712
0.8963
0.0686
0.9784
0.0594
0.9444
Lagergren plot of IACAA at three different temperatures. (a):
Lagergren plot of IACAA at 301 K. (b): Lagergren plot of
IACAA at 306 K. (c): Lagergren plot of IACAA at 311K.Lagergren constants for sorption of arsenic on IACAA at different
temperatureThe plot of t vs. from equation (10) gives a straight line with higher
correlation coefficient r values, which is higher than that observed
pseudo-first-order model indicating the applicability of the pseudo-second-order
model. These values are shown in Table 5. The value
of q
was found to increase with increasing initial As (III) concentration and
temperature. The values of rate constant (k) have also been found to
increase with increasing temperature thus indicating chemisorption.
Table 5
Pseudo-second-order kinetic parameters of IACAA
Temp
Conc
qe
k
h
R2
(K)
(ml/L)
(mg/g)
(g/mg min)
(mg/g min)
301
0.40
0.0382
0.5530
0.8520
1
0.42
0.0422
0.6640
1.1280
1
0.45
0.0451
0.7010
0.9310
0.999
0.50
0.0492
0.8280
0.6220
0.998
0.52
0.0451
0.9230
0.5410
0.997
306
0.40
0.0392
0.9531
1.3951
1
0.42
0.0411
0.9770
1.6941
1
0.45
0.0426
0.9862
0.9340
0.999
0.50
0.0432
1.2100
0.7821
0.981
0.52
0.0512
1.2240
0.7540
0.999
311
0.40
0.0399
0.9870
1.4370
0.999
0.42
0.0413
0.9883
1.5031
0.998
0.45
0.0416
1.3010
1.6010
1
0.50
0.0419
1.3210
1.4130
0.999
0.52
0.0507
1.3301
1.6110
1
Pseudo-second-order kinetic parameters of IACAAThe plot of q
versus t1/2 from equation (11) is shown in Figure 11. All the plots have the same general features of initial curved
portion followed by linear portion and a plateau. The initial portion is
attributed to the bulk diffusion and subsequent linear portion is attributed to
the intraparticle diffusion. The fitness of particle diffusion model gives
further evidence that the arsenic removal is a surface process under the studied
experimental conditions.
Figure 11
Validation of Weber-Morris equation for arsenic sorption on
IACAA.
Validation of Weber-Morris equation for arsenic sorption on
IACAA.The percentage removal of IACAA on As (III) was found to be higher as compared
with percentage removal using Iron Oxide Coated Sand [30], Activated Alumina [38] and Iron oxide Impregnated Activated Alumina [39] as adsorbents and the list is given in Table 6.
Table 6
Comparison of removal efficiency of As (III) using different
adsorbents
Comparison of removal efficiency of As (III) using different
adsorbentsaActivated Alumina, bIron oxide Impregnated
Activated Alumina, cIron Acetate Coated activated Alumina
& dIron Oxide Coated Sand; *Temperature.
Desorption study
It was observed that no desorption of As (III) was detected under normal
condition. The experimental results revealed that eluent NaOH are found to be
more effective to desorp arsenic in comparison to that of HCl. The trend of
desorption percentage of different concentration of NaOH is as follows:
0.1 M < 0.3 M < 0.5 M. The maximum
desorption of arsenic was found to be 34.4% with 0.5 M NaOH solution.
Conclusion
The overall study reveals that the adsorption of arsenic onto IACAA is found to be
dependent on pH, adsorbent dose and contact time. Best removal of As (III) is
achieved at pH = 7.4. The initial As (III) concentration
(0.45 mg/L) comes down to less than 0.01 mg/L with the minimal adsorbent
dose (1 g/100 mL) at contact time 90 minutes. The thermodynamic
studies of sorption of arsenic on IACAA show that the reaction is spontaneous and
endothermic process. The equilibrium data are fitted to both Langmuir and Freundlich
adsorption isotherm. But it is found that Langmuir isotherm model fitted well
followed by Freundlich. The pseudo-second order kinetic model is found to be the
best correlation of the data for sorption of arsenic on IACAA. The kinetic of the
reaction follows intraparticle diffusion model.
Competing interests
The authors declare that they have no competing interests.
Authors’ contributions
BD was the main investigator. He participated in the study design, data analysis and
drafting of manuscripts. RRD was involved in experimental studies including
interpretation of the results of FTIR and XRD. IMU carried out detailed adsorption,
thermodynamic and kinetic studies and their interpretation. KB had done the
quantitative analysis of arsenic and also extended help in other laboratory studies
related to the manuscript. SB was the main advisor, helped in study design and
supervised the study. AKT was responsible for data processing, support in
interpretation of results and proof reading of the manuscript. All authors read and
approved the final manuscript.