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Removal of Cr(VI) From Wastewater by

Adsorption on Iron Nanoparticles


Y. C. Sharma,1 * V. Srivastava,1 C. H. Weng2 and S. N. Upadhyay3
1. Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, Varanasi 221 005, India
2. Department of Civil and Ecological Engineering, I-Shou University, Da-Hsu Hsiang, Kaohsiung County 84008, Taiwan, ROC
3. Department of Chemical Engineering and Technology Institute of Tecnology, Banaras Hindu University, Varanasi 221 005,
India

Due to rapid industrialisation, the presence of heavy metals in water and wastewater is a matter of environmental concern. Though some of the
metals are essential for our system but if present beyond their threshold limit value (TLV), they are harmful and their treatment prior to disposal
becomes inevitable. The present communication has been addressed to the removal of Cr(VI) from aqueous solutions by nanoparticles of iron.
Nanoparticles of iron were prepared by solgel method. The characterisation of the nanoparticles was carried out by XRD and TEM analysis. Batch
experiments were adopted for the adsorption of Cr(VI) from its solutions. The effect of different important parameters such as contact time and
initial concentration, pH, adsorbent dose, and temperature on removal of chromium was studied. The removal of chromium increased from 88.
5% to 99.05% by decreasing its initial concentration from 15 to 5 mg L1 at optimum conditions. Removal of Cr(VI) was found to be highly pH
dependent and a maximum removal (100%) was obtained at pH 2.0. The process of removal was governed by rst and pseudo-second-order
kinetic equations and their rate constants were determined. The process of removal was also governed by intraparticle diffusion. Values of the
thermodynamic parameters viz. G , H , and S at different temperatures were determined. The data generated in this study can be used to
design treatment plants for chromium rich industrial efuents. Adsorption results indicate that nanoiron particles can be effective for the removal
of chromium from aqueous solutions.
A cause de lindustrialisation rapide, la presence de metaux lourds dans leau et dans les eaux usees est une question environnementale dune
importance cruciale. Meme si certains metaux sont essentiels au bon fonctionnement de notre organisme, sils y sont presents dans une concen-
tration superieure a la valeur limite dexposition (VLE), ils deviennent nocifs et leur traitement avant elimination devient inevitable. La presente
communication traite de lenlevement du Cr(VI) present dans les solutions aqueuses au moyen de nanoparticules de fer. Les nanoparticules de fer
ont ete obtenues au moyen du procede sol-gel. La caracterisation des nanoparticules a ete effectuee au moyen dune analyse diffractometrique
et dune analyse par MET. On a effectue des essais a renouvellement periodique pour mesurer ladsorption de Cr(VI) dans les solutions ou on en
trouvait. Leffet de differents parametres importants comme le temps de contact et la concentration initiale, le pH, la dose dagent adsorbant ainsi
que la temperature au moment de lenlevement du chrome ont ete etudies. La proportion de chrome eliminee est passee de 88,5% a 99,05% en
diminuant sa concentration initiale de 15 a 5 mg/l, en conditions optimales. Il a ete etabli que lelimination du Cr(VI) est etroitement liee au pH
et lelimination optimale (100%) ete obtenue a un pH de 2,0. Le processus delimination a ete regi par des equations cinetiques du premier et du
deuxieme ordre et les constantes cinetiques ont ete determinees. Le processus delimination etait aussi regi par la diffusion intraparticulaire. Les
valeurs des parametres thermodynamiques (G , H et S ) ont ete determinees pour differentes temperatures. Les donnees generees dans le
cadre de la presente etude peuvent etre utilisees pour concevoir des installations de traitement des efuents industriels a teneur elevee en chrome.
Les resultats relatifs a ladsorption indiquent que les nanoparticules de fer peuvent etre efcaces pour eliminer le chrome present dans des solutions
aqueuses.

