Separation Science and Technology

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Titanium dioxide, layered hydrazinium titanate

and eggshell as potential sorbents for remediation
of chromium from aqueous stream

Samina H. Shaikh, Sanjukta A. Kumar, Pallavi P. Songire & Suvarna

Sounderajan

To cite this article: Samina H. Shaikh, Sanjukta A. Kumar, Pallavi P. Songire & Suvarna
Sounderajan (2020): Titanium dioxide, layered hydrazinium titanate and eggshell as potential
sorbents for remediation of chromium from aqueous stream, Separation Science and Technology,
DOI: 10.1080/01496395.2020.1742159

To link to this article: https://doi.org/10.1080/01496395.2020.1742159

Published online: 05 Apr 2020.

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SEPARATION SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/01496395.2020.1742159

Titanium dioxide, layered hydrazinium titanate and eggshell as potential

sorbents for remediation of chromium from aqueous stream
Samina H. Shaikha,b, Sanjukta A. Kumara,b, Pallavi P. Songirec, and Suvarna Sounderajana
a
Analytical Chemistry Division, Bhabha Atomic Research Centre, Mumbai, India; bHomi Bhabha National Institute, Bhabha Atomic Research
Centre, Mumbai, India; cProcess Development Division, Bhabha Atomic Research Centre, Mumbai, India

ABSTRACT ARTICLE HISTORY

Titanium dioxide (TiO2), layered hydrazinium titanate (LHT) and eggshell were studied for sorption Received 20 November 2019
of chromium from aqueous streams. Among the three sorbents, the eggshell, a bio-waste is found Accepted 9 March 2020
to have maximum sorption capacity of 315 mg g−1. Sorption of Cr(III) as well as Cr(VI) was found KEYWORDS
to be spontaneous on LHT while TiO2 and eggshell can accumulate only Cr(III). However, sorption Chromium; sorption; TiO2;
of Cr(VI) on these was ensued after in situ reduction of Cr(VI) to Cr(III). Experimental result layered hydrazinium
indicates absence of any interference from ions commonly present in ground water. titanate; eggshell

Introduction In the recent years, various treatment techniques

have been used for the remediation of chromium
The existence of heavy metal pollutants such as chro-
from wastewater and ground water. Some of the tech-
mium, cadmium, lead, mercury and arsenic in the
niques are adsorption,[11] hydroxide precipitation,[12]
ground water has serious threat to the living being
solvent extraction,[13] ion exchange[14] and membrane
and environment. Metals with relatively high density
processes.[15] Among these techniques, sorption techni-
(>5 g/cm3) are referred as heavy metals.[1–5] Most of
que is mostly preferred because of the simplicity and
these heavy metals are toxic and carcinogenic to human
versatility of sorbents. Many organic, inorganic and
health even in relatively low concentrations. Therefore,
biomaterial were investigated for effective removal of
the removal of these metals from ground water is
chromium.[16] Claudia Rosales-Landeros and Mojdeh
a bigger challenge to meet the strict environmental
Owlad have presented an extensive comparison of var-
regulation. Among these heavy metals, chromium is
ious sorbents for chromium sorption; however, none of
the most common contaminant present in the environ-
them is applicable to all situations.[17,18] This demands
ment due to its wide range of applications in industrial
further studies on possible sorbents. TiO2 is a well-
processes.[6] The improper disposal of waste matter
known inorganic metal oxide widely investigated for
from various industrial activities (manufacturing of
its huge application including solar cells/batteries,[19]
stainless steel, surface coating, paints and pigments,
electrochemical sensor[20] and active optical
textile dyeing and leather tanning) leads to contamina-
devices.[21] Besides, TiO2 has great potential for the
tion of surface and ground water. Chromium exhibits
removal of environmental pollutants due its high sur-
in wide range of possible oxidation states from +1 to +6
face area, mechanical strength and photo catalytic
out of which +3 and +6 are most common. Cr(II)
ability.[22] Photo catalysis using TiO2 provide a key
compounds are highly unstable and easily get oxidized
factor for sorption and hence removal of Cr(VI) from
to Cr(III) by oxygen present in air.[7] The two-major
ground water and wastewater.
form of chromium exists in soil and aqueous medium
Currently there is an increasing demand of using bio
are trivalent and hexavalent chromium. Hexavalent
sorbent as an alternate material for removal of toxic
chromium compounds are 500–1000 times more toxic
metals ions from environment because of its low cost
than trivalent chromium,[8] for both acute and chronic
and eco-friendly nature. The bio waste material includ-
exposures because of its high solubility and mobility in
ing saw dust, coir pitch, sugar cane bagasse, orange
water as well as its strong oxidizing nature.[9] The
peel, shell, clay and zeolite,[23,24] are some promising
recommended limit of total chromium in drinking
sorbent for elimination of toxic metals. Among these
water is 0.05 µg L−1.[10]
biomaterials, eggshell is available in huge amount as

