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Biochemical Engineering Journal 23 (2005) 185192

Study on biosorption of Cr(VI) by Mucor hiemalis


Neetu Tewaria , P. Vasudevana , B.K. Guhab,
a

Center for Rural Development and Technology, Indian Institute of Technology, Delhi 110016, India
b Department of Chemical Engineering, Indian Institute of Technology, Delhi 110016, India

Received 9 December 2003; received in revised form 14 September 2004; accepted 5 January 2005

Abstract
Many investigations have been carried on metal binding capacity of different groups of microorganisms. However, the reports on the
kinetic, thermodynamic and desorption study of biosorption process are quite limited. The present study was carried out in a batch system
using Mucor hiemalis for its sorption and desorption study of Cr(VI). M. hiemalis exhibited the highest Cr(VI) uptake of 53.5 mg/g at an initial
pH of 2.0. Equilibrium data fitted well to Langmuir isotherm model. Biosorption showed pseudo-second order rate kinetics at different initial
concentration of Cr(VI) and different dose of M. hiemalis. The activation energy of the biosorption (Ea ) was estimated as 4.0 kJ/mol using
Arrhenius equation. Using the equilibrium constant value obtained at different temperature, the thermodynamics properties of the biosorption
(G , H and S ) were also determined. The biosorption of Cr(VI) onto M. hiemalis was found to be endothermic. Desorption data
showed that nearly 99% of the Cr(VI) adsorbed on M. hiemalis could be desorbed using 0.1N NaOH. Study with the cyclic use of a batch of
M. hiemalis repeatedly after desorption, showed that it retain its activity up to five sorption and desorption cycles.
2004 Elsevier B.V. All rights reserved.
Keywords: Adsorption; Biosorption; Bioremediation; Mucor hiemalis; Wastewater treatment; Chromium; Desorption

1. Introduction
Rapid industrialization and increase in population has led
many-fold increase in the utilization and release of chemicals including heavy metals. As consequences, these metals are found in toxic concentrations in aqueous systems.
Heavy metals like mercury, cadmium, lead, nickel, and
chromium are toxic, even in extremely minute quantities. Anthropogenic sources of chromium are industries viz., electroplating, leather tanning, metal finishing, chemical industries
and many others. Chromium exists in several oxidation states
out of which Cr(III) and Cr(VI) are most stable form. Because
of its high toxicity and potential carcinogenicity Cr(VI) is of
especial concern. In humans, Cr(VI) causes severe diarrhea,
ulcers, eye and skin irritation, kidney dysfunction and probably lung carcinoma [1]. Various methods used for removal of
Cr ions include chemical reduction and precipitation, reverse
Corresponding author. Tel.: +91 11 26591038 (O)/26591813 (R);
fax: +91 11 26581120.
E-mail address: bkguha iitdelhi@rediffmail.com (B.K. Guha).

1369-703X/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.bej.2005.01.011

osmosis, ion exchange and adsorption on activated carbon


or similar material. But all these methods suffer from severe
constraints, such as incomplete metal removal, high reagent
or energy requirements, generation of toxic sludge or other
waste products that require safe disposal. Some of the treatment methods involve high operating and maintenance cost.
There is, therefore, a need for some alternative technique,
which is efficient and cost effective. Biosorption could be
such an alternative method of treatment. It employs wide variety of biomass for removal of metal ions such as algae [2],
fungi [3] and bacteria [4]. Biosorption has distinct advantages over conventional methods of treatments: the process
does not produce chemical sludge, hence non polluting, it is
more efficient, easy to operate. It is very efficient for removal
of pollutants from very dilute solutions also. Since biosorption often employs dead biomass this eliminates the need of
nutrient requirement and can be exposed to environments of
high toxicity [5]. A major advantage of biosorption is that it
can be used in situ, and with proper design may not need any
industrial process operations and can be integrated with many
systems in the most eco-friendly manner. In this study, Mucor

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N. Tewari et al. / Biochemical Engineering Journal 23 (2005) 185192

hiemalis was used as biosorbents for the removal of Cr(VI).