Keywords: adsorption, chromium, nanoiron, wastewater

INTRODUCTION

T
he presence of heavy metals in aquatic systems due to dis-
Author to whom correspondence may be addressed.
charge of industrial efuents is of concern because of their
E-mail address: ysharma.apc@itbhu.ac.in
toxic and non-biodegradable nature (Arslan and Pehlivan, Can. J. Chem. Eng. 87:921929, 2009
2007). Chromium is a useful metallic species and has applications
in different industries such as electroplating, leather tanning, and
2009 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.20230

| VOLUME 87, DECEMBER 2009 | | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 921 |
metal nishing (Bansal et al., 2009). Chromium exists in various solution, acetone, potassium dichromate,1,5diphenyl carbazide,
oxidation states but its trivalent and hexavalent states commonly hydrochloric acid, sulphuric acid, sodium hydroxide, and phos-
exist in water bodies. Cr(III) is an essential metal for living beings phoric acid.
because it takes part in glucose, lipid, and protein metabolism.
It also helps in development of muscles. Chromium has been
reported to be toxic, mutagenic, and carcinogenic and its toxic Preparation of Nanoparticle of Iron Oxide
effects are well documented (Sharma et al., 2007; Bhattacharya There are various methods for preparation of nanoparticles of iron
et al., 2008). The United States Environmental Protection Agency (Thapa et al., 2004; Hironori et al., 2007; Jing et al., 2007; Xiantao
(USEPA) permissible limit of Cr(VI) in wastewater is 0.05 mg L1 et al., 2008). In this study nanoiron particles were prepared by
(Acar and Malkoc, 2004). The chromium containing efuents ferric chloride and ferrous chloride in 2:1 molar ratio. Solution of
must be properly treated prior to their discharge in water bodies. Fe2+ and Fe3+ were prepared by dissolving it in distilled water and
There are many technologies such as ion exchange, reverse this solution was then heated up to 40 C for 10 min. After heating
osmosis, precipitation, reduction, and membrane ltrations, but solution was precipitated by ammonia solution with continuous
most of them are incur high operational and maintenance cost stirring on magnetic stirrer at 40 C. Black coloured particles of
(Weng et al., 2008). In spite of being costly, they are also related to iron were precipitated. These particles were then separated from
sludge generation. Sludge disposal is another major problem with the solution by using a strong magnet and than washed many
most of these techniques (Monteagudo and Ortiz, 2000; Suksabye time with distilled water followed by washing with dilute HCl to
et al., 2008). Amongst several physicocho-chemical techniques, remove excess of OH group. Finally these particles were washed
adsorption is most versatile method for removal of metallic pol- by acetone and then dried overnight in a hot air oven at 60 C.
lutants from aqueous solutions (Elangovan et al., 2008). This After drying, iron particles were characterised by X-ray diffrac-
technique is related with high removal efciency even at very low tometer (XRD). Phase characterisation of calcined powders at
concentrations of metallic ions. There are a number of conven- different temperatures were conducted by XRD technique [X-ray
tional adsorbents viz. activated carbon, y ash, chitosan, zeolite, diffractometer, Scifert and Co., Model ID-3000, Germany] using
montmorillonite, sphagnum moss peat, kaolinite, wollastonite, CuK radiation, 2 = 20 80 . Crystallite size was determined by
bentonite, saw-dust, sea weeds, alumina, soya cake, redmud, etc. using the diffraction peaks from Scherer formula (Sun et al.,
which have been frequently reported for the removal of metal- 2004):
lic pollutants from aqueous solutions and wastewaters (Ayuso
et al., 2007; Baral et al., 2008). Among them activated carbon K
D= (1)
