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Journal of Industrial and Engineering Chemistry 20 (2014) 32343242

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Journal of Industrial and Engineering Chemistry


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

Kinetics, equilibrium and thermodynamics studies of arsenate


adsorption from aqueous solutions onto iron hydroxide
T. Mahmood a, S.U. Din a, A. Naeem a,*, S. Tasleem a, A. Alum b, S. Mustafa a
a
b

National Center of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan
Arizona State University, School of Sustainable Engineering and the Built Environment, Tempe, AZ 85287, USA

A R T I C L E I N F O

Article history:
Received 14 March 2013
Accepted 2 December 2013
Available online 10 December 2013
Keywords:
Sorption
Arsenate
Metal oxide
Film diffusion

A B S T R A C T

This paper reports the equilibrium, kinetics and thermodynamic studies of arsenate adsorption onto
freshly precipitated iron hydroxide. Adsorption of arsenate onto iron hydroxide depends on arsenate
concentration, contact time and temperature. The intrapartical diffusion model indicates that both the
lm and intrapartical diffusion control arsenate adsorption on iron hydroxide. The values of activation
energies (Ea) indicate the chemical nature of adsorption accompanied by diffusion controlled processes
as the rate limiting step. The endothermic nature of the adsorption process suggests that adsorption
reaction consumes energy. The negative values of DS# can be assigned to decreased randomness at the
solid liquid interface.
2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction
The presence of arsenic in drinking water is a serious
environmental problem. Soluble arsenic is present in natural
waters in the forms of arsenate [As(V)] and arsenite [As(III)].
Arsenate (V) is the most stable surface water species under aerobic
conditions and exists as deprotanated oxyanions of arsenic acid
(H2AsO4, HAsO42). Arsenite (III) exists in neutral forms at natural
pH values. Removal of As(III) from water is difcult as compared to
As(V). Generally, As(III) remains undissociated and is neutral and
therefore exhibits only limited adsorption sites as compared to
As(V). It is necessary to oxidize As(III) to As(V) for its effective
removal from drinking water [1]. Natural processes such as
volcanic exhalations, weathering reactions, and biological activities are responsible for the mobilization of arsenic. The anthropogenic sources responsible for the release of arsenic to the
environment are mining activities, smelting operations, fertilizers,
combustion of fossil fuels and arsenic pesticides [2].
Arsenic uptake through drinking water causes various chronic
diseases such as epidermal, cardiovascular, respiratory, neurological and hematological and renal diseases. Arsenic uptake also
causes cancer of lung, bladder, liver, kidney and prostate [37]. In
addition, the notorious black foot disease which results in the
amputation of feet, arm and other parts of the body is also one of
the toxicological effects of arsenic contaminated water. The use of

* Corresponding author. Tel.: +92 91 9218480; fax: +92 91 9216671.


E-mail address: naeeem64@yahoo.com (A. Naeem).

arsenic contaminated water may also result in diabetes mellitus.


Arsenic intake in large quantity may lead to hallucination,
impaired memory, emotional disorder and perplexity [5,7].
The World Health Organization (WHO), the US Environmental
Protection Agency (USEPA) and European Commission (EC) have
laid the guidelines [4] for arsenic in ground water to be 10 mg L1.
Arsenic concentration is higher than the permissible limit of WHO
in some parts [5,6] of Mexico, India, Argentina, USA, Bangladesh,
Chile and Pakistan.
Different technologies such as precipitationcoagulation,
membrane separation, ion exchange, and adsorption have been
used for the removal of toxic elements from water. Adsorption is
considered to be one of the most preferred techniques due to its
high efciency, economy and easy operation [79]. Adsorbents
like activated alumina, activated carbon, natural laterite, orange
juice residues, mixed rare earth oxides, lanthanum compounds
and plant biomasses have been tested for the adsorption of
arsenic from drinking water [10]. Many of them have low
adsorption afnity for the removal of arsenic from water. On the
other hand, iron containing compounds have been found more
promising, efcient and versatile for the adsorption of both As(III)
and As(V) [5].
Several researchers have carried out kinetics investigation on
the adsorption of arsenic onto metal oxides. Fuller et al. [11]
examined the kinetics of arsenate adsorption on ferrihydrite in
coprecipitation and post-synthesis adsorption experiments in the
pH range from 7.5 to 9.0. Ping et al. [12] investigated the kinetics of
arsenic adsorption onto oxides of iron and aluminum which was
inuenced by the contact time and the surface coverage. Ping and

1226-086X/$ see front matter 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.12.004

