Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 6371

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Process Safety and Environmental Protection

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

Adsorption of Cr(VI) from aqueous phase by high

surface area activated carbon prepared by chemical
activation with ZnCl2

Arvind Kumar, Hara Mohan Jena

Department of Chemical Engineering, National Institute of Technology (NIT), Rourkela, Odisha 769008, India

a r t i c l e i n f o a b s t r a c t

Article history: Prepared activated carbon from fox nutshell by chemical activation with ZnCl2 in the N2
Received 4 August 2016 atmosphere was used for Cr(VI) removal from aqueous solution. Activated carbon was pro-
Received in revised form 18 March duced at 600 C activation temperature with a 2.0 impregnation ratio for 1 h of activation time
2017 has been found as 2869 m2 /g, 1.96 and 1.68 cm3 /g of highest BET surface area, total pore vol-
Accepted 26 March 2017 ume and micropore volume, respectively. Batch mode adsorption studies were carried out by
Available online 3 April 2017 varying agitation speed, pH, temperature, agitation time and initial Cr(VI) concentration. The
adsorption of Cr(VI) was pH dependent and showed maximum removal efficiency of Cr(VI)
Keywords: at pH 2.0. Adsorption studies of 1025 mg/L initial Cr(VI) concentration were conducted at
Activated carbons pH of 2.0 and temperature of 30 C. The equilibrium, kinetics, and thermodynamics of Cr(VI)
Fox nutshell adsorption were studied. The adsorption capacity of Cr(VI) from the synthetic wastewa-
Chemical activation ter was 43.45 mg/g. The experimental adsorption equilibrium data was fitted to Langmuir
Impregnation adsorption model with an adequate adsorption capacity of 46.21 mg/g.
Cr(VI) 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Adsorption

1. Introduction (Pagilla and Canter, 1999), membrane separation (Chakravarti et al.,

Chromium is a primary metal pollutant introduced into the water
bodies from a variety of industrial processes such as plastic, leather
tanning, electroplating, metal processing, paint manufacturing, steel
fabrication and fertilizer, and also used in explosives, ceramics, and
photography (Selvi et al., 2001; Zhou et al., 2016). Chromium occurs as
both trivalent [Cr(III)] and hexavalent [Cr(VI)] states in the aquatic envi-
ronment. Cr(VI) is primarily present in the form of chromate (CrO4 2 )
and dichromate (Cr2 O7 2 ). Cr(VI) possesses significantly higher levels of
toxicity than the other valency states which can cause severe diseases
such as dermatitis, kidney circulation, lung cancer and even death
(Selvi et al., 2001; Sharma and Forster, 1995; Zhou et al., 2016). The toler-
ance limit of Cr(VI) for discharge into inland surface waters is 0.1 mg/L
and in potable water is 0.05 mg/L (Kobya, 2004). So, the removal of Cr(VI)
from contaminated water is important to protect the environment.
Various methods such as chemical precipitation (Zhou et al., 1993),
ion exchange (Tiravanti et al., 1997), reduction (Seaman et al., 1999),
adsorption (Cronje et al., 2011; Yang et al., 2015), solvent extraction
1995), and biological method (Sahinkaya et al., 2012) have been devel-
oped for chromium removal from wastewater. Among these methods,
the adsorption technique by using activated carbon is the most suit-
able method due to its efficiency; high adsorption capacity and low
operational cost (Acharya et al., 2009; Kumar and Jena, 2016b).
Adsorption process has proved to be the most efficient for the
removal of heavy metals from wastewaters (Acharya et al., 2009; Cronje
et al., 2011). The high cost of adsorbents is the main barrier to the appli-
cation by the industries. The cost of adsorption technology application
can be reduced if the adsorbent is inexpensive. So there is a need to
develop low-cost and easily available adsorbents for the removal of
heavy metal ions from the wastewater (Cronje et al., 2011; Kumar and
Jena, 2016a). Agricultural waste, biomass, and various solid waste sub-
stances are used to prepare activated carbons for reducing the cost.
In recent years, activated carbon are being produced from agricultural
products like Paulownia wood (Yorgun and Yldz, 2015), marigold straw
(Qin et al., 2014), candlenut shell (Prahas et al., 2008), corncob (Sych
et al., 2012), coconut shells (Cazetta et al., 2011), reedy grass leaves (Xu
et al., 2014), lotus stalks (Liu et al., 2013), and buriti shells (Pezoti et al.,
2014).