is most promising, but its high cost always limits its large-scale b cos
application to developed nations (Acar and Malkoc, 2004). In
recent years, scientists have shown signicant interest in search- where D is the crystallite size (nm),  is wavelength of the
ing alternatives of activated carbon. Nanotechnology has opened monochromatic X-ray beam (0.154056 nm for CuK radiation),
an area for development of new adsorbent with unique charac- b is full width at half maximum for the diffraction peak under
teristics. At nanoscale materials shows high catalytic properties, consideration (rad), K is constant(0.9),  is diffraction angle
high surface area, and greater active sites to interact with metallic (degree). Size of the particles was also conrmed by TEM. Fur-
species (Khaleel et al., 1999; Ling et al., 2006; Hristovski et al., ther, the method of preparation of the nanoiron is very simple
2007). As adsorption is a surface phenomenon, nanoadsorbents and an uncontaminated material is obtained by the method
offers high efciency due to their high surface area. Application adopted.
of nanoadsorbents in the eld of wastewater treatment is becom- The advantages associated with application of nanoiron for
ing an interesting area of research. Iron oxide, aluminium oxide, removal of pollutant species from aqueous solutions are its large
and titanium oxides have been used for the removal of metallic controllable surface area, non-toxic nature, economic viability,
pollutants from aqueous solutions and industrial efuents. Iron and the dispersed nature of its particles. This dispersed nature
oxide has high surface area and can easily be synthesised, sev- of the particles diminishes the problems related to clogging of
eral researchers have used it as an adsorbent (Deliyanni et al., the columns. Another aspect of using nanoiron in separation
2004; Huang et al., 2007). It has been found to be effective in processes is their extremely smaller size which offers almost neg-
removing metallic ions. Different forms of Iron (III) oxides such as ligible mass transfer resistance. These advantages are specic to
goethite, amorphous ferric oxide, and crystalline ferric oxide have the nanoiron particles.
been used for removal of heavy metals (Jhonson, 1990; Manceau
and Charlet, 1994; Fendrof et al., 1997; Venema et al., 1998;
Zeng, 2003; Deliyanni et al., 2004; Pokhrel and Viraraghavan, Adsorption Studies
2007). Numerous studies demonstrate that bulk iron oxides have Batch adsorption experiments were conducted to investigate the
good efciency to remove heavy metals from aqueous solutions. efciency of nanoiron particles for the removal of chromium from
But due to high surface area, nanoparticles have better efciency aqueous solutions. Stock solution of chromium was prepared
than bulk particles of same materials (Ponder et al., 2001). The by adding potassium dichromate to distilled water and used for
non-toxic and non-corrosive nature is another benet with these preparation of chromium solution of various concentrations rang-
adsorbents (Lazaridis et al., 2005). In present study, nanoparti- ing from 5 to 15 mg L1 . For determination of equilibrium time
cles of iron were prepared and used for removal of hexavalent 0.20 g of adsorbent was added in 50 mL of chromium solution
chromium from its solutions. in 150 mL of stoppard conical ask. After attaining equilibrium
time, adsorbent was separated from solution by centrifugation at
10,000 rpm for 10 min. All experiments were conducted at the pH
MATERIALS AND METHODS of working solution viz. 6.7 and room temperature 25 C (0.5)
All the chemicals used were of analytical grade. Chemicals used except in the experiments of effect of temperature. The effect of pH
in this study were ferrous chloride, ferric chloride, ammonia was studied at pH values of solutions at 2.0, 4.0, 8.0, and 10.0,