T. Mahmood et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 32343242

his co-workers further studied arsenic desorption from the arsenic


loaded surface by phosphate at pH 6.0. Raven et al. [13] studied the
kinetics of arsenic adsorption on ferrihydrite with an initial arsenic
concentration of 13.3 mol kg1, and at pH 4.6 and 9.2. The different
reaction rates for arsenate was explained on the basis of binding of
the arsenate to the surface through the formation of monodentate
complexes and the slower bidentate complexes at lower and
higher surface coverage respectively.
The determination of equilibrium time and rate limiting step at
different temperatures are of great importance due to economical
reason and also to have an understanding of the adsorption
mechanism. However, temperature effect on the kinetics of arsenic
adsorption is ignored by these researchers. The objective of this
research is to evaluate the impact of temperature on kinetics of
arsenate adsorption and to have an insight into the sorption
mechanism via determining the rate-limiting step of the process
and also to describe and evaluate some activation parameters. In
the current study both the adsorption equilibrium and kinetics
experiments were conducted at 298, 308, 318 and 328 K which
also correspond to the seasonal temperature changes in the Indian
subcontinent where arsenic contamination is a serious problem of
concern.
2. Materials and methods
Iron nitrate was provided by Riedel-de Haen. All the test
solutions were prepared from H3AsO4 standard solution provided
by Merck. The pHs of the system were adjusted with 0.1 M NaOH
and HNO3 solutions. All the glassware was rst washed with nitric
acid and then with deionised water of 18.2 MV cm resistivity
before their use.
2.1. Preparation of iron hydroxide
Iron hydroxide was prepared in the laboratory by the method
reported elsewhere [14]. Drop wise mixing of equimolar solutions
of sodium hydroxide and iron nitrate lead to the formation of iron
hydroxide according to the following reaction:
FeNO3 3 3NaOH ! FeOH3 3NaNO3

(1)

The suspension pH was adjusted to 7  0.2 in order to facilitate


the precipitate of iron hydroxide. After the ltration of the
suspension, the precipitate was dried for 24 h in the oven at
110 8C. After grinding the precipitate, it was passed through 140 mesh
size and was dried in oven for overnight. Finally powdered precipitate
was stored in desiccators for 18 h to remove moisture content.
2.1.1. Characterization
Surface area of iron hydroxides was determined using
Quantachrome NOVA 1200e by nitrogen adsorption method after
degassing for 1 h at 105 8C. The scanning electron micrographs
(SEM) of the material was obtained using SEM model JSM 5910
(JEOL Japan) equipped with an energy dispersive X-ray (EDX)
micro analyzer model INCA 200 (UK) at 20 keV. TG/DTG analyzer
Perkin Elmer model 6300 was used for recording thermogravimetric analyses and differential thermo-gravimetry (TGA/
DTG) of iron hydroxide. X-ray diffraction (XRD) patterns of the iron
hydroxide were recorded by X-ray diffractometer (JEOLJDX-3532)
at room temperature. Point of zero charge (PZC) was determined
using the salt addition method [15].
2.1.2. Equilibrium adsorption study
The equilibrium adsorption study was carried out at 298, 308,
318 and 328 K and at pH 8 whereas pH effect was studied at
initial arsenate concentration of 50 mg L1 and at 298 K. In the