The objective of the present investigation was to study the
biosorption equilibrium, kinetic, thermodynamics and desorption.
1.1. Equilibrium study of biosorption
The equilibrium established between adsorbed phase on
the biosorbents and that in solution can be represented by
adsorption isotherms. The most widely used isotherms for
modeling equilibrium are Freundlich and Langmuir isotherm
equations. The Freundlich isotherm equation is an empirical
equation based on the sorption on a heterogeneous surface
suggesting that binding sites are not equivalent and/or independent. The monocomponent Freundlich isotherm equation
[6] is given below:
1/n

qeq = Kf Ceq

(1)

where Kf and n are Freundlich constants related to sorption


capacity and sorption intensity, respectively. From the linearized plot of log qeq versus log Ceq , these constants can be
determined.
Langmuir isotherm equation is based on monolayer sorption onto a surface with finite number of identical sites, which
are homogeneously distributed over the sorbent surface and
is given by the Eq. (2) [7]
qeq =

Qmax bCeq
1 + bCeq

(2)

where Qmax and b are Langmuir constants denoting maximum adsorption capacity and the affinity of the binding sites,
respectively. These constants can be determined from the
1/Ceq versus 1/qeq . This also represents the physical bondage
between the component and adsorbent.

Similarly, pseudo-second order rate equation is expressed


as
dq
= k2 (qeq qt )2
dt

(5)

where k2 is pseudo-second order rate constant. After integration and applying the same boundary conditions t = 0 and
qt = 0 to t = t and qt = qeq at equilibrium, Eq. (5) becomes
t
1
t
=
+
2
qt
q
k2 (qeq )
eq

(6)

where value k2 can be determined from the intercept of


linearized plot of t/qt versus t.
1.3. Thermodynamics of biosorption
1.3.1. Activation energy
Activation energy is determined according to the Arrhenius equation
ln k =

Ea
+ ln A0
RT

(7)

where Ea is activation energy and A0 is constant called the


frequency factor. Value of Ea can be determined from the
slope of ln k versus 1/T plot.
1.3.2. Gibbs free energy change (G )
G is the fundamental criterion of spontaneity. Reaction
occurs spontaneously at given temperature if the value of
G is negative. Value of G can be determined from the
following equation
G = RT ln b

(8)

1.2. Kinetic model

where R is gas constant (8.314 J/mol K), b is Langmuir constant and T is absolute temperature.

Pseudo-first order and pseudo-second order rate equation


have been used for modeling the kinetics of Cr(VI) biosorption. Pseudo-first order rate equation is expressed as follows
[8]

1.3.3. Enthalpy (H ) and entropy (S ) change


Relation between G , H and S can be expressed
by the following equations

dqt
= k1 (qeq qt )
dt

(3)

(9)

Eq. (9) can be written as

where qt and qeq is sorption capacity at time t and at equilibrium, respectively and k1 is pseudo-first order rate constant.
After integration and applying boundary conditions t = 0 and
qt = 0 to t = t and qt = qeq at equilibrium, Eq. (3) becomes
k1 t
log(qeq qt ) = log qeq
2.303

G = H TS

(4)

where value of k1 can be determined from the slope of the


plot of the log (qeq qt ) versus t.

RT ln b = H TS

(10)

or
ln b =

S
H
+
RT
R

(11)

where values of H and S can be determined from the


slope and the intercept of the plot between ln b versus 1/T.