| 922 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 87, DECEMBER 2009 |
respectively. The concentration of Cr in the solution was main-
tained at 10 mg/L and pH was maintained by adding 0.1 M HCl
and 0.1 M NaOH. The residual concentration of Cr(VI) was deter-
mined by UVVis spectrophotometer at 540 nm with 1,5 diphenyl
carbazide by following the APHA, AWWA standard method for
examination of water and wastewater (Standard Methods, 1975).
The % removal of Cr(VI) was calculated by using following for-
mula:
 
Cnal
% removal of Cr(VI) = Cinitial 100 (2)
Cinitial

DETERMINATION OF pHzpc OF NAOPARTICLES


OF IRON
pHzpc is an important property of any adsorbent. This parame-
ter indicates the electrical neutrality of the adsorbent surface at a
particular value of pH. Determination of pHzpc was done to inves-
tigate the surface behaviour of nanoiron particles (Namdeo and
Bajpai, 2008). For its determination 0.01 M NaCl was prepared
and its pH was adjusted in the range between 2 and 12 by using
NaOH and/or HCl. Then 50 mL of 0.01 M NaCl was taken in con-
ical ask and then 0.20 g of alumina powder was added to this.
These asks were then kept for 48 h and nal pH of the solu-
tions was measured by using a pH meter (IKON Ltd, New Delhi, Figure 2. a: TEM of nanoiron particles. b: SADP (select area diffraction
India). Graphs were then plotted between pHnal versus pHinitial . pattern) of nanoiron particles.
The point of intersection of the two curves has been recorded as
pHzpc of nanoiron powder (Namdeo and Bajpai, 2008). Effect of Adsorbent Dose
Figure 3 shows effect of adsorbent dose on removal of Cr(VI). Dose
was varied in the range of 0.100.40 g. Increasing the adsorbent
RESULT AND DISCUSSIONS dose increases the percent removal presumably due to an increase
in the number of active sites. However, the removal increased from
Characterisation of Adsorbents 97.5% to 100% in 15 min time by increasing dose up to 0.40 g
(Figure 4).
XRD of prepared sample (Figure 1) shows the formation of Fe3 O4 .
The peaks were conrmed by JCPDS (19-0629). Crystallite size
was calculated to be 15 nm. TEM of the nanoiron also conrms
Kinetic Studies
that prepared powder was in nanorange (Figure 2a,b). In present studies, removal of chromium decreased from 99%
to 88.5% by increasing concentration of chromium from 5 to

200 100

98
180
96

160 94
Intensity (a.u)

% Removal

140 92

90
120
88

100
86 5mg/l
10mg/l
80 84 15mg/l
0 10 20 30 40 50 60
60 Contact time(min)
20 30 40 50 60 70 80
Angle2 Figure 3. Effect of contact time and initial concentration on the removal
of Cr(VI) by adsorption on nanoiron. [Colour gure can be viewed in the
Figure 1. XRD of nanoiron powder. online issue, which is available at www.interscience.wiley.com.]

| VOLUME 87, DECEMBER 2009 | | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 923 |
-1.5
100.0
-1.6
99.5 -1.7

99.0 -1.8
-1.9
% Removal

98.5

log(qe-q)
-2.0
98.0 -2.1

97.5 -2.2
-2.3
97.0 25 oC
-2.4 35 oC
96.5 -2.5 45 oC

96.0 -2.6
0.10 0.15 0.20 0.25 0.30 0.35 0.40 4 6 8 10 12 14 16
Adsorbent dose(g) Contact time(min)

Figure 4. Effect of adsorbent does on the removal of Cr(VI) by Figure 5. Lagergrens plot for the adsorption of Cr(VI) on nanoiron at
adsorption on nanoiron. different temperatures. [Colour gure can be viewed in the online issue,
which is available at www.interscience.wiley.com.]

15 mg L1 at room temperature. It is due to saturation of avail-


able active sites on adsorbent surface. It is observed that for The value of k2 at 25 C was found to be 6.72 g mg1 min1
xed dose of adsorbent, the number of active sites to interact for 5 mg/L. The value of R2 was found 0.977 and 1 for
with the adsorbate is also xed. By increasing concentration these pseudo-rst-order and pseudo-second-order model, respectively.
sites becomes saturated by chromate ions which nally result in On comparison of R2 values, it was found that adsorption reaction
decreased removal. There was no signicant change in percent was well tted in pseudo-second-order model also.
removal of Cr(VI) ions after 30 min, after attainment of equilib-
rium. Intraparticle diffusion study
To explain the adsorption process, data generated by batch
studies was investigated for its tness in expression of pseudo- In usual batch experiments, the adsorption can also occur by intra-
rst-order reaction. Pseudo-rst-order reaction can be expressed particle diffusion. To conrm this the value of rate constant kid
by following equation (Bhattacharya et al., 2008): was calculated from the slopes of the linear portion of the plots
of amount adsorbed versus square root of time at different tem-
  perature for 5 mg L1 of Cr(VI) concentration by using following
kad
log(qe q) = log qe t (3) equation (Weber and Morris, 1963):
2.303