3235

adsorption isotherm experiments, the optimized amount (0.1 g) of


iron hydroxide was taken in polythene bottles containing 40 mL
arsenate solution. All the arsenate solutions were prepared in the
concentration range of 1100 mg L1. The initial pH values of the
suspensions were adjusted using 0.1 M HNO3/NaOH. The reaction
vessels were shaken in a WiseBath shaker for 24 h at 120 rpm and
the equilibrium pH of the suspensions was noted and the
suspensions were ltered with Whattmann lter paper 42. The
difference between initial and the nal arsenate concentration of
the suspension was taken as the amount of arsenate adsorbed. The
pH was observed with the help of Boeco Germany pH meter BT600. The co-precipitation of As(V) was frequently reported to occur
with dissolved Fe(III). However, this possibility was ruled out in the
present study because no dissolution of iron hydroxide was
observed in the pH range selected in the present investigation.
Some of the experiments were conducted in duplicate in order to
check the reproducibility of the results. Blank experiments
(without adsorbents) showed neither precipitation nor adsorption
of arsenate onto the walls of the reaction vessels and lter
materials. All the experiments were performed in a nitrogen
atmosphere to bubble out the carbon dioxide from the solution.
2.1.3. Kinetic study
The simple batch adsorption technique was used for the kinetic
studies. Iron hydroxide (0.1 g) was taken separately in 40 mL of
300 mg L1 and 50 mg L1 arsenate solution in several reaction
vessels. The pH of the each suspension was adjusted to pH 8 which
is considered as the representative pH of the natural waters. The
reaction vessels were taken out at different time intervals after
agitation in a WiseBath shaker at an optimum shaking rate of
120 rpm and at constant temperature. The suspensions were then
ltered through a 0.45 mm lter paper and Perkin Elmer Model 800
atomic absorption spectrophotometer was used for arsenic
analyses before and after adsorption. Flame technique was used
for the solutions having concentrations in mg L1 while graphite
technique was used for arsenic solutions in mg L1 at a wavelength
193.7 nm. The adsorption kinetics experiments were conducted at
pH 8 at 298, 308, 318 and 328 K which correspond to the seasonal
temperature changes in the Indian subcontinent where arsenic
contamination is a serious problem of concern.
3. Results and discussion
3.1. Characterization
The BET surface area of iron hydroxide is found to be
78  2 m2 g1 which is closer to surface area (65 m2 g1) of
ferrihydrite [16]. The XRD image showed that the iron hydroxide is
amorphous in nature. The point of zero charge (PZC) is observed to be
7.0 which is closer to the one reported in the literature for metal
oxides and hydroxides [17]. SEM image indicated that the surface of
the iron hydroxide is irregular in shape having an average particle size
of 0.75 mm. The weight loss for iron hydroxide occurs in two steps
(Fig. 1). The rst weight loss is observed to be 3.92% at 75 8C which is
attributed to the loss of physiosorbed water. This is also conrmed by
the appearance of an endothermic peak in this region in the
differential thermal gravimetry (DTG) curve (Fig. 1). The second
weight loss 5.2% occurs at 300 8C which is due to the loss of interstitial
water. The sample of iron hydroxide remains stable in pH range 38
except at pH 2 where the dissolution of iron from the sample is found
to be 3.3 mg L1.
3.2. Equilibrium adsorption studies
In the present investigation, arsenate removal efciencies are
studied in the temperature range of 298328 K to determine the

T. Mahmood et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 32343242

3236

Table 1
Freundlich parameters for arsenate adsorption on iron hydroxide at pH 8.
Temperature

Experimental
Xm  104 (mol g1)

Theoretical
Xm  104 (mol g1)

R2

1.43
1.52
1.53
1.61

16.11
8.29
8.02
6.81

0.884
0.847
0.841
0.875

(K)
298
308
318
328

molecule to be independent of neighboring sites. The Langmuir


model in its linear form [21] is represented as follows:
Ce
Ce
1

X
Xm XmK b
Fig. 1. TG/DTG of iron hydroxide.

X x 105 (mol g-1)

20.2

16.2

12.2
298K
308K
318K
328K

8.2

(2)

where X is the amount of arsenate sorbed (mol g1), Ce is the


equilibrium concentration (mol L1), the values of constants Xm
and Kb, denoting monolayer capacity and binding energy are
calculated from the slope and intercept of the graph plotted
between Ce/X and Ce (Fig. 3A). In the present investigation, all the
calculated linear functions show good correlation coefcient
(0.99). As is obvious from Table 2, the values of both the Xm and
Kb slightly increase with the temperature of the system. This trend
indicates that the adsorption of arsenate onto iron hydroxide to be
endothermic in nature. The close agreement between the
theoretical and experimental Xm values further validates the
applicability of the Langmuir model to the current experimental
data. The direct comparison of the adsorption capacity with
different oxides/hydroxides reported in the literature is difcult
because of different experimental conditions, i.e. concentration

4.2
0

20

40

60

80

100

120

Ce x 105 (mol L-1)

(A)
6

298K
308K
2

318K
328K

0
0.01

(B)

5.01

10.01

Ce x 104 (mol L-1)


70
60

% Desorpon

impact of temperature on arsenate adsorption by iron hydroxide.


The adsorption isotherms shown in Fig. 2 show that adsorption of
arsenate by iron hydroxide gradually increases with the increase in
arsenate concentration, reaches to a maximum and then the
equilibrium is established in the system at all the temperatures.
The data in Fig. 2 shows an increase in the adsorption of arsenate
onto the surface of iron hydroxide with the increase in the
temperature of the system. The arsenic adsorption data at pH 8
indicates that the sorption capacity of iron hydroxide increases
from 1.49  104 to 1.57  104 (mol g1) as the temperature is
increased from 298 to 328 K. As expected, the diffusion rate of
arsenate anions into the pores of iron hydroxide increases with
increase in temperature which is responsible for the substantial
adsorption of arsenate at higher temperature. Similar observations
are described by many researchers for different oxides/hydroxides
[1820].
Frenudlich model was applied to the experimental data for
interpretation of the arsenate adsorption mechanism. However,
Freundlich model is not applicable due to its low values of
regression coefcient (R2) which are observed to be 0.88, 0.84, 0.84
and 0.87 at 298, 308, 318 and 328 K respectively. Moreover, no
agreement was observed between the experimental and the
calculated adsorption capacities derived from the Freundlich
model (Table 1).
The conventional Langmuir model is used for dening the
potential use of adsorbent for certain applications. The Langmuir
model assumes monolayer coverage, energetically equivalent
surface sites and the adsorbing ability at a particular site of a

Ce/X x (g L-1)

Fig. 2. Arsenate adsorption on iron hydroxide at pH 8 at different temperatures.