N. Tewari et al. / Biochemical Engineering Journal 23 (2005) 185192

2. Materials and methods


2.1. Procurement and culturing of M. hiemalis
Pure strain of M. hiemalis was obtained from Department of Biochemical Engineering and Biotechnology, IIT
Delhi (India). It was cultured in potato dextrose broth and the
biomass was harvested after 7 days. Harvested biomass was
washed thoroughly and was killed by autoclaving at 121 C
and a pressure of 15 lb.
2.2. Chemicals
A stock solution (1000 mg/l) of Cr(VI) was prepared by
dissolving 2.828 g of K2 Cr2 O7 (AR grade) in distilled water.
The stock solution was then appropriately diluted to get the
test solutions of desired strength.
2.3. Analysis of Cr(VI) ions
The concentration of the Cr(VI) ions was determined spectrophotometrically after complexation of the metal ion with
1,5-diphenylcarbazide [9]. The absorbance was recorded at
540 nm using UV spectrophotometer (UV-160, Shimadzu)
and concentration was determined from the calibration curve.
2.4. Biosorption studies
Biosorption experiments were carried out in batch in 250ml Erlenmeyer flasks to elucidate the best conditions at which
the maximum Cr(VI) sorption was observed. These flasks
were kept on a rotatory shaker at 27 2 C and 120 rpm. After
agitating the solutions for desired time period solutions were
centrifuged at 3000 rpm for 10 min and then the supernatant
solution was analyzed for Cr(VI) concentration.
2.4.1. Effect of pH of solution on Cr(VI) sorption
The pH of the solution was varied from 1.0 to 8.0. It was
adjusted by using 0.1N HCl/NaOH. Dried M. hiemalis (0.1 g)
was added to 100 ml of solution having 100 mg of Cr(VI)/l,
in 250-ml Erlenmeyer flasks.
2.4.2. Effect of dose of sorbent on Cr(VI) sorption
The dose of sorbent was varied by using different sorbent
to solute ratio in the adsorption solution. Different amounts
of sorbent were added to vary the sorbent to solute ratio in
the range of 20100 g/g, 100 ml of solution having 100 mg
Cr(VI)/l at pH 2.0.
2.4.3. Effect of initial Cr(VI) concentration on Cr(VI)
sorption
The effect of initial Cr(VI) concentration was studied in
the range 10600 mg/l. Sorbent (0.1 g) was added to 100 ml
of solution having varying Cr(VI) concentration, in 250-ml
Erlenmeyer flasks at a pH of 2.0.

187

2.4.4. Equilibrium study


All the data were analyzed using Langmuir and Freundlich
isotherm equilibrium. Corresponding correlation were used
to draw the plots of concentration in terms of the mass of
solute adsorbed per unit mass of adsorbate against the concentration of sorbent.
2.4.5. Kinetic study
Kinetics of Cr(VI) sorption was studied at varying initial
Cr(VI) concentration in the range of 10500 mg/l. Sorbent
(0.1 gm) was added to 100 ml of Cr(VI) solution in 250-ml
Erlenmeyer flasks. Kinetics of Cr(VI) sorption was also studied at doses of sorbent to solute ratio from 10 to 100 g/g of
the solute. Different doses of sorbents were added to 100 ml
of 100 mg Cr(VI)/l in 250-ml Erlenmeyer flasks to achieve
this variation. In both the above-mentioned experiments the
pH of the solutions was adjusted to 2.0 and samples were
analyzed after every 15 min for 90 min.
2.4.6. Effect of temperature on sorption
Kinetic experiments were also carried out at 27, 40 and
50 C, at initial concentration varying from 10 to 500 mg/l.
0.1 g of the sorbent was added to 100 ml of Cr(VI) solution
in 250-ml Erlenmeyer flasks. The results were analyzed to
determine rate parameter at different temperature. The effect
of temperature on sorption process was studied in terms of
the thermodynamic parameters like activated energy, Gibbs
free energy, enthalpy and entropy change.
2.4.7. Desorption of Cr(VI)
Desorption of Cr(VI) from previously loaded M. hiemalis
was studied by using 0.1N NaOH as eluent. For this purpose,
0.2 g of previously loaded M. hiemalis was added to 20 ml
of eluent in a 150-ml conical flasks. After 90 min of shaking,
the supernatant was analyzed for the Cr(VI) concentration.
The desorption cycle was carried out five times.

3. Results and discussion


3.1. Effect of pH of solution on Cr(VI) sorption
The experimental result show that M. hiemalis could
biosorb substantial quantity of Cr(VI) as shown in Fig. 1. Further, it was observed that the extent of sorption of chromium
ions by the sorbent increased with increase in acidity up to
a pH of 2.0. Further reduction in the pH value of the solution showed reduction in biosorption. The figure shows that
maximum sorption was observed at the pH 2.0. The sorption
capacity of Cr(VI) at pH 2.0 by M. hiemalis was 30.1 mg/g,
which reduced to 3.0 mg/g at pH 6.0. Several other authors
have also found that adsorption of Cr(VI) on biomass increased with lowering of pH and is highest at pH value of 2.0
[1012]. Cr(VI) occurs in the form of oxy anion as HCrO4 ,
Cr2 O7 2 , CrO4 2 , Cr4 O13 2 , Cr3 O10 2 [13]. The lowering
of pH causes the surface of the sorbent to be protonated to

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N. Tewari et al. / Biochemical Engineering Journal 23 (2005) 185192

Fig. 1. Effect of pH of solution on sorption of Cr(VI) on M. hiemalis.