where q is the amount of Cr(VI) adsorbed at time t; qe is the q = kid t 1/2


amount of Cr(VI) adsorbed (mg g1 ) at equilibrium time; kad is
the rate constant(min1 ) of adsorption. The value of kad at dif- where q is the amount adsorbed at time t (mg/g) and t is the
ferent temperatures were determined by the slope of the graphs square root of the time of contact (min ). The straight lines in
log(qe q) versus t (Figure 5). Linear plot indicates applicabil- graphs thus conrming the occurrence of intraparticle diffusion.
ity of Lagergrens model in this study. The value of kad at 25 C was The values of kid were calculated from the slopes of Figure 5 and
found to be 0.1099 min1 for 5 mg L1 . 25 C, its values were found to be 0.04 102 mg g1 min0.5 .
The adsorption data were also analysed by pseudo-second-order
kinetic equation. This can be expressed as follows (Ho and McK-
kay, 1999): pHzpc of Nanoadsorbent
pHzpc plays important role in characterising the nature of surface
dq of any adsorbent and removal of metals depends upon pHzpc of
= k2 (qe qt )
dt adsorbent. pHzpc of nanoiron is shown in Figure 6 and found to
be 7.1. Its lower value indicates that there are some impurities in
Where k2 (g mg1 min1 ) is the rate constant of pseudo-second- prepared powder. In previous studies it was found to be between
order reaction. The integrated form of above equation can be 6.5 and 8.0 (Kosmulski, 2004; Namdeo and Bajpai, 2008).
expressed as follows:

t 1 1 Effect of pH
= + t
qt k2 qe2 qe The pH is an important parameter which affects the removal of
chromium from the solution. Also, changing pH does not remove
all solutes, only some, and specically chromium which is being
h = k2 qe2 discussed here. The effect of pH on removal of chromium has
been shown in Figure 7. It is clear from this gure that removal
where h is known as initial sorption rate. The value of qe and k2 is highly dependent on pH of Cr(VI) solution. The removal was
can be determined by the slope and intercept of the straight line high in acidic range with a maximum (100%) at pH 2.0 and min-
of the plot of t/qt versus t (gure not given). imum in alkaline range, minimum (84.31%) at pH 10.0. The

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a 1
12

Fraction of Cr(VI) species


0.8 HCrO4- CrO42-
10

0.6
8
pH final

0.4
6
H2CrO4 5 mg/L Cr(VI)
0.2
Cr2O72-
4
0
0 2 4 6 8 10 12
2 pH
pH initial versus pH final
1
0
pH final- pH final line b
0 2 4 6 8 10 12

Fraction of Cr(VI) species


pH initial 0.8 HCrO4- CrO42-

Figure 6. Plot for determination of pHzpc of nanoiron. [Colour gure can 0.6
be viewed in the online issue, which is available at www.interscience.
wiley.com.]
0.4

H2CrO4 15 mg/L Cr(VI)


present ndings are supported by the speciation of chromium 0.2
Cr2O72-
(Figure 8a,b).
Different species which are commonly exist in aqueous solu- 0
2 0 2 4 6 8 10 12
tion are Cr2 O27 , HCrO4 , CrO4 , and HCr 2 O7 . It is clear from pH
Figure 8(a,b) that maximum removal occurs at pH 2.0. Removal
of Cr(VI) from its aqueous solution decreases by increasing pH Figure 8. a: Distribution diagram of Cr(VI) species as a function of pH for
from 2.0 to 10.0. Similar ndings were also investigated by other total Cr(VI) of 5 mg L1 . b: Distribution diagram of Cr(VI) species as a
investigators (Weng et al., 2008). function of pH for total Cr(VI) of 15 mg L1 .
It is clear from speciation diagram of Cr(VI) that at this
pH, HCrO 4 are major species. At lower pH, OH

group
are neutralised by hydrogen ions and favours to adsorb this
species.
EFFECT OF TEMPERATURE
HCrO 4 introduces in solution by following reaction:
Temperature is also an important parameter in adsorption pro-

7 + H2 O 2HCrO4
Cr2 O2 (4) cesses. Effect of temperature on removal of Cr(VI) from its
aqueous solutions was carried out and is shown in Figure 9. It
At higher pH Cr2 O2 2
7 , CrO4 are present in aqueous solution. In
is clear from this gure that by increasing temperature from 25
this condition presence of larger number of OH hinders the diffu- to 45 C, removal percentage also increased from 99% to 99.7%
sion of dichromate ions. Thats why removal percentage decreases at 5.0 mg L1 initial concentration of Cr(VI) solution. It shows
by increasing pH. endothermic nature of adsorption reaction.