50
40
30
20
10
0
9

10

11

12

pH
Fig. 3. (A) Langmuir plots at pH 8 for arsenate adsorption on iron hydroxide and (B)
reversibility of arsenate from the surface of iron hydroxide at 308 K.

T. Mahmood et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 32343242


Table 2
Langmuir parameters for arsenate adsorption on iron hydroxide at pH 8.

3237

(A)

Experimental
Xm  104 (mol g1)

Theoretical
Xm  104 (mol g1)

Kb  104
(L mol1)

R2

298
308
318
328

1.43
1.52
1.53
1.61

1.49
1.51
1.55
1.57

3.02
4.42
5.48
6.85

0.99
0.99
0.99
0.99

range, pH, and temperature, etc. However, the iron hydroxide used
in this study has comparatively better adsorption capacity than
iron oxide impregnated activated carbon [22], titanium dioxide
loaded Amberlite XAD-7 resin [23], molybdate impregnated
chitosan beads [24], oxisol and its constituents [25] and synthetic
hydrous stannic oxide [26]. The values of binding energy are in the
range reported for the adsorption of arsenate by Streat et al. [27].
The reversibility of arsenate is studied for the loaded surface of
Fe(OH)3 in the pH range of 312. The desorption of the arsenate
(Fig. 3B) from loaded surface of iron hydroxide back into the
solution starts in the alkaline pH range, i.e. at pH 9 and above and
no desorption is observed in the pH range 38. The maximum
desorption of arsenate (57.7%) from the surface of iron hydroxide is
recorded at pH 12 which can be assigned to the higher
concentration of hydroxyl anions which lead to the ion exchange
desorption of arsenate anions. The decrease in desorption of
arsenate with a decrease in pH is attributed to the lowering of
hydroxyl anions. Raichur and Pavenkar [28] also reported similar
results for arsenate desorption from mixed rare earth oxides.

Iron hydroxide
Iron hydroxide (after arsenate adsorption)

%T

4000

2000
Wave number (cm

1000
-1

(B)

(C)
3

3.3. Correlation of structural parameters with arsenate adsorption on


iron hydroxide

Arsenate adsorbed

110

% Adsorption

During the course of this investigation an attempt has been


made to correlate structural parameters with adsorption behavior
of arsenate on iron hydroxide. The FTIR spectrum of iron hydroxide
prior and subsequent to adsorption is shown in Fig. 4A. All the
observed peaks in the FTIR spectra are the characteristics peaks of
iron hydroxide. However, some additional peaks at 3257, 3421,
3493, 3560 cm1 are observed after arsenate adsorption which
correspond to Fe coordinated OH at the iron hydroxide surface. The
splitting of the broad peak in the region 32003600 shows
dislocation of surface hydroxyl groups after arsenate sorption.
Comparable results were reported by Myneni et al. [29] for
arsenate adsorption on ettringite. Moreover, the peak at 1641 is
not only bifurcated but its intensity is also enhanced which
validates that the arsenate anions is going to replace the OH anions
from the solid surface. The above vibration bands are in agreement
with the reported spectra for arsenate adsorption on clay [30].
The EDX analysis (Fig. 4B) of the arsenate loaded iron hydroxide
also illustrates the existence of arsenate which further veries the
conclusion drawn from the FTIR studies. Thus, FTIR analysis further
conrms that arsenate is chemically adsorbed onto the surface of
iron hydroxide.
Point of zero charge (PZC) determination is used to compute the
electrical charges on the surface of the adsorbents. The adsorption
behavior of an adsorbate greatly depends on the surface charge
properties of the adsorbent. The effect of surface charges on
the adsorption of arsenate by iron hydroxide is shown in Fig. 4C.
The pHpzc of iron hydroxide is found to be 7.0. As the pH of the
solution approaches to the pHpzc, the adsorption of arsenate onto
iron hydroxide decreases correspondingly, i.e. arsenate adsorption
decreases from 98% at pH 2 to 58% at pH 8. The enhanced
adsorption below pHpzc is due to electrostatic attraction between
the positive surface and the negative arsenate anions. Similarly, the
decrease in adsorption with the increase in pH is due to

3000

Change in pH

2
1

90

pH

Temperature
(K)