Corresponding author.
E-mail addresses: arvindkr202@gmail.com (A. Kumar), hmjena@nitrkl.ac.in (H.M. Jena).
http://dx.doi.org/10.1016/j.psep.2017.03.032
0957-5820/ 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
64 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 6371

In the present study, the prepared fox nutshell activated carbon

by chemical activation method with ZnCl2 is used as an adsorbent for
Cr(VI) removal. To the best of our knowledge, no study is reported on
the removal of hexavalent chromium from aqueous solution by the
prepared fox nutshell activated carbon.

2. Experimental

2.1. Material

Preparation of activated carbon from fox nutshell was carried

out by chemical activation process with a ZnCl2 activating
agent. The details of the preparation of high surface area acti-
vated carbon was published in the separate study (Kumar and
Jena, 2015). The resulting fox nutshell activated carbon (FNAC)
was kept in sealed container and used as an adsorbent for the
adsorption of Cr(VI) from synthetic wastewater. The charac-
teristics of the prepared activated carbon are summarized in
Table 1.
2.2. Adsorbate and analytical method
A stock solution (1000 mg/L) of Cr(VI) was prepared by dissolv-
ing 2.829 g analytical grade K2 Cr2 O7 in 1000 mL distilled water.
Standard solutions of Cr(VI) ions concentration range from 10
to 25 mg/L were obtained by dilution of the stock solution. 0.1N
HCl and 0.1N NaOH solutions were used to adjust the solution
pH. Some experimental variables such as agitation speed, pH
(27), contact time (03 h) and concentration (1025 mg/L) were
studied to investigate the Cr(VI) removal process. Samples at
different time intervals were taken and centrifuged (2 mL) at
10,000 rpm for 5 min. The concentrations of Cr(VI) before and
after adsorption was analyzed by spectrophotometer (Jasco,
Model V-530, Japan) using 1,5-diphenyl carbazide method at
540 nm.
2.3. Batch adsorption and kinetic experiment
The batch adsorption experiments were conducted in a set of
250 mL of Erlenmeyer flasks containing 100 mL of Cr(VI) (10,
15, 20 and 25 mg/L) solution with a fixed adsorbent dosage of
0.05 g. The flasks were agitated in a temperature-controlled
shaker at optimized 150 rpm and 30 C temperature for 3 h
study. The equilibrium adsorption capacity, qe (mg/g) and per-
centage removal, R (%) were calculated by using the equations
given below.
(C0 Ce ) V
qe = , (1)
ms
C0 Ce
R (%) = 100,
C0
The adsorption capacity qt (mg/g) at different contact time
t (min) was determined using the following equation:
Fig 1 FESEM of FNAC.
3. Results and discussion
3.1. Surface morphologies of the prepared activated
carbon
Field emission scanning electron microscopy (FESEM) image
of the FNAC is shown in Fig. 1. The prepared activated car-
bon has well-developed pores which are of different sizes
and different shapes. Due to well-developed pores, the acti-
vated carbon possessed high BET surface area (2869 m2 /g).
The pores development on the surfaces of the activated car-
bon resulted from the evaporation of the activating agent of
ZnCl2 during carbonization, leaving space previously occu-
pied by the activating agent (Deng et al., 2010; Prahas et al.,
2008).
Energy dispersive X-ray spectrometer with the field emis-
sion scanning electronic microscope (EDX) was used to
determine the chemical composition of FNAC, and it is shown
in Fig. 2. It shows clearly the presence of C and O peaks as
component elements of the FNAC. The result shows that the
carbon has the maximum value (89.15%). From Fig. 2, Zn is
not present in the prepared activated carbon means that 0.5N
HCl washing was important step for complete removal of Zn
and released closed pores to open pores. Also, the EDX result
confirms that ZnCl2 is a suitable dehydrating agent that pro-
motes the decomposition of carbonaceous material during
the pyrolysis process for obtaining high carbon content car-
bon.
Transmission electron microscope (TEM) visualized the
microporous network of the FNAC. The TEM image is shown
in Fig. 3. It clearly shows the uniform pore distribution of
micropores like honeycomb due to which the prepared acti-
vated carbon attained high micropore volume. From Fig. 3, the
(2)
average pore diameter of the micropore present on the FNAC
surface is 0.64 nm.
3.2. Cr(VI) adsorption onto FNAC