CONTACT Sanjukta A. Kumar sanjuktaak301@gmail.com Analytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai, India
© 2020 Taylor & Francis
2 S. H. SHAIKH ET AL.
a waste product from poultry and food industries
which is disposed in landfill without any prior treat-
ment. The major constituent of shell is calcite (95%)
bounded with proteins and traces amount of inorganic
minerals which makes it a valuable sorbent for uptake
of ions. Eggshells and modified eggshell are proved to
be potential sorbent for the capture of hazardous
gases[25] and toxic metal ions.[26]
In our previous studies a synthesized organic poly-
mer (polyhydroxamic acid) was evaluated as efficient
sorbent for the removal of chromium from aqueous
medium.[27] In present work titanium dioxide and
layered hydrazinium titanate (LHT) (a TiO2 –
Hydrazine composite) as synthetic sorbent together
with powdered eggshell as biosorbent were explored
for sorption and removal of Cr from aqueous media.
LHT was found to remove Cr(III) as well as Cr(VI)
efficiently with appreciable sorption capacity. However,
TiO2 and eggshell was found to remove only Cr(III).
The sorption of Cr(VI) on TiO2 was facilitated by
photocatalytic reduction of Cr(VI) to Cr(III) using sun-
light as TiO2 is a well known photo catalyst, whereas
for Cr(VI) sorption on eggshell reducing agents were
used. Literature survey discloses use of various reducing
agents for reduction of highly toxic hexavalent chro-
mium to relatively nontoxic trivalent chromium.[28–30]
In the present case, ascorbic acid, hydroxylamine and
hydrazine salt were used and optimized for reduction
of Cr(VI). The inconvenience in getting sun light inside
laboratory has prompted the use of reducing agent even
in the case of sorption on TiO2 even though it is known
as a good photo catalyst.
Experimental details
Reagents and standards
All reagents used were of AR grade. Potassium hexa-
fluorotitanate, hydrazine hydrate, ascorbic acid and
hydroxylamine were procured from Sigma-Aldrich
and S.D. Fine Chem. respectively. The standard solu-
tions of chromium were prepared from chromium
nitrate and potassium dichromate respectively. For
interference study either chloride or sulfate salts of
sodium, potassium, magnesium and calcium were
used. The eggshell was obtained from fresh hen eggs
and were washed, air dried and powdered. All the
calibration standards were prepared by serial dilution
of stock solutions using 1% nitric acid. Nano pure
water measuring 18.2 M Ω cm−1 of specific resistance,
collected from a Millipore system was used throughout
the experiments. Nitric acid and hydrochloric acid used
were of supra pure grade procured from E. Merck.
Either dilute HCl or dilute NaOH solutions were used
for adjustment of pH.
Instruments used for characterization and
quantification of Cr
All the pH measurements were carried out using
a Mehtrom 780 pH meter. Total chromium concentration
in aqueous solution was quantified by a Continuum Source
Flame Atomic Absorption Spectrometer (Contra AA 300
BU, Analytik Jena, Germany). A Spectrophotometer
(Ocean optics Spectrophometer, DH-2000-BAL) was used
for spectrophotometric determination of Cr(VI) by diphe-
nylcarbazide method. The successful incorporation of
hydrazine in TiO2 was confirmed by attenuated total reflec-
tion Fourier transform infrared spectrometer (FTIR,
Bruker ALPHA-P). The powder X-ray diffraction (XRD)
pattern was obtained using SIEMEN’S KRISTALLOFLEX
D-500 X-Ray diffractometer. Energy dispersive X-ray
fluoresce spectrometer (EX 3600-M Xenemetrix, Jordon
valley AR Ltd. Israel) was used to confirm the uptake of
Cr on sorbents. Valence state of chromium on LHT was
analyzed by X-ray photoelectron spectroscopy using VG
make CLAIM 2 analyzer. The surface area of TiO2 and
LHT measured by in house built surface area analyzer and
calculated according to Brunauer-Emmett-Teller method.
Synthesis and characterization of TiO2 and LHT
The TiO2 was synthesized by dissolving potassium hex-
afluorotitanate (K2TiF6) in hot deionized water in
Teflon beaker with continuous stirring. The resultant
clear solution was heated to boiling temperature in
microwave for 1 h. Precipitate of TiO2 obtained was
filtered, washed and dried in air at room temperature
and used as it is for sorption studies. The hydrazine
modified TiO2 (layered hydrazinium titanate) was
synthesized freshly as per the method discussed
earlier.[31] In brief, aqueous solution of K2TiF6 and
hydrazine hydrate were mixed in Teflon beaker and
subjected to hydrolysis for an hour in microwave
oven. The product formed was thoroughly washed in
deionized water and air dried. The formation of layered
compound was ensured from XRD analysis.
Preparation of eggshell powder
The eggshell was obtained from fresh hen eggs. After
removing yolk and egg white the shell was washed
several times with deionized water and kept in deio-
nized water for 48 h and air dried. The inner thin layer
was removed from the dried eggshell and crush in to
small pieces. Then crushed shell was grinded in a mixer