Dose of M. hiemalis1 g/l; initial Cr(VI) concentration100 mg/l; contact time24 h; agitator speed120 rpm.

Fig. 2. Effect of dose of M. hiemalis on removal of Cr(VI). Initial


Cr(VI) concentration100 mg/l; pH2.0; contact time4 h; agitator
speed120 rpm.

a higher extent. This results in a stronger attraction for negatively charged Cr(VI) complex ions in the solution. Hence,
the sorption increases with the increase in the acidity of
the solution. But as the pH rises, the concentration of OH
ions increases and overall charge on the sorbent surface becomes negative which causes hindrance in the sorption of
negatively charged Cr ions like Cr2 O7 2 , CrO4 2 , etc., results in the decreased sorption of Cr(VI) at higher pH. M.
hiemalis biomass contains 3040% chitin and chitosan units
[14], which serves as a matrix of COOH and NH2 groups.
The FTIR spectroscopic analysis of Rhizopus cell wall has
indicated the involvement of amino group in Cr binding [15].
At pH 2.0, the negatively charged chromate ions would interact more strongly with the positively charged functional
groups of M. hiemalis biomass resulting in high Cr(VI) uptake. It is known that the dominant form of Cr(VI) at pH 1.0
is the acid chromate ion species (HCrO4 ) and increasing pH
shifts the concentration of HCrO4 to other forms, CrO4 2
and Cr2 O7 2 . Since there is an increase in sorption of Cr(VI)
as pH increased to 2.0 so it may be suggested that probably
the CrO4 2 and Cr2 O7 2 are the active forms of Cr(VI), which
are being sorbed by the biomass. Reduction in the biosorption
of Cr(VI) at pH value lower than 2.0 is probably due to the
change in the chemical nature of the M. hiemalis due to hydrolytic activity of the acid at high concentration. This might
change the surface characteristics of M. hiemalis including
surface area availability.

shown in Fig. 3. The specific uptake capacity of M. hiemalis


reduced from 27.3 to 8.1 mg/g. Similar trend has been also reported by other authors for Cr(VI) sorption on Chlorella vulgaris, Senedesmus obliquus and Synectiocystis sp. [10] and
Rhizopus nigricans [12]. Increasing the dose of sorbent, the
total removal of Cr(VI) from the solution increased because
the availability of sorption sites increased, which resulted in
higher uptake of Cr(VI) ions at constant concentration. Specific uptake capacity is a measure of the amount of Cr(VI)
bound by unit weight of sorbent. The competition of the ions
for the sites available caused decrease in the specific uptake
rate thus uptake capacity decreased with increment in sorbent
dose.
3.3. Effect of initial concentration of Cr(VI) on its
sorption
The initial concentration of Cr(VI) in the solution remarkably influenced the equilibrium uptake of Cr(VI) at all the
temperature studied (2750 C). It was noted that, as the initial concentration increased the sorption of Cr(VI) increased
as is generally expected due to equilibrium process. When the
initial concentration of Cr(VI) increased from 10 to 600 mg/l,
the uptake capacity increased from 5.6 to 41.8 mg/g at 27 C,

3.2. Effect of dose of sorbent on sorption of Cr(VI)


Increased amount of sorbent resulted in higher sorption of
Cr(VI) from the solution as is expected. This is evident from
Fig. 2 where the amount of Cr(VI) sorbed on M. hiemalis is
plotted against sorbent/solute ratio expressed by dosage of
sorbent for a particular amount of solute. At the lower dose
(2 g/l), the total amount of Cr(VI) removed by M. hiemalis
was 54.6 mg/l. At higher dose (10 g/l), the total amount of
Cr(VI) removed from the solution by M. hiemalis increased
to 81.0 mg/l. However, the uptake capacity of the sorbent was
found to reduce with increasing sorbent to solute ration as

Fig. 3. Effect of dose of M. hiemalis on its sorption capacity for Cr(VI). Initial Cr(VI) concentration100 mg/l; pH2.0; contact time4 h; agitator
speed120 rpm.