(C0 Ct ) V 3.2.1. Effect of agitation speed

qt = , (3)
ms
where C0 , Ce , and Ct are the initial, equilibrium, and at time t
(min) of Cr(VI) concentrations (mg/L) respectively, V is the vol-
ume of solution (L) and ms is the dry weight of the adsorbent
(g).
Fig. 4 shows the effect of agitation speed on Cr(VI) removal
was examined in the range of 90170 rpm. The results reveal
that the Cr(VI) removal efficiency did not change above the
agitation speed of 150 rpm. This result indicates that an effec-
tive transport of Cr(VI) ions toward the adsorbent surfaces
occurred due to a decrease in boundary layer thickness around
 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 6371 65

Table 1 Characteristics of FNAC.

Proximate analysis Activated Ultimate Activated Pore structure
carbon (wt%) analysis carbon (wt%) characteristics

Moisture 2.21 C 89.77 SBET (m2 /g) 2869

Volatile matter 19.05 H 2.33 VT (cm3 /g) 1.96
Ash 1.02 N 0.43 Vmicro (cm3 /g) 1.68
Fixed carbona 77.72 S 0.06 Vmeso (cm3 /g) 0.28
a
By difference Oa 7.41 Vmicro /VT (%) 85.71
SBET : BET surface area, Smicro : micropore Dp (nm) 2.75
surface area, Smeso : mesopore surface
area, VT: total pore volume, Vmicro :
micropore volume, Vmeso : mesopore
volume, microporosity = (Vmicro /VT ) 100,
Dp : average diameter.

Fig. 2 EDX spectrum of FNAC.

Fig. 3 TEM image of FNAC.

66 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 6371

Fig. 4 Effect of agitation speed on the removal of Cr(VI)

onto FNAC (C0 = 10 mg/L, FNAC weight = 0.02 g, pH = 2,
Fig. 5 Effect of pH on the Cr(VI) removal onto FNAC
temperature = 30 C, and contact time (t) = 3 h).
(C0 = 10 mg/L, FNAC weight = 0.02 g, temperature = 30 C, and
contact time (t) = 3 h).
the adsorbent particles by increasing agitation speed (Gupta
et al., 2011). Hence, for the further experiments, the agitation
speed of 150 rpm was selected as the optimal mixing speed.

3.2.2. Effect of pH
The pH of the system determines the adsorption capacity due
to its influence on the surface properties of the FNAC and
different ionic forms of the chromium solutions. Hexavalent
chromium, Cr(VI) exists in different ionic forms in aqueous
solution and the stability of these forms, such as HCrO4 ,
CrO4 2 or Cr2 O7 2 , depend on the pH of the aqueous solution
and chromate concentration. The following are the equilib-
rium reactions and corresponding pKa values reported in few
literature for different Cr(VI) species.

H2 CrO4 H+ + HCrO
4 (i)
pKa = 0.8 (Sengupta and Clifford, 1986), 0.75 (Kotas and
Stasicka, 2000), 0.26 (Cox, 2000).
Fig. 6 Effect of adsorbent dosage of FNAC on Cr(VI)
removal (C0 = 10 mg/L, pH = 2.0, contact time (t) = 3 h,
temperature = 30 C).