100
100

95 99
% Removal
% Removal

90
98

85
97
25 oC
80 35 oC
45 oC
96
0 10 20 30 40 50 60
75
2 4 6 8 10 Contact time(min)
pH of Cr(VI) solution
Figure 9. Effect of temperature on the removal of Cr(VI) by adsorption
Figure 7. Effect of solution pH on the removal of Cr(VI) by adsorption on on nanoiron. [Colour gure can be viewed in the online issue, which is
nanoiron. available at www.interscience.wiley.com.]

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ADSORPTION ISOTHERMS
0.6
The different isotherms were studied to understand adsorption
mechanism. The data generated by batch experiments were inves-
tigated by Langmuir, Freundlich, and DubininRadushkevich 0.5
isotherms.
0.4
Langmuir Isotherm

log qe
The Langmuir equation is expressed by the following expression 0.3
(Sharma et al., 2007):
0.2
Ce 1 Ce
= + (6) 25oC
qe Q b Q 35oC
0.1
1
45oC
where Ce (mg L ) is the equilibrium concentration of the solute
(mg L1 ), qe is amount adsorbed at equilibrium (mg g1 ), and Q0 0.0
(mg g1 ) and b (L mg1 ) are constants related to the adsorption -2.0 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4
capacity and energy of adsorption, respectively. Plots of Ce /qe log Ce
versus Ce (Figure 10) are straight lines showing suitability of the
proposed isotherm. The values of Q0 and b were determined by Figure 11. Freundlich plot for on the removal of Cr(VI) by adsorption on
nanoiron. [Colour gure can be viewed in the online issue, which is
the slopes and intercepts of Figure 11. The values for Langmuir
available at www.interscience.wiley.com.]
constant are given in Table 1.
For Langmuir isotherm, a dimensionless separation factor can
be expressed by following equation:
  Table 1. Langmuir constants for the removal of Cr(VI) by adsorption
1
RL = (7) on nanoiron
1 + bC0
Temperature ( C) Q0 (mg g1 ) b (L mg1 )
where C0 is the initial concentration (mg L1 ), b is Langmuir
25 3.55 7.58
adsorption equilibrium constant (L g1 ).
The dimensionless constant separation factor RL is used to 35 3.56 9.49
determine that whether the adsorption is favourable or not.
The value of RL indicates the type of the isotherm to be either 45 3.53 12.55
unfavourable (RL > 1), linear (RL = 1), favourable (0 < RL < 1), or
irreversible (RL = 0). The values of RL at different temperatures in
the experiments are given in Table 2. It is clear from this table
that RL values are greater than zero and less than unity indicating
that adsorption of Cr onto nanoiron is favourable. Table 2. RL values for the removal of Cr(VI) by adsorption on
nanoiron at different temperatures

Temperature ( C) RL
0.6
25 0.03
35 0.02
0.5 45 0.02

0.4
In this study adsorption capacity of nanoiron was compared
Ce/qe

0.3 with some of commonly used adsorbents. Adsorption capacity of


different adsorbents are shown in Table 3.
0.2

25oC Freundlich Isotherm


0.1 35oC The Freundlich isotherm assumes that the uptake of metal ions
45oC occurs on a heterogeneous adsorbent surface (Sharma et al.,
2007). The Freundlich equation is expressed as:
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 qe = Kf Ce1/n (8)
Ce
its linear form is as under:
Figure 10. Langmuir plot for the removal of Cr(VI) by adsorption on
nanoiron. [Colour gure can be viewed in the online issue, which is 1
available at www.interscience.wiley.com.] log qe = log Kf + log Ce (9)
n

| 926 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 87, DECEMBER 2009 |
Table 3. Comparison of adsorption capacities of different adsorbents
1.2
for the removal of Cr(VI)