N. Tewari et al. / Biochemical Engineering Journal 23 (2005) 185192

189

Fig. 4. Effect of initial concentration of Cr(VI) on its sorption by M.


hiemalis. Dose of M. hiemalis1 g/l; pH2.0; contact time4 h; agitator speed120 rpm.

Fig. 5. Linearised Langmuir isotherms at different temperature. Dose of M.


hiemalis1 g/l; pH2.0; contact time4 h; agitator speed120 rpm.

from 6.6 to 45.8 mg/g at 40 C and from 7.0 to 46.8 mg/g at


50 C (Fig. 4). This trend is in agreement with the earlier work
on sorption of Cr(VI) [1012,16]. This is also in line with the
equilibrium uptake capacity at higher solute concentration.
The increase in uptake capacity of sorbent with the increase
of Cr(VI) ion concentration is due to higher availability of
Cr(VI) ions in the solution, for the sorption. Moreover, higher
initial concentration provides increased driving force to overcome all mass transfer resistance of metal ions between the
aqueous and solid phases resulting in higher probability of
collision between Cr(VI) ions and sorbents. This also results
in higher metal uptake.

sites are energetically equivalent and there is no interaction


between sorbed molecules.
It was also observed that as the temperature was increased
the maximum sorption capacity of the Mucor increased. Sag
and Kutsal [3] have reported similar results and mentioned
that sorption capacity of Zoogloea ramigera and Rhizopus
arrhizus for Cr(VI), Fe(III) and Pb(II) increased with the
increase in temperature. Similarly, Nuhoglu and Oguz [18]
have reported an increase in sorption capacity of Thuja orientalis for Cu(II) with the rise in temperature. The rise in
sorption capacity with temperature is because of rise in the
kinetic energy of sorbent particles. Thus, the collision frequency between sorbent and sorbate increases; which results
in the enhanced sorption on to the surface of the sorbent. Secondly, at high temperature due to bond rupture there may be
an increase in number of active sorption sites. Which may
also lead to enhanced sorption with the rise in temperature.

3.4. Equilibrium study


In the present study, data of Cr(VI) sorption was analyzed
for Freundlich and Langmuir isotherms. The linearized plots
of Langmuir isotherm model for sorption of Cr(VI) on M.
hiemalis at different temperatures are presented in Fig. 5. In
view of the values of linear regression coefficients, it was
noted that the Langmuir isotherm model exhibited better fit
to the sorption data of Cr(VI) than the Freundlich isotherm
model, in the studied concentration and temperature range
studied (Table 1). The Qmax for Cr(VI) on M. hiemalis was
increased from 47.4 to 53.5 mg/g with the increase in temperature from 27 to 50 C. Similar results have been reported
by other workers for systems like Spirogyra [2], Rhizopus
arrhizus [12,17] and Dunaliella sp. [16]. All these results
showed that Langmuir isotherm model fitted the results quite
well suggesting that the surface of the sorbent is homogenous. Each binding site accepts only one Cr(VI) molecule,
that sorbed molecules are organized as a monolayer and all

3.5. Effect of initial concentration of Cr(VI) on kinetic


parameters of Cr(VI) sorption
Analysis of data showed that the biosorption of Cr(VI),
followed pseudo second order kinetic model for all three
initial concentrations tested. Varying initial concentration of
Cr(VI) influenced the kinetic parameters of the sorption process. With the increase in initial concentration of Cr(VI),
values of equilibrium uptake capacities (qeq ) and initial sorption rate (h) increased as expected but the change in pseudosecond order rate constant (k2 ) was found to decrease. This
is indicative of the fact that the kinetics is strongly dependent
on mass transfer phenomenon in the sorption of the component. The rate of sorption increases at a slower rate compared

Table 1
Isotherm parameters for Cr(VI) sorption on M. hiemalis
Temperature ( C)

27
40
50

Langmuir constants

Freundlich constants

Qmax (mg/g)

b (l/mg)

r2

Kf

r2

47.4
51.0
53.5

0.0307
0.0448
0.0534

0.9990
0.9928
0.9675

4.56
6.59
7.84

2.53
2.88
3.10

0.8790
0.8585
0.8365

pH2.0; dose of M. hiemalis1 g/l; contact time4 h; agitator speed120 rpm.