HCrO + 2
4 H + CrO4 (ii)
pKa = 6.5 (Sengupta and Clifford, 1986), 6.45 (Kotas and
Stasicka, 2000), 5.9 (Ajouyed et al., 2010; Cox, 2000).
2HCrO 2
4 Cr2 O7 + H2 O (iii)
pKa = 1.52 (Sengupta and Clifford, 1986), 2.2 (Ajouyed
et al., 2010; Cox, 2000; Kotas and Stasicka, 2000).
HCr2 O
7 = Cr2 O7 + H
+
(iv)
pKa = 0.07 (Sengupta and Clifford, 1986), 0.85 (Cox, 2000).
The Reaction (iii) does not contain any H+ terms, i.e., in
a certain pH range (25) this reaction is independent of pH
and depends only on total Cr(VI) concentration. This may be
regarded as a dimerization reaction for HCrO4 at acidic pH.
In the pH ranging from 2.0 to 6.0, HCrO4 ions mainly exist
in equilibrium and the predominant form of HCrO4 shifts to
chromate ion (CrO4 2 ) as pH increases. Above pH 7 only CrO4 2
ions exist in solution throughout the concentration range and
in the pH between 1.0 and 6.0, HCrO4 is the predominant
form up to the Cr(VI) concentration 102 M then it starts to
condense yielding the orange-red dichromate ion. HCrO4 ion
only needs one active site whereas chromate ion (CrO4 2 )
needs two active sites due to its two minus charges (Yang
et al., 2014). The behavior for better adsorption at low pH by
activated carbon may be attributed to the large number of H+
ions present which in turn neutralize the negatively charged
hydroxyl group (OH) on the adsorbent surface, thereby reduc-
ing hindrance to the diffusion of chromate ions (Demiral et al.,
2008). At higher pH values, the reduction in adsorption may be
possible due to the abundance of OH ions causing increased
hindrance to diffusion of dichromate ions.
Fig. 5 shows the influence of solution pH on Cr(VI) adsorp-
tion by FNAC in the pH range of 2.07.0. From Fig. 5, the removal
of Cr(VI) from aqueous solution is greatly influenced by the pH
of the solution, and the maximum removal of 85.35% occurs
at pH 2.0. The Cr(VI) adsorption decreases from 2.0 to 7.0. This
result indicates that the adsorption of the adsorbent is clearly
pH dependent. Other investigators have also reported simi-
lar observations (El-Sikaily et al., 2007; Hamadi et al., 2001;
Karthikeyan et al., 2005; Sharma and Forster, 1994; Yang et al.,
2015).
3.2.3. Effect of adsorbent dose
The effect of the AC dosage on the adsorption of Cr(VI) was
studied. The percentage removal of Cr(VI) varied linearly with
the amount of the adsorbent as shown in Fig. 6. With the
increase of adsorbent dosage, the time needed to reach equi-
 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 6371 67

Fig. 8 Langmuir isotherm for the adsorption of Cr(VI) onto

FNAC.

3.2.5. Adsorption isotherms

At equilibrium state, the adsorption isotherm is very useful to
describe how the adsorbed molecules distribute between the
liquid phase and the solid phase. The Langmuir, Freundlich
and Temkin isotherm models were used for the adsorption
isotherm. The results of the fitting done for used models of
Cr(VI) adsorption are listed in Table 2.
The Langmuir isotherm is valid for monolayer and homo-
geneous sites within the adsorbent surface with a uniform
distribution of energy level. The model assumes uniform
adsorption and no transmigration in the plane of the adsor-
bent surface (Langmuir, 1918). The linear form of the Langmuir
equation is represented as follows:
Fig. 7 Effects of contact time on the adsorption capacity at
different initial concentrations (FNAC
Ce 1 Ce
weight = 0.05 g, C0 = 10 mg/L, pH = 2.0, temperature = 30 C). = + , (4)
qe kL qm qm

where qm represents the maximum adsorption capacity of the

librium is reduced due to the increase of efficient adsorption
solid phase loading, and kL (L/mg) is the Langmuir constant.
sites at higher dosages. FNAC dosage was ranged from 0.01 to
Fig. 8 shows a linear relationship of Ce /qe versus Ce using
0.07 g/100 mL of Cr(VI) solution and equilibrated for 3 h. From
experimental data obtained for Cr(VI) adsorption. The qm and
Fig. 6, the percentage uptake capacity of Cr(VI) is increased
kL values are obtained from slope and intercept of the plot and
with the increase in adsorbent dose up to 0.05 g significantly
are tabulated in Table 2.
and after that remains unchanged. Thus, to get the better
The Freundlich isotherm equation is based on sorption
Cr(VI) removal, 0.05 g was chosen as an optimal mass of the
onto a heterogeneous surface and given as (Freundlich, 1906):
adsorbent for the further experiments.