grinder and sieved to obtain < 200 μm size particles.
The sieved eggshell was stored in high density poly-
ethylene bottle and used for experiments without any
further modification. The sorbent eggshell was charac-
terized by FTIR spectroscopy, X-ray fluorescence and
X-ray diffraction for chemical and structural analysis.
Batch equilibrium studies
All the sorption experiments were conducted in batch
mode at room temperature (28 ± 1°C). The effects of
various parameters on the rate and efficiency of sorp-
tion process were observed by varying contact time,
initial chromium concentration, pH of the solution
and temperature. Experimental solution volume (V)
was kept constant throughout the sorption studies.
For kinetic and pH study 5 mg L−1 Cr(VI) and
Cr(III) solution was equilibrated separately with fixed
amount TiO2, LHT and eggshell. The percentage
uptake of metal ion was calculated as follows:
%Uptake ¼ ðC0 Ce Þ100=C0 (1)
Where C0 and Ce are initial and equilibrium concen-
tration of “Cr” in mg L−1.
The sorption capacities of these sorbents, for Cr(III) and
Cr(VI) were evaluated separately by equilibrating 25 mL of
respective “Cr” solution of concentration 10–2000 mg L−1
with 50 mg of sorbents separately, at optimized condition.
In case of Cr(VI) sorption on TiO2 and eggshell various
reducing agents were attempted for reduction of Cr(VI) to
Cr(III). The amount of “Cr” sorbed at equilibrium was
calculated using following formula:
qe ¼ ðC0  Ce ÞV=w (2)
Where, qe is the amount of “Cr” sorbed per gram of
sorbent, C0 and Ce are the “Cr” concentration in mg L−1
at initial and at equilibrium respectively. V is the volume
of the solution taken in L and w is the mass of dried
sorbent used in gram.
Reduction of Cr(VI) to Cr(III)
Quantitative sorption of Cr(VI) on TiO2 and eggshell
was ensured by in situ reduction of Cr(VI) to Cr(III).
The reduction rate of hexavalent chromium significantly
depends on the type and concentration of reducing
agent. Initially the photocatalytic property of TiO2 was
utilized for this reduction by exposing the experimental
solutions to sun light in case of sorption on TiO2. For
this 25 mL 0.1 to 1000 mg L−1 Cr(VI) solution was
equilibrated with 50 mg TiO2 for 6 h in sunlight, after
equilibration residual solution was quantified for total
chromium using Atomic Absorption Spectrometer.
SEPARATION SCIENCE AND TECHNOLOGY 3
Chemical reducing agents such as ascorbic acid, hydro-
xylamine hydrochloride and hydrazine hydrochloride
were used in case of sorption on eggshell and as an
alternative of sun light in case of TiO2. For the determi-
nation of reduction rate using a reducing agent, fixed
volume of 0.1 M each reducing agents were added indi-
vidually to the 100 mg L−1 Cr(VI) solution. Residual
Cr(VI) was determined spectrophotometrically by
diphenylcarbazide method[32] after predetermined time
intervals. The quantity of reducing agent required for
quantitative reduction of Cr(VI) to Cr(III) was evaluated
experimentally by spectrophotometric analysis of Cr(VI)
in experimental solution.
Determination of point of zero charge of sorbent
(pHPZC)
Point of zero charge (pHPZC) is the pH value at which
the actual charge on sorbent surface is zero. The pHPZC
for TiO2, LHT and powdered eggshell was measured by
pH drift method. For this, a series of 25.0 mL 0.01 M
NaCl solution were adjusted to pH values between 1
and 12 by adding either dilute HCl or dilute NaOH
solution. About 50 mg of sorbent was added to the
solution and kept for equilibration at room tempera-
ture (28 ± 1°C). The final pH, after 48 h was recorded
and plotted against initial pH. The point at which curve
intersect with the line pHinitial = pHfinal (black dotted
line) is taken as pHPZC (Fig. 1).
Characterization of Cr species on sorbent
About 25 mL aqueous solution of Cr(III) and Cr(VI)
was separately equilibrated with 50 mg of LHT at
optimized pH. The mixture was shaken in mechanical
shaker for 3 h at room temperature. After equilibration
the mixture was centrifuged and filtered. The residue
was collected, washed several times with deionized
water and air dried. The chromium [Cr(III) and
Cr(VI)] loaded LHT was characterized by X-ray photo-
electron spectroscopy. Also Cr(III) loaded TiO2 and
eggshell were characterized for chromium species.
Tolerance study
The chromium sorption experiments on TiO2, LHT
and powdered eggshell were performed in the presence
of known concentration of common ground water
matrix elements viz; Na+, K+, Mg2+, Ca2+, Cl−, NO3−
SO42-, CO32-. Three different concentrations of these
ions: 100 mg L−1, 500 mg L−1 and 1000 mg L−1 were
used for these studies. Appropriate quantities of these
ions were added to 25 mL of 5 mg L−1 Cr(III) and
4 S. H. SHAIKH ET AL.