Adsorbents Adsorption Refs. 1.0


capacity (mg g1 )

Raw rice bran 0.07 Oliveira et al. (2005) 0.8


Riverbed sand 0.15 Sharma and Weng (2007)

lnqe
0.6
Activated rice husk carbon 0.8 Bishnoi et al. (2004)

Wollastonite 0.83 Sharma (2001)


0.4
Coconut shell powder 1.23 Pino et al. (2006)

Flyash 1.4 Banarjee et al. (2004) 0.2

Activated alumina 1.6 Bishnoi et al. (2004)


0.00E+000 1.50E+007 3.00E+007 4.50E+007 6.00E+007
Nanoiron 3.56 Present study 2

Saw dust 3.6 Baral et al. (2006) Figure 12. DubininRadushkevich adsorption isotherm for the removal
of Cr(VI) by adsorption on nanoiron. [Colour gure can be viewed in the
Distillary sludge 5.7 Selvaraj et al. (2003) online issue, which is available at www.interscience.wiley.com.]

The linear form of above equation can be expressed as:

ln qe = ln qm B2 (11)
Table 4. Freundlich constants for the removal of Cr(VI) by adsorption  
on nanoiron 1
2 = RT ln 1 + (12)
Ce
Temperature ( C) Kf n

25 2.94 3.62 where R is the gas constant (8.314 J/mol K) and T is the abso-
lute temperature. The value of qm and B can be obtained by the
35 3.06 3.88 intercept and slope of the graph of ln qe versus 2 (Figure 12).
The value of B and qm were found to be 15.95 107 and
45 3.14 4.53 1.14 mg g1 , respectively at 298 K.
 
1
E= (13)
2B
where Kf and 1/n are related to the adsorbent capacity and sorp-
tion intensity of the adsorbent, respectively. The values of the E is the mean free energy of sorption per molecule of the sorbate
Freundlich constants, Kf and 1/n, were determined by slopes and (kJ mol1 ).
intercepts of Figure 11. The value of Kf is referred to the bonding The DR plot gives straight line which indicates that adsorption
energy of adsorption. The value of n can be used to determination follows DR equation in this study (Figure 12). The magnitude of
of deviation of linearity of the adsorption. E determines the type of adsorption process. Value of E was found
The values of Freundlich constants are given in Table 4. When to be 5.59 106 kJ mol1 .
the value of n is 1, the adsorption is a linear isotherm. When
the value of n < 1 or n > 1, which implies that the adsorption
reaction is related to a chemical or favourable physical process, THERMODYNAMIC STUDIES
respectively. As shown in Table 4, the value of all n are >1, indi- Thermodynamic studies are used to explain any reaction in a
cating favourable adsorption and conrming that adsorption is a better way. In the present investigations, thermodynamic studies
physical process. were performed and the parameters, namely, G , H , and S ,
were determined at 25, 35, and 45 C, respectively. The thermody-
namic parameters were calculated using the following equations
DR Isotherm (Sharma et al., 2008):
To investigate the nature of adsorption process DR isotherm was Cac
applied for experimental data. DR isotherm does not assume Kc = (14)
Ce
a homogeneous surface or constant sorption potential. The DR
equation can be expressed as follows (Demiral et al., 2008): G = RT ln Kc (15)
   