70
-1
50

-2

pHi 6

Fig. 4. (A) FTIR, (B) EDX spectra of iron hydroxide and (C) plots of DpH and %
adsorption of arsenate on iron hydroxide vs. pHi at 298 K.

the electrostatic repulsion between the negative surface and the


negative arsenate anions. Thus the above discussion conrms that
surface electrical charges play an important role in the adsorption
of arsenate onto iron hydroxide.
Furthermore, the maximum adsorption (98%) at pH 2 may also
be due to the leaching of iron hydroxide. It is deduced that more
reactive sites are exposed after dissolution of iron hydroxide which
contribute to the signicant adsorption of arsenate anions. As
discussed earlier, the relatively greater sorption of arsenate on iron
hydroxide than the other adsorbents [23,26] is probably due to its
greater surface area.
3.4. Adsorption kinetics
The kinetics study for the removal of arsenate by iron hydroxide
was conducted for the investigation of the sorption behavior of the
system. The effect of contact time on the adsorption of arsenate by
iron hydroxide is studied at different temperatures. The time
dependent adsorption of arsenate by iron hydroxide is shown in
Fig. 5A and B. The initial rapid increase in arsenate adsorption in

T. Mahmood et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 32343242

3238

-4

17.5
15.5

-4.4

13.5

-4.8

11.5

log (qe-qt)

X x 105(mol g-1)

(A)

298K

-5.2
298K

308K

9.5

-5.6

308K
318K

O 318K

-6

7.5
0

500

1000

1500

2000

2500

3000

200

400

600

800

1000

t (min)

t (min)
Fig. 6. Pseudo rst order plot for arsenate adsorption on iron hydroxide at pH 8 at
initial concentration 50 mg L1.

80
(B)

X x 106 (mol g-1)

60

40
298K
308K

20

318K
328K
0
0

500

1000
1500
t (min)

2000

2500

Fig. 5. Kinetics of arsenate adsorption on iron hydroxide at different temperatures


at pH 8 at (A) 50 mg L1 and (B) 300 mg L1.

the rst 30 min is then followed by a gradual and slower uptake


rate for the rest of 15 h and nally the adsorption equilibrium in
the system is established. The equilibrium time is observed to be
15 h. The initial rapid adsorption of arsenate on iron hydroxide is
due to the availability of larger number of vacant adsorption sites
for the arsenate species of the bulk solution. The subsequent
slower adsorption is likely because of the competition among the
arsenate ions for the limited number of vacant adsorption sites.
Thus the driving concentration gradient between the bulk solution
and the solid surface is the main factor controlling the kinetics of
the system. A similar trend of rapid initial and subsequent slower
adsorption was reported by many researchers [3134]. The initial
slopes of Fig. 5 show that the uptake rate of arsenate by iron
hydroxide is greatly dependent on the initial arsenate concentration. The rapid adsorption rates indicate that the predominant
mechanism for arsenate adsorption on iron hydroxide is lm
diffusion which is activated by the high concentration difference
between the bulk solution and the pores of the adsorbent. Kundu
and Gupta [35] reported similar results for arsenic adsorption on
iron coated cement.
3.5. Effect of temperature
The time dependent uptake of arsenate adsorption by iron
hydroxide for the arsenate concentrations of 300 mg L1 and
50 mg L1 at different temperatures and at pH 8 is depicted in
Fig. 5A and B. Temperature effect on arsenate adsorption by iron
hydroxide during the rst 3 h is almost negligible because more
active and energetic sites are occupied easily and rapidly during
this time (Fig. 5A). However, the less active sites of the surface are
slowly and gradually occupied during the rest of the contact time

where the temperature effect becomes visible. The reason may be


the increased availability of the active adsorption sites and the
desolvation of the adsorbing species. The viscosity of the solution
decreases with the increase in temperature due to which the
arsenate anions become more mobile which consequently results
in increased diffusion through an external boundary layer and into
the pores of the adsorbent. It shows that the high temperature
favors the uptake of arsenate by iron hydroxide through anion
exchange process. Gua et al. [36] found a similar increase in uptake
rate while studying arsenic removal by synthetic siderite.
3.6. Kinetic modeling
Several kinetics models were used in the kinetic data to
investigate the mechanism of the arsenate adsorption on iron
hydroxide.
3.6.1. Pseudo rst order model
The pseudo rst order kinetic model was applied to the current
data in its linearized form as follows:
logqe  qt logqe 

k1
2:303t

(3)

