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ScienceDirect
Procedia Technology 24 (2016) 585 – 594

International Conference on Emerging Trends in Engineering, Science and Technology (ICETEST

- 2015)

A study on effects of pH, adsorbent dosage, time, initial

concentration and adsorption isotherm study for the removal of
hexavalent chromium (Cr (VI)) from wastewater by magnetite
nanoparticles
Padmavathy K. S.a, G.Madhub, Haseena. P.V.a
a
Government Engineeirng College, Thrissur-680009, Kerala, India
b
Cochin University of Science and Technology, CUSAT-682022, Kerala, India

Abstract

Magnetite nanoparticles synthesized in the laboratory were used for the removal of Hexavalent chromium (Cr (VI))
from synthetically prepared wastewater. The synthesized particles were characterized using scanning electron
microscopy equipped with energy dispersive X-Ray spectroscopy, X ray diffraction and thermogravimetric analyzer.
Batch adsorption studies were conducted to study the effects of pH, magnetite dosage, time and initial concentration
on Cr (VI) removal. Adsorption isotherm study was also conducted. Optimum pH for the present work was 3.0 and
all the other studies were done at this pH.The adsorption followed Freundlich isotherm model.UV-VIS
spectrophotometer was used to measure the concentration of Hexavalent chromium in water.
© 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2016 The Authors.Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICETEST – 2015.
Peer-review under responsibility of the organizing committee of ICETEST – 2015
Keywords:Adsorption; hexavalent chromium; magnetite nanoparticles; wastewater.

1. Introduction

Heavy metal pollution due to rapid industrialization and growth in world pollution is a serious threat to environment
and all forms of life [1, 2].The toxic metals are emitted to the environment from various industries in such a quantity
that pose risk to human health [3].Chromium is used in industries such as wood preservation, leather tanning, steel

2212-0173 © 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICETEST – 2015
doi:10.1016/j.protcy.2016.05.127
586 K.S. Padmavathy et al. / Procedia Technology 24 (2016) 585 – 594

fabrication and metal finishing [4]. The two oxidation states in which chromium exists are III and VI. Cr (III) is
hazardous only at high concentration whereas Cr (VI) is toxic even at low concentrations. Cr (VI) containing
wastewater is treated by reducing to trivalent chromium in most cases [13]. Concentration of Cr (VI) in drinking
water that is allowable is 50 ppb according to world health organization (WHO). Cr (VI) present in water causes
cancer and other adverse effects in human beings [11].

For the removal of Chromium (VI) from wastewater, adsorption is highly effective when compared to other
conventional methods. Adsorption method is used for removing a large number of pollutants from wastewater.
Adsorption is used for removal of low concentration pollutants. In adsorption solid surface is bounded with
molecules of liquid. Adsorbents possess large internal surface area that permits adsorption. Principle of adsorption is
adhesion [12].

Adsorption is also an economical method and is very effective at low concentration of metal ions. Activated carbon,
biological materials, chitosan, fly ash etc are some of the commonly used adsorbents for Cr (VI) removal [11, 15].
The disadvantages of commercial available adsorbents are high cost, low adsorption capacity, difficulty of
separation after adsorption etc. Nanotechnology deals with particles of nanosize. When nanomaterials are used as
adsorbents mass transport resistance is greatly reduced due to size of adsorbents [10]. Nanoparticles are now a day’s
widely used in wastewater due to their high surface area and adsorption capacity [5, 9].

Magnetite nanoparticles have got wide applications in the field of data storage, ferrofluids, nano adsorbents,
biomedicine, bio sensor etc. They can be easily separated after adsorption in the presence of magnetic field [6, 14,
16, and 17]. In the present study magnetic nanoparticles were prepared by sol gel method in the laboratory and
characterized using scanning electron microscopy equipped with energy dispersive X-Ray spectroscopy and
thermogravimetric analyzer. Batch adsorption studies were conducted to study the effect of parameters like pH,
time, initial concentration and adsorbent dosage.
1.1 Materials and methods
Materials
Stock solution of Chromium (VI) was prepared using potassium dichromate purchased from Sigma Aldrich. Ferric
nitrate nonahydrate and ethylene glycol were used for preparation of magnetic nanoparticles. Water from Millipore
water purification system was used for conducting the experiments. Batch adsorption tests were conducted in
incubated shaker.
Methods
1000 ppm of stock solution was prepared by dissolving 2.835 g of potassium dichromate in one liter distilled water.
Various concentration of the solution was obtained by dilution of 1000 mg/l of stock solution. Concentration of
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chromium solution was measured using UV-VIS spectrophotometer [Hitachi U-2900).1, 5 Diphenyl carbazide was
used for spectrophotometric determination of Cr (VI). Spectrophotometer was first calibrated using various
concentration of Cr (VI) solution (0, 10 ppm, 20 ppm, 30 ppm, 40ppm and 50 ppm). A straight line calibration curve
is obtained which is used to measure the concentration of hexavalent chromium.