qe = kF + Ce n ,
1
(5)
3.2.4. Effect of contact time and initial Cr(VI)
concentrations
Fig. 7 displays the impact of contact time and initial concen- where kF ((mg/g)(L/mg)1/n ) is the Freundlich constant related
trations of the solution. It can be readily observed that the to adsorption capacity, and 1/n is dimensionless heterogeneity
adsorption capacity of Cr(VI) on FNAC drastically increased factor. The linear form of Eq. (5) is
during the initial stage and then at a slow speed. The grow-
ing trend stopped when a state of equilibrium was reached. 1
ln qe = ln kF + ln Ce , (6)
FNAC is removed a larger amount of Cr(VI) in the first 20 min n
of contact time, and the equilibrium is established in 60 min
for all different absorbent concentration studied [Fig 7(a)]. It is A linear plot of ln qe versus ln Ce confirms the validity of
clear that the adsorption of Cr(VI) ion is rather quick because the Freundlich model and is shown in Fig. 9. The value of n
it reaches its maximum removal in 60 min and after that, no (4.66) > 1 represents a favorable condition.
more adsorption occurs. A large number of vacant sites with Temkin and Pyzhev have suggested that the heat of
active functional groups were available on FNAC at an early adsorption should decrease linearly with the surface coverage
stage of adsorption for the Cr(VI). The equilibrium adsorp- because of the existence of adsorbateadsorbate interactions
tion increases from 19.18 to 43.45 mg/g while % removal of (Temkin and Pyzhev, 1940). The following equation can adjust
Cr(VI) observed in reverse behavior, as decreases from 99.08 to the corresponding adsorption isotherm:
86.89% when initial concentrations are increased from 10 to
25 mg/L [Fig. 7(b)]. qe = B ln (A) + BlnCe , (7)
68 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 6371

Table 2 Langmuir, Freundlich, and Tempkin parameters of Cr(VI) adsorption onto FNAC.
Freundlich Langmuir Tempkin
1/n 2 2
kF (mg/g(L/mg) ) n R qm (mg/g) kL (L/mg) R b A (L/g) R2

32.10 4.66 0.960 46.21 3.02 0.971 394.64 201.14 0.890

Fig. 10 Pseudo-first order kinetic plot for the Cr(VI)

Fig. 9 Freundlich isotherm for the adsorption of Cr(VI) adsorption onto FNAC (FNAC weight = 0.05 g, pH 2.0, and
onto FNAC. temperature = 30 C).

where B = RT/b is related to the heat of adsorption (L/g), and

A is the dimensionless Tempkin isotherm constant. The con-
stant A and b values are listed in Table 2.
The R2 values of these isotherm models are shown in
Table 2. In this study, the Langmuir model is best fitted for
Cr(VI) adsorption onto fox nutshell AC. Thus, from Table 2,
the comparison of tested models for the description of Cr(VI)
adsorption equilibrium isotherms on the fox nutshell AC is as
follows: Langmuir > Freundlich > Tempkin.

3.2.6. Adsorption kinetic studies

The study of adsorption kinetics of Cr(VI) adsorption is signifi-
cant as it provides valuable insights into the reaction pathways
and the mechanism of the reactions. Three diffusion steps
usually control any adsorption process: (i) transport of the Fig. 11 Pseudo-second order kinetic plot for the Cr(VI)
solute from the bulk solution to the film surrounding the adsorption onto FNAC (FNAC weight = 0.05 g, pH 2.0, and
adsorbent, (ii) from the film to the adsorbent surface, (iii) from temperature = 30 C).
the surface to the internal sites followed by binding of the
metal ions to the active sites. The slowest steps determine the To evaluate the goodness of fitting and suitability of the
overall rate of the adsorption process, and usually, it is thought model, the linear correlation coefficient (R2 ) and normalized
that the step (ii) leads to surface adsorption, and the step (iii) standard deviation q (%) were used in the kinetic model
leads to intra-particle adsorption (Demiral et al., 2008). In the study. A higher value of R2 and lower value of q denoted bet-
present study, the most used kinetic models of pseudo-first- ter model fitting. The standard deviation q (%) was calculated
order (Budinova et al., 2006) and pseudo-second-order (Ho and from given equation (10).
McKay, 1999) were used to fit the experimental data. Linear 
forms of pseudo-first-order and pseudo-second-order kinetic
 2
(qexp qcal ) /qexp
equations are given in Eqs. (8) and (9), respectively. q (%) = 100, (10)
N1