Figure 1. (a) Point of zero charge of TiO2, LHT and eggshell.

Cr(VI) solutions separately and equilibrated for

a predetermined time interval. The sorbent were then
filtered out and residual metal ion concentrations were
determined. For sorption of Cr(VI) ascorbic acid is
used for its reduction to Cr(III).

Result and discussion

Characterization of TiO2, LHT and eggshell
Fourier transform infrared (FTIR) spectra of TiO2 and
LHT are shown in Fig. 2a, peaks observed at 3349 and
Figure 2. FT-IR spectra of (a) TiO2 and LHT and (b) eggshell.
3223 cm−1 are mainly due to asymmetric and sym-
metric stretching vibration of -NH2 of hydrazine func-
tional group which is absent in TiO2 which confirms CaCO3 which elucidate that calcite is a major consti-
the presence of hydrazine in LHT. The peaks at tuent of eggshell.
1646 cm−1 and 807 cm−1is due to strong in-plane
NH2 scissoring absorptions and out-of-plane wagging
Sorption of Cr(III) and Cr(VI) in TiO2, LHT and
absorption respectively. Figure 3a shows XRD profile
eggshell
of LHT. The appearance of 9A° interlayer distance at
2θ ~ 9° indicates formation of a layered hydrazinium Sorption of Cr(VI) and Cr(III) using TiO2, modified
structure.[33] The surface area of TiO2 and LHT were TiO2 (LHT) and eggshell were studied extensively by
found to be 43 m2 g−1 and 120 m2 g−1 respectively. batch equilibration method under varying analytical
The increased surface area of LHT enhances the chro- parameters such as pH of solution, initial chromium
mium uptake. FTIR spectra (Fig. 2b) of eggshell shows concentration and contact time.
the broad peaks at 3240 cm−1 which corresponds to
the O-H stretching vibration and the absorption peaks
Effect of pH
at 1470, 1377 cm−1 and 836 cm−1 are associated with
the C-O stretching and bending vibrations which is pH of the solution is one of the important parameter in
characteristics peaks of carbonate group. The crystal sorption studies. pH influences the chemical species of
structure of eggshell was analyzed by XRD. The dif- the metal ion and surface chemistry of sorbent in aqu-
fraction peaks (Fig. 3b) appeared at 2θ = 23.5, 29.8, eous medium. Therefore, the uptake studies of Cr(III)
36.6, 40 and 43.8 corroborate with calcite structure of and Cr(VI) as a function of pH of the solution has been