Sol-gel method was used for the synthesis of magnetite nanoparticles.0.02 mol ferric nitrate nonahydrate and 25 ml
ethylene glycol was stirred using a magnetic stirrer for 3 hours at room temperature. The solution turned to a brown
sol which is heated at 80oC in a constant temperature bath. Brown gel was obtained and for 1 hour it was aged at
room temperature and dried in a muffle furnace. Then finally it was annealed at 400 oC for 8 hours. Black magnetite
powder was obtained [7]. Nanoparticles obtained were characterized using scanning electron microscopy equipped
with energy dispersive X-ray spectroscopy (SEM-EDX), X-Ray Diffraction (XRD) and Thermogravimetric analyzer
(TGA).
1.2 Experiments
Adsorption experiments were performed in the laboratory in an incubated shaker by varying the parameters that
affects adsorption of chromium (VI) on to magnetite nanoparticles. The effect of adsorbent dosage, pH, time of
shaking and initial concentration was studied by taking 100 ml of potassium dichromate solution in Erlenmeyer
flasks and at 30oC. Adsorbent dosage was varied from 5 to 10 g/l by taking all other parameters constant. Initial
concentration was varied from 10 to 60 ppm and pH varied from 3-10 which was adjusted using 0.1M HCl and
0.1M NaOH. Time of shaking was changed from 20 to 120 minutes. After the predetermined time is achieved, the
adsorbate solution was withdrawn and filtered to separate the adsorbent. 0.2 μm cellulose nitrate membrane filter
paper was used for filtration of the solution after adsorption. Then magnetic field was also applied for removal of
magnetic nanoparticles. After filtration the concentration of solution was determined using previously calibrated
UV-VIS spectrophotometer at 540nm [8].
Chromium (VI) adsorption efficiency (E %) is given by

E = [(C0-Ct)/Co] ×100 (1)

Metal adsorption is given by

Q (mg/g) = (C0-Ct)/m (2)

where C0 is the concentration of Chromium (VI) in the solution before adsorption in mg/l and Ct is the concentration
of Chromium (VI) in the solution after adsorption in mg/l and m (g) is the amount of adsorbent in one liter of
solution [8]. After adsorption the adsorbent can be regenerated using proper solvent to desorb the adsorbed particles.
588 K.S. Padmavathy et al. / Procedia Technology 24 (2016) 585 – 594

Thus the adsorbent can be reused.

2. Results and discussion

2.1 Effect of Initial Concentration

The effect of change in adsorption efficiency with initial concentration is shown in the figure. Initial concentration
was varied from 10 to 60 ppm. pH, time, adsorbent dosage, temperature was kept constant. The variation of
efficiency with change in initial concentration varies from 70 to 66% as shown graphically. Chromium uptake
versus initial concentration is also shown in figure. Eventhough removal efficiency and Cr (VI) uptake decreases
with increase in initial concentration, the change is only very less. This shows that initial concentration has only a
very little effect on adsorption.

Fig. 1. Effect of Initial concentration on Cr uptake and Efficiency

2.2 Effect of pH
Maximum removal efficiency of hexavalent chromium is higher at low pH. As the pH was increased from 3 to 10
efficiency decreases as shown in the figure. Optimium pH was at 3.0 and all other experiments were done at this pH.
As pH increases the surface of magnetite nanoparticles become more negatively charged. This causes increased
repulsion between Cr (VI) and magnetite nanoparticles. Hence the removal efficiency decreases with increase in pH.
Also change in chromium uptake with pH is shown graphically.