T2 T1 K2
H = R ln (16)
qe = qm exp(B ) 2
(10) T2 T1 K1

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Processing Agricultural Waste: A Case Study of Rice Husk, J.
Table 5. Values of thermodynamic parameters for the removal of
Hazard. Mater. 162, 312320 (2009).
Cr(VI) by adsorption on at different temperatures
Baral, S. S., S. N. Das and P. Rath, Hexavalent Chromium
Temperature ( C) G (cal/mol) H (cal/mol) S (cal/mol K) Removal From Aqueous Solution by Adsorption on Treated
Sawdust, Biochem. Eng. J. 31, 216222 (2006).
25 2,757.14 +7,452.31 +34.26 Baral, S. S., S. N. Das, G. R. Chaudhury, Y. V. Swamy and P.
35 3,099.74 Rath, Adsorption of Cr(VI) Using Thermally Activated Weed
45 3,640.35 Salvinia Cucullata, Chem. Eng. J. 139, 245255 (2008).
Bhattacharya, A. K., T. K. Naiya, S. N. Mandal and S. K. Das,
Adsorption, Kinetics and Equilibrium Studies on Removal of
H G Cr(VI) From Aqueous Solutions Using Different Low-Cost
S = (17)
T Adsorbents, Chem. Eng. J. 137, 529541 (2008).
Bishnoi, N. R., M. Bajaj, N. Sharma and A. Gupta, Adsorption
where Kc is the equilibrium constant and Cac and Ce (both mg L1 ) of Cr(VI) on Activated Rice Husk Carbon and Activated
are the equilibrium concentrations of metal ions on the adsor- Alumina, Bioresour. Technol. 91, 305307 (2004).
bent surface and the equilibrium concentration of metal ions in Deliyanni, E. A., N. K. Lazaridis, E. N. Peleka and K. A. Matis,
the solution, respectively. The values of these parameters have Metals Removal From Aqueous Solution by Iron-based
been given in Table 5. Positive values of entropy change S Bonding Agents, Environ. Sci. Pollut. Res. 11, 1821 (2004).
and enthalpy change H also indicate the endothermic nature of Demiral, H., I. Demiral, F. Tumsek and B. Karabacakoglu,
adsorption of Cr(VI) on nanoiron powder. Theromodynamic stud- Adsorption of Chromium(VI) From Aqueous Solution by
ies revealed that a greater adsorption can be obtained at higher Activated Carbon Derived From Olive Bagasse and
temperatures. Applicability of Different Adsorption Models, Chem. Eng. J.
144, 188196 (2008).
Elangovan, R., L. Philip and K. Chandraraj, Biosorption of
Hexavalent and Trivalent Chromium by Palm Flower
CONCLUSIONS
(Borassus aethiopum), Chem. Eng. J. 141, 99111 (2008).
The adsorption studies on removal of Cr(VI) by nanoiron indi- Fendrof, S., M. J. Eick, P. Grossl and D. L. Sparks, Arsenate and
cate that nanoiron can be an effective adsorbent for chromium Chromate Retention Mechanisms on Goethite. 1. Surface
removal. It was found that adsorption is highly dependent on Structure, Environ. Sci. Technol. 31, 315320 (1997).
pH. Lower pH favours adsorption of Cr(VI) ions from its aqueous Hironori, I., K. Takayanagi, T. Nakanishi and T. J. Osaka,
solutions. Adsorption increases by increasing temperatures which Synthesis of Fe3 O4 Nanoparticles With Various Sizes and
shows endothermic nature of reaction. Kinetic studies indicate Magnetic Properties by Controlled Hydrolysis, J. Colloid
that removal process was governed both by rst-order and pseudo- Interf. Sci. 314, 274280 (2007).
second-order kinetic equations. Equilibrium data were replaced Ho, Y. S. and G. McKkay, Pseudo-Second Order Model for
in Langmuir, Freundlich, and DR isotherm equations and their Sorption Processes, Process Biochem. 34, 451465
constants were determined. Thermodynamic studies revealed fea- (1999).
sibility of adsorption reaction and also conrm endothermic Hristovski, K., A. Baumgardener and P. Westerhoff, Selecting
nature of the process of removal. Metal Oxide Nanomaterials for Arsenic Removal in Fixed Bed
Columns: From Nanopowders to Aggregated Nanoparticle
Media, J. Hazard. Mater. 147, 265274 (2007).
ACKNOWLEDGEMENTS Huang, Y. H., C. I. Hsueh, H. P. Cheng, L. C. Su and C. Y. Chen,
The authors are thankful to AICTE, Govt. of India for providing Thermodynamics and Kinetics of Adsorption of Cu(II) Onto
nancial assistance to V.S. Waste Iron Oxide, J. Hazard. Mater. 144, 406411
(2007).
Jhonson, B. B., Effect of pH, Temperature and Concentration on
the Adsorption of Cadmium on Goethite, Environ. Sci.
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