Figure 3. XRD plot of (a) TiO2 and LHT and (b) eggshell.
carried out by batch experiments as explained in see
section on “Batch equlibrium studies.” The effect of pH
on the sorption of Cr(III) is studied in the range 0 < pH
< 7 as Cr(III) forms insoluble hydroxide beyond pH 7.
The percentage uptake of Cr(III) and Cr(VI) as
a function of pH of the solution is shown in Fig. 4. It
has been observed that the uptake of Cr(VI) on TiO2
and eggshell was negligible and the uptake pattern
widely differ from LHT where as no significant change
in uptake pattern was observed for Cr(III). At pH 1,
Cr(III) shows negligible uptake for TiO2 and LHT. The
% uptake was observed to increase up to pH 3 and
remains constant thereafter. At low pH Cr(III) primar-
ily exist as positive species. The sorbents (TiO2 and
LHT) also acquires a positive charge at lower pH due
to strong surface protonation. Therefore, they repel
Cr(III) species at low pH values and hence % uptake
was less. The protonation of sorbent weakens as pH
increases which resulted in enhancement of
SEPARATION SCIENCE AND TECHNOLOGY 5
Figure 4. Effect of pH on sorption of (a) Cr(III) and (b) Cr (VI).
electrostatic attraction between sorbent and positively
charged Cr(III) species and hence a gradual increases in
% uptake Cr(III) was noticed.
The effect of pH on the sorption of Cr(VI) is stu-
died in the range 0–10. Cr(VI) exist as negatively
charged ions and as the sorbent acquires a positive
charge at lower pH, the % uptake of Cr(VI) was
appreciable at pH 1 in TiO2 and LHT. As pH increases
the protonation of sorbent weakens which resulted in
decrease of electrostatic attraction between sorbent
and negatively charged Cr(VI) species and hence the
% uptake of Cr(VI) was found to be negligible in case
of TiO2. However, in LHT, the % uptake of Cr(VI) is
like Cr(III) beyond pH 2. This difference in behavior
of TiO2 and LHT may be because of the presence of
hydrazine in LHT. The hydrazine in LHT may be
reducing Cr(VI) to Cr(III) and so the % uptake follows
the pattern of Cr(III). In the case of powdered eggshell
the Cr(III) uptake was very high in entire pH range
6 S. H. SHAIKH ET AL.

which might be due to the high electrostatics attrac-

tion between the negatively charge eggshell (Fig. 1)
and positively charged Cr(III) species. Whereas the
uptake of Cr(VI) was negligible because of the repul-
sion between eggshell and negatively charged Cr(VI)
species. The results obtained indicate that TiO2-
hydrazine composite could be effectively used in the
remediation of trivalent and hexavalent chromium
from ground water in the wide pH range. All the
further experiments were carried out at pH 4 as Cr
(III) (in case of TiO2, LHT and eggshell) and Cr(VI)
(in case of LHT) showed maximum uptake in the pH
range 3–7 (Fig. 4). The slight increase in pH was
observed in equilibrium solution for Cr(VI) sorption
on LHT. The increase in pH due to generation hydro-
xide ions during redox reaction between Cr(VI) and
hydrazine which was incorporated in LHT.
Equation (3) represent the theoretical reaction of
Cr(VI) and hydrazine.[34]
4CrO4 2 þ 3N2 H4 þ 4H2 O ! 3N2 þ 20OH
(3)
þ 4Cr3þ :

Sorption kinetics: effect of contact time for LHT

The uptake of Cr(VI) and Cr(III) having concentration
5 mg L−1 on LHT was carried out at different time intervals
from 0 to 6 h and the results are shown in Fig. 5. As can be
seen from Fig. 5(a,b) the sorption rate was very fast for
Cr(III) attaining equilibrium in 30 min whereas that for
Cr(VI) the rate is slow attaining equilibrium in 3 h.
The delayed sorption equilibrium in Cr(VI) may be
attributed to occurrence of additional process before sorp-
tion. On sorption of Cr(III) as well as Cr(VI), the sorbent
becomes green in color which is a qualitative indication of
presence of Cr(III) species in sorbent irrespective of the
initial chromium species. The finding was supported by
XPS results (Fig. 6) which confirms the presence of Cr(III)
in the sorbent irrespective of the chromium species in the
equilibrating solution. The slower sorption rate in case of
Cr(VI) therefore may be attributed to the additional step of
its reduction to Cr(III) before sorption by the hydrazine
functional group present in LHT.
The experimental data for Cr (III) and Cr(VI) sorp-
tion on LHT were analyzed using pseudo-first-order
and pseudo-second-order kinetics model.[35] The linear
pseudo first-order and pseudo-second-order equation
are represented in the following form:
logðqe  qt Þ ¼ logqe  ðk1 t=2:303Þ (4)
t=qt ¼ 1=k2qe 2þt=qe (5)
Figure 5. Effect of contact time on sorption by LHT (a) Cr(VI)
and (b) Cr(III).
where qe (mg g−1) and qt (mg g−1) are the amount of
chromium ions sorbed on LHT composite at equili-
brium and at time t respectively. k1 and k2 are the
rate constant of pseudo first-order and pseudo-second-
order rate equation. The plot of t/qt verses time t gives
straight line with better fitment of experimental data
(Fig. 7) which suggest that the sorption process is
following a pseudo second order kinetics. The correla-
tion coefficients (R2) for both Cr(VI) and Cr(III) are
0.99 or better which indicates the mechanism as
pseudo-second order. The pseudo-second-order rate
law suggests that the uptake of chromium on LHT is
a chemisorption process which involves the sharing or
exchange of electrons between sorbent and sorbate
(metal ion).[36]