where k1 (min1) is the rate constant of the rst order equation,


qe (mol g1) is the amount of solute adsorbed at equilibrium. Both
k1 and qe are obtained from the slopes and intercepts respectively
of the linear plot of log(qe  qt) vs. t (Fig. 6), where qt is the arsenate
adsorbed at time t (min). The Lagergren plots are linear having
small values of correlation coefcients. The difference between the
theoretical and experimental adsorption capacities (Table 3)
shows that the kinetic data for the adsorption of arsenate by iron
hydroxide cannot be reported by a pseudo rst order model which
is similar to the one reported by Maji et al. [37] for the adsorption
of arsenic on laterite soil.
3.6.2. Pseudo second order model
The kinetic data was analyzed by pseudo second order model.
The linear form of the pseudo second order equation is given as
follows:
t
1
1

t
q k2 qe2 qe

(4)

where q and qe is the amount of arsenate adsorbed at time t and


equilibrium respectively, and k2 is the equilibrium rate constant of
the pseudo second order equation. The plot of t/q vs. t was linear
with a correlation coefcient >0.97 (Fig. 7A and B). The pseudo

T. Mahmood et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 32343242

80

Table 3
Pseudo rst order rate parameters for arsenate adsorption on iron hydroxide at pH 8
(initial concentration 50 mg L1).

70

k1  10
(min1)

Experimental
qe  104
(mol g1)

Theoretical
qe  105
(mol g1)

298
308
318

5.21
4.34
4.78

1.35
1.38
1.42

5.24
5.33
5.16

0.95
0.98
0.96

60
50
40

-1

Temperature
(K)

q x 10 (mol g )

3239

298K

30

308K

20

318K
10

second order rate constant (k2) and the equilibrium adsorption


capacity (qe) obtained from this model are presented in Tables 4
and 5. As suggested by Sheela et al. [38], a close agreement
between theoretical and experimental adsorption capacities
supports that the adsorption of arsenate by iron hydroxide is
well described by pseudo second order kinetic model. The increase
in theoretical qe with the increase in temperature is typical of
chemisorption process. The rate constant values are comparable in
magnitude with Chio et al. [39].

The rate limiting step determines the adsorption mechanism.


Three stages are considered to be involved during the sorption of
arsenate on iron hydroxide:
(i) Transfer of the sorbate molecules from the bulk solution to the
solid surface, i.e. lm diffusion.

10

(A)
40

30

308K
10

318K
328K

0
500

1000

1500

2000

2500

t (min)
7
(B)
6
5
4
3
2

298K
308K

318K
0
100

40

Out of these three stages, step (iii) is assumed to be very fast and
it is kinetically of no importance. Steps (i) and (ii) can be
considered to be acting individually or in combination. In the
present study, two kinetics models namely Weber Morris and Boyd
models were employed to describe the mechanism of arsenate
adsorption on iron hydroxide.

200

300

400

500

600

700

800

(5)
1

298K

30

Fig. 8. Intra particle diffusion plot for arsenate adsorption on iron hydroxide at pH 8
at initial concentration 300 mg L1.

q kid t 0:5 C
20

20
t0.5

3.7.1. Weber and Morris (intraparticle diffusion) model


This model is of great importance since intraparticle diffusion is
the rate limiting step in the liquid adsorption system. The current
kinetic data is subjected to the Weber Morris model to investigate
the possibility of intraparticle diffusion as the rate limiting step. It
is an empirical equation where adsorption is a function of t0.5 and
can be dened as follows:

50

t/q X 10-6 (min g mol-1)

(ii) Intraparticle diffusion within the interior of the adsorbent.


(iii) Adsorption of the adsorbate at an internal site [37].

3.7. Adsorption kinetics mechanism

t/q x 10-6(min g mol-1)

328K

900

t (min)
Fig. 7. Pseudo second order plot for arsenate adsorption on iron hydroxide at (A)
50 mg L1 and (B) 300 mg L1.

0.5

) represents the intraparticle diffusion


where kid (mol g min
rate constant and its values are obtained from a plot of q vs. t0.5
(Fig. 8). The C values are obtained from the intercept of the plot
and represent a constant depicting resistance to mass transfer in
the boundary layer. The larger the value of C, the greater is the
boundary layer effect. For pure intraparticle diffusion to take place,
the plot of q vs. t0.5 should be linear passing through the origin with
no intercept. But if the plot shows multilinearity, then the
adsorption process may be controlled by the combination of lm
and intraparticle diffusion, i.e. more than one step is involved in
the adsorption process [39]. The rst and the second straight-line
portions of the plot (Fig. 8) indicate macropore and micropore
diffusions respectively. The intercepts obtained by the extrapolation of the second portion of the plots back towards the y-axis
shows intraparticle diffusion is not the only controlling step of the
process because the plot does not pass through the origin. The rst
curved portion indicates the adsorption to be the lm diffusion
whereas the second linear portion shows the adsorption to be the
intraparticle diffusion in nature. The intraparticle diffusion rate
constant (kid) at different temperatures obtained from the linear
portions of the plots is depicted in Tables 6 and 7. As discussed
earlier, the increase in the values of kid with the increase in
temperature points towards the increased diffusion of the
molecules into the pores of the adsorbent. Similar observations
were reported by many researchers while studying the adsorption
behavior of different substrates [40].