Fig.2. Effect of pH on efficiency and Cr uptake

2.3 Effect of adsorbent dosage
As adsorbent dosage increases keeping all the other parameters at constant value removal efficiency first increases,
reaches maximum and then decreases. As adsorbent dosage increases chromium uptake decreases as shown in the
figure. At lower adsorbent concentration number of active sites is higher. With the increase in adsorbent dosage
aggregation of particles take place, as a result efficiency and Cr uptake decreases.
 K.S. Padmavathy et al. / Procedia Technology 24 (2016) 585 – 594 589

Fig.3. Effect of adsorbent dosage on efficiency and Cr uptake

2.4 Effect of time
As time of adsorption is changed from 20 to 120 minutes, efficiency first decreased from 72 to 69% and further
increased to 72 % and afterwards no change is observed. As time progresses the surface coverage of the adsorbent is
high and further no adsorption take place. Figure shows the effect of time on adsorption. Also change in Cr (VI)
uptake with time is shown in figure.

Fig.4. Effect of time

2.5 Adsorption isotherm
Langmuir isotherm represents monolayer adsorption and Freundlich model represents multilayer adsorption.
Langmuir isothem is given by the equation

qmax bCt
q= (3)
1 + bCt

where Ct is the equilibrium concentration, b is constant related to affinity of binding sites, qmax is the maximum
amount of metal ion per unit weight of adsorbent to form a complete monolayer on the surface. The Langmuir
equation can be represented in other form as given below.

Ct C 1
= t + (4)
q qmax bqmax

Freundlich isotherm is given by the equation

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q = KCt1/n (5)

In this isotherm binding sites are considered different. K is related to adsorption capacity and n refers to adsorption
intensity[Foo et al. (2010)]. Taking logarithm on both sides

1
log q = log K + log Ct (6)
n
In the present work Freundlich model gives a better value of adsorption capacity when compared to Langmuir
model. The values of isotherm constants are given in table 1. Langmuir and Freundlich plots are shown in figure 5.

Fig.5. Adsorption Isotherms

Table 1 Isotherm Parameters for adsorption at 303K

T(K) Langmuir Model

R2 0.994

q max(mg/g) 0.015

b(l/mg) 5128

T(K) Freundlich Model

R2 0.996

1/n 1.025

K 3.81

2.6 Characterization Thermogravimetric Analyzer

STA-6000 Perkin Elmer thermogravimetric analyzer was used to study the thermal stability of nanoparticles. The
weight loss of the material was noted when it was heated to 600 oC at the rate of 5 o
per minute. TGA curve of
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synthesized nanoparticles is shown in figure.

Fig.6. TGA Curve for magnetite nanoparticles

The weight decreases initially at a slow rate and after 200oC weight loss is at a faster rate and further weight loss
rate decreases.
2.7 Characterization using SEM-EDX
The synthesized nanoparticles are characterized using Scanning electron microscopy (SEM) equipped with energy
dispersive X-Ray spectroscopy (EDX). The SEM image of synthesized nanoparticles indicates that the particles are
nano in size. EDAX image shows that the synthesized nanoparticles indicate that only iron and oxygen are present.
SEM image and EDAX image are shown below.

Fig.7.scanning electron microscopy equipped with energy dispersive X-Ray spectroscopy of magnetite nanoparticles

2.8 Characterization using XRD

Using X-Ray diffraction the average particle size of particles was found to be 56nm. XRD pattern of the synthesized
magnetite nanoparticles is shown in figure.
The average particle size of synthesized magnetite nanoparticles were calculated using Deybe-Scherrer Formula

Kλ
D= (7)
β cos θ

Where D =mean diameter of nanoparticles

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β =The full width at half maximum value of XRD diffraction lines

λ = the wavelength of X-ray radiation source

θ = the half diffraction angle –Bragg angle

K = the Scherrer constant with value from 0.9 to 1.

Fig.8. XRD of magnetite nanoparticles

3. Conclusions

Magnetite nanoparticles were synthesized using sol gel method in the laboratory and were used to remove
hexavalent chromium from wastewater. The effect of initial concentration, adsorbent dosage, pH and time was
studied at constant temperature of 30oC. Langmuir and Freundlich isotherm parameters were determined. The
synthesis of magnetite nanoparticles are of low cost. Scale up of the process can be accomplished by designing a
suitable column using magnetite nanoparticles as adsorbent. For scaling up the nanoparticles shall be impregnated in
a suitable matrix to form a polymer nano composite. Removal of hexavalent chromium is therefore effectively
performed using adsorption on magnetite nanoparticles.
Acknowledgements
The financial support received from Centre for Engineering Research and Development (CERD/RSM/63/2012)
established by Government of Kerala, India for conducting this study is gratefully acknowledged.
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