Figure 6. XPS plots of (a) Cr(III) loaded LHT (b) Cr(VI) loaded
LHT.
Sorption capacity of LHT
The maximum sorption capacity of LHT was determined
by batch experiments as explained in section on “Batch
equilibrium studies.” Langmuir and Freundlich adsorption
isotherm models[37,38] were applied to the experimental
data to predict the sorbate behavior. The Langmuir adsorp-
tion isotherm is based on monolayer, uniform, and finite
adsorption site assumptions, therefore a saturation value is
reached beyond which no further adsorption takes place. It
also assumes that there is no interaction between the mole-
cules adsorbed on adjacent sites. The Langmuir equation
which is valid for monolayer adsorption on a sorbent sur-
face is given by Eq. (6):
qe ¼ Q  bCe =1 þ bCe (6)
Ce =qe ¼ 1=Q  b þ Ce =Q  (7)
−1
Where qe is the metal loading (mg g ) at equili-
brium, Ce is metal concentration in the solution at
SEPARATION SCIENCE AND TECHNOLOGY 7
equilibrium (mg L−1), Q° maximum adsorption capa-
city (mg g−1) and b is the equilibrium sorption con-
stant which depends on the affinity of the sorption
sites (L mg−1). Q° and b can be determined from the
linear plot of Ce/qe versus Ce according to Eq. (7).
The sorption data obtained were best fit in Langmuir
model than the Freundlich adsorption isotherm sug-
gesting that the sorption of chromium on LHT are
monolayer coverage which may due to chemisorption
process. The maximum sorption capacity of LHT
composite for Cr(VI) and Cr(III) were 75.5 and
86.2 mg g−1 respectively (Fig. 8). A separation factor
RL (dimensionless constant) which indicates whether
the adsorption is “favorable” or “unfavorable” was
calculated according to following equation.
RL¼ð1=1 þ bCo Þ (8)
Where Co and b is the initial chromium concentration
(mg L−1) and equilibrium sorption constant (L mg−1)
respectively. The value of RL indicates irreversible equi-
librium when RL = 0, favorable equilibrium (0 < RL < 1),
linear (RL = 1) or unfavorable equilibrium (RL > 1). The
calculated separation factor was in the range of 0.95
(5ppm) to 0.02 (2000 ppm) which shows the effective
interaction between chromium and LHT at optimized
conditions.[39]
Sorption of Cr(VI) and Cr(III) on TiO2
As can be seen from Fig. 4, Cr(III) shows similar sorption
behavior on TiO2 and LHT throughout the pH range,
whereas Cr(VI) has different behavior. The different beha-
vior has been attributed to the presence of hydrazine in the
LHT matrix which reduces Cr(VI) to Cr(III) in situ.
Therefore, to improve the Cr(VI) sorption on TiO2 its
reduction was carried out using external agents. Since
TiO2 is known to have photocatalytic reduction properties,
sunlight was the first choice for reduction of Cr(VI) to
Cr(III). The experimental procedure was explained in sec-
tion on “Reduction of Cr(VI) to Cr(III).” Sorption of
Cr(VI) in sunlight was found to be useful only up to an
initial Cr(VI) concentration up to 10 mg L−1. Therefore,
other reducing agents such as ascorbic acid, hydroxylamine
hydrochloride and hydrazine hydrochloride are evaluated
for reduction of Cr(VI) to Cr(III). The reduction rate of
Cr(VI) using ascorbic acid, hydroxylamine hydrochloride
and hydrazine hydrochloride is shown in Fig. 9a. It is
evident from the figure that the reduction rate of Cr(VI)
was rapid in case of ascorbic acid and hydroxylamine
hydrochloride. Complete reduction of Cr(VI) occurred
within 15 and 45 min with ascorbic acid and hydroxyla-
mine hydrochloride respectively. However, the rate of
Cr(VI) reduction is comparatively slow with hydrazine
8 S. H. SHAIKH ET AL.
Figure 7. Pseudo second-order and pseudo-first-order plots of Cr(VI) (a and c) and Cr(III) (b and d).
hydrochloride, with 10% residual Cr(VI) even after 80 min.
Ascorbic acid has an instant reduction effect which is
evident from Fig 9a. Figure 9b represents the quantification
of Cr (VI) by diphenylcarbazide method. For the quantifi-
cation of Cr(VI) the salt of hydrazine, hydroxylamine and
ascorbic acid (each 1.0 mL of 0.1 M concentration) was
added to 50 mL of 100 mg L−1 Cr(VI) solution and after
15 min the spectra was recorded. The result as represented
in Fig. 9b shows complete reduction of Cr(VI) within
15 min using ascorbic acid as reducing agent. Also, it is
environmentally benign and hence used for Cr(VI) reduc-
tion in the sorption experiment with TiO2 and eggshell. The
removal of Cr(VI) by TiO2 as sorbent was carried out in
presence of ascorbic acid. The amount of ascorbic acid was
optimized experimentally and found to be 80 mg for com-
plete reduction of 50 mg Cr(VI). The sorption capacity of
TiO2 for Cr(VI) (after reduction) was similar as that Cr(III)
and followed Langmuir adsorption isotherm (Fig. 10).
Sorption of Cr(VI) and Cr(III) on eggshell
The sorption experiment was carried out as
per section on “Batch equilibrium studies.” For
Cr(VI) optimized quantity of Ascorbic acid was
used for reduction of Cr(VI) to Cr(III) before
subjecting it for sorption (section 2.6). After
equilibration, two separated green color compound
was observed in the solution, one is gelatinous
present in suspended form and other is settled at
bottom of the solution. It is noticeable from Fig. 11
that the sorption of Cr on eggshell powder
increased linearly up to 1500 mg L−1 and reached
saturation point. The solution after filtration was
clear and colorless. The chromium loaded eggshell
and gelatinous chromium hydroxide precipitate was
separated and subject to X-ray diffraction analysis.
Cr(OH)3 is amorphous in nature when it precipi-
tates out at room temperature and XRD analysis
confirmed the gelatinous precipitate was amorphous
chromium (III) hydroxide [Cr(OH)3]° (Fig. 12a).[40]
The other green compound is eggshell loaded with
Cr(III) which has same XRD pattern (Fig. 12b) as
that of eggshell (CaCO3) with reduced intensity
which might be due to the sorption of “Cr” on
eggshell. The sorption of “Cr” on eggshell was con-
firmed by XRF analysis. The XRF spectra of
 SEPARATION SCIENCE AND TECHNOLOGY 9