ln (qe qt ) = lnqe k1 t, (8) where qexp and qcal (mg/g) are the experimental adsorption
capacity and calculated adsorption capacity, respectively, and
t 1
1
N is the number of experimental data points.
= + t, (9)
qt k2 q2e qe The adsorption kinetics of pseudo-first-order and pseudo-
second-order for Cr(VI) onto FNAC is shown in Figs. 10 and 11.
where qe and qt (mg/g) are the adsorbed Cr(VI) amounts onto The derived kinetic parameters of pseudo-first-order and
FNAC at the equilibrium and at any time t (min), respectively pseudo-second-order are listed in Table 3. As observed, the
and k1 (min1 ) and k2 (g/min/mg) are the rate constant of the experimental kinetic data are better fitted by the pseudo-
pseudo-first-order and pseudo-second-order adsorption. second-order model (R2 = 0.999 for all Cr(VI) concentrations).
 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 6371 69

Table 3 Kinetic constants obtained for the adsorption

of Cr(VI) adsorption onto FNAC.
Parameters Cr(VI), C0 (mg/L)

10 15 20 25

qe,exp (mg/g) 19.18 28.38 36.39 43.45

Pseudo-first-order
qe,cal (mg/g) 1.01 4.98 7.18 11.46
h0 (mg/g/min) 0.431 0.705 1.39 1.18
K1 (min1 ) 0.0431 0.047 0.0693 0.0472
R2 0.570 0.898 0.978 0.967
q (%) 31.58 27.48 26.76 24.54

Pseudo-second-order
qe,cal (mg/g) 19.93 28.48 36.58 43.99
k2 (g/(mg min)) 0.0705 0.039 0.027 0.012
h0 (mg/g/min) 28.00 31.63 36.13 23.22
R2 0.9999 0.9999 1 0.9999 Fig. 13 Thermodynamic study of Cr(VI) adsorption onto
q (%) 1.30 0.12 0.17 0.41 FNAC.
Intraparticle diffusion
Ki (mg/g min1/2 ) 0.372 0.436 0.571 1.355 Table 4 Thermodynamic parameters for the adsorption
R2 0.424 0.229 0.493 0.610 of Cr(VI) onto FNAC.
C 16.24 23.88 30.68 29.83 T (K) G (kJ/mol) H (kJ/mol) S (J/mol K)

298 7.59 14.74 0.075

303 7.99
308 8.28
313 8.64
318 9.14

tion (Sharma and Bhattacharyya, 2005). The plot shows two

portions: the first straight portion depicting macropore and
mesopore diffusion and the second representing micropore
diffusion (Fierro et al., 2008). If the value of c is zero, then the
rate of adsorption is controlled by intraparticle diffusion for
the entire adsorption period but in the present study, c is not
zero which confirms more than one process affect the Cr(VI)
adsorption process onto the FNAC.