T. Mahmood et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 32343242

3240

Table 4
Pseudo second order parameters for arsenate adsorption on iron hydroxide at pH 8 (initial concentration 300 mg L1).
Temperature (K)

k2 (g min1 mol1)

Experimental qe  105 (mol g1)

Theoretical qe  105 (mol g1)

R2

Ea (kJ mol1)

298
308
318
328

115
138
147
169

5.29
6.12
7.08
7.44

5.24
6.28
6.63
7.35

0.97
0.99
0.99
0.99

9.94

Table 5
Pseudo second order parameters for arsenate adsorption on iron hydroxide at pH 8 (initial concentration 50 mg L1).
Temperature (K)

k2 (g min1 mol1)

Experimental qe  104 (mol g1)

Theoretical qe  104 (mol g1)

R2

Ea (kJ mol1)

298
308
318

207
234
254

1.35
1.38
1.42

1.33
1.37
1.41

0.99
0.99
0.99

9.53

F 1

X
1 

p2


1
expm2 Bt
m2

(6)

where F is the fractional attainment of equilibrium at time t and is


obtained by the following expression:where F = qt/qe.
Rearranging the above equation gives
F values > 0.85, Bt = 0.4977  ln(1  F)and for F values < 0.85,
hp pi2
p  p  p2 F=3 where qe (mol g1) is the amount of
Bt
solute adsorbed at time t, qe (mol g1) is the maximum amount of
arsenate adsorbed at equilibrium, Bt is the mathematical function
of F, m is an integer that denes the innite series solution. The Bt
values calculated from the above equations are plotted against
time t (Fig. 9A and B). The linearity of the plot is used to distinguish
between intraparticle diffusion and lm diffusion process. If the
plot is linear passing through the origin then the rate controlling
step of the adsorption process is intraparticle diffusion; otherwise,
the lm diffusion process is the rate controlling mechanism of the
adsorption process. In the present study, the poor linearity as well
as the intercept of the plots conrms that lm diffusion is the ratelimiting step which is primarily responsible for the adsorption of
arsenate on iron hydroxide. Similar results have been reported in
the literature by many authors [41,42].

3.8. Estimation of activation energy


As mentioned in an earlier section, the present investigation
clearly shows that the adsorption of arsenate on iron hydroxide is
favored at high temperature. The inuence of temperature on the
arsenate adsorption rate is studied thermodynamically by the use
of the linearized form of the Arrhenius equation which is expressed
as follows:
lnk2 lnA 

Ea
RT

(7)

where k2 is the pseudo second order rate constant, A is the preexponential factor, R is the general gas constant, T is the absolute
temperature and Ea is the activation energy. Activation energy (Ea)

(A)

2
Bt

3.7.2. Boyd model


In order to estimate the actual rate limiting step (lm or
intraparticle diffusion) involved in the adsorption process, the
kinetic data was further analyzed by Boyd model.

298K
308K

318K
328K
0
0

500

1000

1500

t (min)
5
(B)

Table 6
Intra particle diffusion parameters for arsenate adsorption on iron hydroxide at pH
8 (initial concentration 300 mg L1).
1

Temperature (K)

kid  10 (mol g

298
308
318
328

6
7
7
8

min

0.5

0.97
0.88
0.97
0.97

3
Bt

2
298K
1

Table 7
Intra particle diffusion parameters for arsenate adsorption on iron hydroxide at pH
8 (initial concentration 50 mg L1).
Temperature (K)

kid  107 (mol g1 min0.5)

R2

298
308
318

8.7
8.9
9.3

0.97
0.99
0.99

308K
318K

0
0

500

1000

1500

2000

2500

t (min)
Fig. 9. Boyd plot for arsenate adsorption on iron hydroxide at pH 8 at initial
concentration (A) 300 mg L1 and (B) 50 mg L1.