Figure 9. (a) Rate of Cr(VI) reduction using ascorbic acid, hydro-

xylamine hydrochloride and hydrazine hydrochloride (b) DPC-Cr
(VI) absorption peak after 15 min of interaction with reductant.
Figure 8. Langmuir adsorption isotherm for (a) Cr(VI) and (b)
Cr(III) on LHT.

eggshell and Cr(III) loaded eggshell are shown in

Fig 13a,b respectively. The appearance of Kα
(5.39 keV) and Kβ (5.92 keV) peaks in XRF spectra
of Cr loaded eggshell confirmed the sorption of
“Cr” on eggshell. Peaks at 3.68 and 4.01 keV energy
correspond to the Kα and Kβ of calcium which
a major constituent of eggshell. In aqueous solution
Cr(III) exist as [Cr(H2O)6]3+, [Cr(H2O)5(OH)]2+,
[Cr(H2O)4(OH)2]1+ species at pH<7 and at neutral
pH Cr(III) precipitate out as gelatinous [Cr(H2O)3
(OH)3]° compound (from Eh-pH relation).[16] The
hexaaquachromium(III) complex ion is fairly acidic
in nature having a pH range 2–3 in aqueous solu-
tion. The eggshell being alkaline in nature, removes
the H+ from the hexaaquachromium (III) complex Figure 10. Langmuir adsorption isotherm for Cr(VI) sorption on
TiO2 with ascorbic acid as reductant.
10 S. H. SHAIKH ET AL.

and produced neutral insoluble compound [Cr(H2

O)3(OH)3]°(Equation 9). The precipitation of chro-
mium hydroxide in presence of eggshell can be
represented as follows:
 3þ

2 CrðH2 OÞ6 ðaqÞþ3CaCO3 Eggshell
 
! 2 CrðH2 OÞ3 ðOHÞ3 0 þ 3Ca2þ þ3CO2 þ3H2 O
(9)
The mixed XRD pattern of Cr(III) and Cr(VI) oxide
was obtained (Fig. 12c) when Cr(OH)3 (gelatinous pre-
cipitate) incinerated at 600ºC for 3 h. The formation of
Cr(VI) compound might be due to oxidation of
Cr(OH)3 during incineration in air atmosphere. To
ensure the presence Cr(VI) compound, the residue
(after heating to 600°C) was dissolved in hydrochloric
Figure 11. Effect of initial Cr concentration on sorption for the quantification of Cr(VI) (by diphenylcarbazide).
capacity. It was found that 45% chromium was in hexavalent

Figure 12. XRD plot of (a) Cr(OH)3 gelatinous precipitate (b) eggshell and “Cr” loaded eggshell. (c) After heating Cr(OH)3to 600ºC for
3 h. (d) Left over residue after dissolution in HCl.
 SEPARATION SCIENCE AND TECHNOLOGY 11

Table 1. Effect of interfering ions on chromium uptake by LHT.