3.2.7. Thermodynamic studies

Fig. 12 Intraparticle diffusion kinetic plot for the Cr(VI)
adsorption by FNAC (FNAC weight = 0.05 g, pH 2.0, and
temperature = 30 C).
Also, the calculated value (qe,cal = 43.99 mg/g) that was derived
from the second-order equation is quite similar to those
obtained experimentally (qe,exp = 43.45 mg/g), which indicates
that the second-order model is suitable for the observed
kinetics. Moreover, all the determined normalized standard
deviation q (%) of pseudo-first-order and pseudo-second-
order are shown in Table 3. The resulted q (%) values are
relatively lower for the pseudo-second-order kinetic model
than the pseudo-first-order kinetic model.
The diffusion mechanism can not identify either by the
pseudo-first-order or the pseudo-second-order kinetic model.
The intraparticle diffusion varies with the square root of time
is given by (Weber and Morris, 1963) as:
qt = ki t0.5 + c, (11)
where ki is the intraparticle diffusion rate constant
(mg g1 min1/2 ), and c is the intercept. The constant (ki )
for Cr(VI) adsorption was calculated and are tabulated in
Table 3 and plot of qt versus t0.5 is shown in Fig. 12. From
Fig. 12, the plots are not linear over the whole time range,
that confirms more than one process affect the Cr(VI) adsorp-
The measurement of thermodynamic parameters such as
Gibbs free energy (G ), change in enthalpy (H ) and change
in entropy (S ) has been vital in the adsorption studies. Its
original concept assumes that the energy cannot be gained or
lost, where entropy change is the driving force. The values of
H , G and S were calculated according to the following
equations:
qe(W/V)
KC = , (12)
Ce
G = RTlnKC , (13)
S H
lnKC = , (14)
R RT
where R (8.314 J/mol.K) is the universal gas constant, T (K) is
the absolute solution temperature, and KC is the Langmuir
isotherm constant. The values of Ho and So were deter-
mined from the slope and intercept of the vant Hoff plot of ln
KC versus 1/T (Fig. 13). Thermodynamic parameters obtained
from Fig. 13 are tabulated in Table 4. From Table 4, the negative
Gibbs free energy (G ) of the experimental value indicates a
typical physical process. The positive value of the enthalpy
change (Ho = 14.74 kJ/mol) shows that the Cr(VI) adsorption
process onto FNAC is endothermic in nature. The positive
value of So indicates an increase in the degree of freedom (or
70 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 6371

Table 5 The adsorptive capacities of various adsorbents for Cr(VI).

Adsorbents Optimum pH Max. Cr. concentration Qm (mg/g) Reference
used (mg/L)

Tyres activated carbon 2 60 58.50 Hamadi et al. (2001)

F400 (CAC) 2 60 48.54 Hamadi et al. (2001)
Hevea brasilinesis sawdust AC 2 200 44.05 Karthikeyan et al. (2005)
Leaf mould 2 1000 43.10 Sharma and Forster (1995)
Coconut shell carbon 2 20.00 Alaerts et al. (1989)
Hazelnut shell 2 30 17.70 Cimino et al. (2000)
Beech sawdust 1 200 16.10 Acar and Malkoc (2004)
Sugarcane bagasse 2 500 13.40 Sharma and Forster (1994)
Coconut shell carbon 4 25 10.88 Babel and Kurniawan (2004)
Treated sawdust of Indian rosewood 3 10 10.00 Garg et al. (2004)
Aegle marmelos fruit shell 2 10 4.27 Gottipati and Mishra (2016)
Coconut tree sawdust 3 20 3.6 Selvi et al. (2001)
FNAC 2 25 43.45 In this study

disorder) of the adsorbed Cr(VI) onto FNAC means adsorption
is increased with increasing temperature.
3.3. Comparison to some other adsorbents
A comparison of the maximum adsorption capacities of the
FNAC with other reported values for some adsorbents is listed
in Table 5. From Table 5, the FNAC seems to be an alterna-
tive precursor for the commercial AC preparation, in which
its sorption capacity of Cr(VI) is higher than others agricul-
tural waste-based carbonaceous adsorbents. FNAC could be
employed as an efficient carbonaceous adsorbent to compare
with the commercial ones for the removal Cr(VI) from wastew-
ater.
4. Conclusions
In the present study, prepared activated carbon of high sur-
face area with a well-developed pore structure was used for
Cr(VI) adsorption from aqueous solution. The results illus-
trated that the prepared adsorbent showed a high efficiency
in adsorption of Cr(VI). The optimum pH was 2 at which the
Cr(VI) removal was maximum. The maximum Cr(VI) removal
efficiency was found to be 99.08% of 10 mg/L concentration at
pH 2 and temperature of 30 C for 3 h study. Different ther-
modynamic parameters as G , S and H were evaluated
and concluded that the adsorption was feasible, spontaneous
and endothermic in nature. Due to favorable performance of
FNAC in the removal of Cr(VI) from the aqueous solutions, it
can be used as an efficient adsorbent in the treatment of water
and wastewater with no need for further filtering and centrifu-
gation, etc., and also it could be utilized as an alternative to
commercial activated carbons.
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