T. Mahmood et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 32343242

3241

Table 8
Thermodynamic parameters for arsenate adsorption on iron hydroxide at pH 8.
Initial arsenate concentration (mg L1)

DS# (J mol1)

DH# (kJ mol1)

DG#298 K (kJ mol1)

DG#308 K (kJ mol1)

DG#318 K (kJ mol1)

300
50

181
175

7.33
6.55

61.19
58.74

62.99
60.49

64.80
62.24

3.9. Activation parameters


The activation parameters, i.e. entropy (DS#) and enthalpy
(DH#) of activation are calculated by applying the well known
Eyring equation as follows:

  
k2
lnkB
DS
DH
(8)


ln
R
RT
T
hp
The values of (DS#) and (DH#) are utilized for the calculation of
Gibbs free energy (DG#) according to the following equation:

DG DH  T DS

(9)

where k2, kb and hp represent the pseudo second order, Boltzmann


and Planks constant respectively. The entropy (DS#) and enthalpy
(DH#) of activation are calculated from the intercept and slopes of
the graphs plotted between ln k2/T vs. 1/T (Fig. 11). The negative
values of DS# (Table 8) imply the decrease randomness at the solid

-1.4

-1.7

ln k2

-2

-2.3

-2.6

-2.9
0.003

0.0031

0.0032

0.0033

0.0034

T-1 (K-1)
Fig. 10. Arrhenius plot for arsenate adsorption on iron hydroxide at pH 8 at initial
concentration 300 mg L1.

0
-0.2
-0.4
ln (k2/T)

is calculated from the slope of the linear plot of ln k2 vs. 1/T


according to Arrhenius equation (Fig. 10). The values of the
activation energy (Tables 4 and 5) are found to be 9.94 kJ mol1 for
the arsenate concentration of 300 mg L1 and 9.53 kJ mol1 for the
arsenate concentration of 50 mg L1. These values are closer to the
reported value in the literature [43]. The current values of Ea (9.53
and 9.94 kJ mol1) are within the range 8.483.7 kJ mol1 which
indicates the chemical type of adsorption as suggested elsewhere
[44,45]. These observations are contrary to the ndings reported
by Haron et al. [46] while studying arsenate adsorption by titanium
oxide loaded poly (hydroxamic acid) resin. Activation energy also
gives idea of the rate-limiting step of the adsorption process. If
Ea < 42 kJ mol1, the adsorption is diffusion controlled whereas if
Ea > 42 kJ mol1, the adsorption process is believed to be
chemically controlled [47]. The values of Ea < 42 kJ mol1 suggest
the rate limiting step to be diffusion controlled. This is not
conicting since before the occurrence of the chemical reaction at
the sorption sites, the ions are transported to the corresponding
sorption sites through bulk diffusion, surface diffusion and pore
diffusion which occur in series rather than parallel. Thus the
slowest step of these is the rate limiting step of the process [48].

-0.6
-0.8
-1
-1.2
0.003

0.0031

0.0032

0.0033

0.0034

T-1 (K-1)

Fig. 11. Eyring plot for arsenate adsorption on iron hydroxide at pH 8 at initial
concentration 50 mg L1.

liquid interface and also suggest that the arsenate adsorption on


iron hydroxide is an associative mechanism [49]. The positive
values of DG# reveal that the process of arsenate adsorption onto
iron hydroxide is non-spontaneous and also signify the existence
of energy barrier in the system. As suggested elsewhere [50], the
hydration of arsenate ions in the solution may also contribute
partially to the existence of energy barrier in the system. The
positive values of DH# show that the adsorption reaction consumes
energy while converting reactants to products [38]. Similar
positive values of DG# and DH# and negative values of DS# are
reported by Anirudhan et al. [51] for the adsorption of
chromium(VI) by iron(III) complex of an amino-functionalized
polyacrylamide-grafted lignocellulosuis.
4. Conclusions
The kinetic data for arsenate adsorption onto iron hydroxide
is well interpreted with the pseudo-second-order kinetics
model. The increase in arsenate adsorption and rate constant
values with the increase in temperature indicates the endothermic nature of the process. The intraparticle diffusion model
demonstrates that both the lm and intraparticle diffusion
controls the arsenate adsorption onto iron hydroxide. Nevertheless, the poor linearity and the intercept of the Boyd model
strongly supports that the lm diffusion process is the main
controlling step. The values of the activation energy conrm the
chemical nature of arsenate adsorption on iron hydroxide
through the formation of an activated complex once the
arsenate anions through diffusion-controlled processes reach
to the adsorption sites. The adsorption equilibrium study reveals
that both the values of sorption maxima (Xm) and binding
energy constant (Kb) increase with increase in temperature. The
value of the enthalpy of activation (DH#) conrms the process of
adsorption is endothermic in nature. The negative values of DS#
can be assigned to the decreased randomness at the solid liquid
interface. The freshly prepared iron hydroxide behaves as an
efcient exchanger for the anion exchange adsorption of
arsenate from aqueous solution.

3242

T. Mahmood et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 32343242

Acknowledgments
We greatly appreciate the productive suggestions of the
anonymous reviewers. One of the authors Mr. Salah ud Din is
also thankful to the higher education commission (HEC) of
Pakistan for partial support of this project.

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