% Uptake of Cr(III) % Uptake of Cr(VI)
Concentration of Concentration of
Interfering ions interfering ions (µg mL−1) interfering ions (µg mL−1)
100 500 1000 100 500 1000
Na+ 100 100 100 100 100 100
+
K 100 100 100 100 100 100
2+
Mg 100 100 100 100 100 100
Ca2+ 98 98 97 96 92 90
Cl− 100 100 99 100 100 99
NO3− 100 100 99 100 100 97
2-
SO4 100 100 99 100 100 96
CO3 2-
– – – 99 98 96
Combined ions 100 99 99 99 93 82
n = 5; RSD = 5%.

Table 2. Adsorption capacities of other similar types of adsor-

bent for Cr(VI).
Sorption capacity
Adsorbent pH (mg g−1) References
Silica 2–4 1.5 [42]
La(III) Silica-Chitosan 2–4 5.5 [42]
Oxidized multiwalled carbon 2.05 4.26 [43]
nanotubes
γ-alumina nanoparticles 5 30.3 [44]
Zeolite HDTM 6 39.47 [45]
ZnO nanoparticles on biochar Natural 43.48 [46]
pH
Ethylenediamine 2.5 61.35 [47]
functionalized Fe3O4
Graphene oxide 3.0 67.66 [48]
functionalized with
magnetic cyclodextrin–
chitosan
Layered hydrazinium titanate 3–10 75 Present
work
TiO2 (After reduction of Cr(VI) 3–7 69 Present
to Cr(III) using ascorbic work
acid)
Eggshell (After reduction of 3–7 315 Present
Cr(VI) to Cr(III) using work
ascorbic acid)
Figure 13. X-ray fluorescence spectra of (a) eggshell and (b) Cr
loaded eggshell.
negligible effect on chromium uptake up to
1000 µg mL−1. However small decrease in uptake
form. The left over residue after dissolution of Cr(VI)
was observed in case of Ca2+ ions which may due
was confirmed to be Cr2O3 from XRD (Fig. 12d).[41]
to complexing ability of calcium ions. Cr(VI)
uptake was reduced to 82% in the presence of
combined ions (each 1000 µg mL−1) while Cr(III)
Tolerance of Cr(III) and Cr(VI) sorption
uptake was not affected. No significant interference
The studies were conducted to determine selective was observed in case of uptake on eggshell as well
sorption of chromium in presence of coexisting as TiO2 up to 1000 µg mL−1 concentration of inter-
ions as per section 2.9. The tolerance for Cr(VI) fering ions (individual and mixed ions).
and Cr(III) sorption on LHT, TiO2 and eggshell
was seen in presence of ions such as Na+, K+,
Mg2+, Ca2+, Cl− SO42-, NO3− and CO32- which are
Comparison with other similar sorbents
commonly present in natural water and ground-
water. For sorption of Cr(VI) on TiO2 and eggshell, The sorption capacity of various similar kind of sorbent
ascorbic acid was added to the experimental solu- were compared and listed in Table 2. It is clear from the
tion prior to equilibration with the sorbent to comparison table that most of the sorbents (listed in
reduce Cr(VI) to Cr(III). The experimental data table) work in some particular pH while LHT and egg-
for LHT is shown in Table 1. From the results, it shell can be applied in wide pH range for the removal
is evident that the influence of most of the ions has chromium from aqueous solution. The sorption
12 S. H. SHAIKH ET AL.
capacity of LHT and eggshell is higher as compared to
other similar type of adsorbents.
Conclusion
In this work the TiO2, LHT and Eggshell were employed as
sorbent for removal of trivalent and hexavalent chromium.
LHT was found to remove Cr(III) as well as Cr(VI) effi-
ciently with a sorption capacity of 86.2 and 75.5 and mg g−1
respectively. However, TiO2 and eggshell was found to
remove only Cr(III). The sorption of Cr(VI) on TiO2 and
eggshell was facilitated by adding ascorbic acid to the
experimental solution. About 80 mg Ascorbic acid was
sufficient to reduce 50 mg of Cr(VI) quantitatively.
Eggshell was found to have a high sorption capacity of
315 mg g−1 for Chromium. Comparison with similar sor-
bents from literature reveals a higher capacity for the pre-
sent sorbents TiO2, LHT and eggshell.
Acknowledgements
Authors are grateful to Associate Director of Chemistry
Group and Head of Analytical Chemistry Division (Bhabha
Atomic Research Centre) for providing support throughout
the work. Authors are grateful to Dr Jagannath, TPD, BARC
for providing XPS data.
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