190

N. Tewari et al. / Biochemical Engineering Journal 23 (2005) 185192

Fig. 6. Linearised pseudo-second order kinetic plots at different initial concentration of Cr(VI). pH2.0; dose of M. hiemalis1 g/l;
temperature27 C; agitator speed120 rpm.

to the increase in concentration due to sorption site saturation, which thus shows up the decrease in apparent rate constant (k2 ). As the initial concentration of Cr(VI) increased,
time to achieve equilibrium decreased. At lower concentration (10 mg/l), equilibrium was attained after 90 min of sorption while at higher concentration (500 mg/l) equilibrium was
achieved in 45 min (figure not shown). The linearised plots for
pseudo-second order rate kinetics and the values of various
kinetic parameters obtained for various systems are presented
in Fig. 6 and Table 2. The value of qeq increased from 7.7 to
41.5 mg/g while value of h increased from 0.99 to 6.72 mg/g
min. Value of k2 decreased from 0.0167 to 0.0039 g/mg min.
3.6. Effect of dose of sorbent on kinetic parameters of
Cr(VI) sorption

Fig. 7. Linearised pseudo-second order kinetic plots at different


dose of M. hiemalis. pH2.0; initial Cr(VI) concentration100 mg/l;
temperature27 C; agitator speed120 rpm.

process. Analysis of data showed that chromium biosorption


followed pseudo second order kinetic model. With the increase in dose of sorbents values of equilibrium uptake capacities (qeq ) decreased but initial sorption rate (h) and pseudosecond order rate constant (k2 ) increased. The linearised plots
for pseudo-second order rate kinetics and the values of various kinetic parameters obtained are presented in Fig. 7 and
Table 3. The value of qeq decreased from 30.5 to 8.2 mg/g
while h increased from 5.11 to 6.57 mg/g min. As the dose
of M. hiemalis was increased from 1.0 to 10 mg/l the values
of k2 also increased from 0.0055 to 0.0977 g/mg min. Similar trends and pseudo-second order kinetics of biosorption of
Cr(VI) have also been reported by other workers [14,1721].
3.7. Effect of temperature on sorption of Cr(VI)

As amount of sorbent added increased, sorption become


faster and equilibrium was achieved earlier. As the dose increased, time to achieve equilibrium decreased. At dose of
1.0 g/l equilibrium was achieved in 45 min whereas at 10 g/l
it was attained within 15 min (figure not shown). It has been
observed from the results of experiment that varying dose
of sorbents influenced the kinetic parameters of the sorption

It was observed that Cr(VI) sorption followed pseudosecond order kinetics at all the temperatures studied. The rise
in temperature increased the values of qeq , k2 and h. The
linearised plots for pseudo-second order rate kinetics and the
values of various kinetic parameters obtained are presented in
Fig. 8 and Table 4. The magnitudes of qeq , k2 and h increased

Table 2
Effect of initial concentration of Cr(VI) on kinetic parameters for sorption of Cr(VI) on M. hiemalis
Co (mg/l)

Pseudo-first order kinetics


k1

10
100
500

(min1 )

0.0748
0.0845
0.8284

Pseudo-second order kinetics

r2

qeq (mg/g)

k2 (g/mg min)

h (mg/g min)

r2

0.9440
0.8372
0.8388

7.7
30.5
41.5

0.0167
0.0055
0.0039

0.99
5.11
6.72

0.9987
0.9926
0.9967

pH2.0; dose of M. hiemalis1 g/l; temperature27 C; agitator speed120 rpm.


Table 3
Effect of dose of M. hiemalis on kinetic parameters for sorption of Cr(VI)
m (g/l)

Pseudo-first order kinetics


k1

1.0
5.0
10.0

(min1 )

0.0845
0.0562
0.0438

Pseudo-second order kinetics

r2

qeq (mg/g)

k2 (g/mg min)

h (mg/g min)

r2

0.8372
0.7885
0.7559

30.5
10.7
8.2

0.0055
0.0522
0.0977

5.11
5.98
6.57

0.9926
0.9995
0.9995

pH2.0; initial Cr(VI) concentration100 mg/l; temperature27 C; agitator speed120 rpm.

N. Tewari et al. / Biochemical Engineering Journal 23 (2005) 185192

191

Table 5
Gibbs free energy change for the sorption of Cr(VI) on M. hiemalis
Temperature ( C)

Free energy
change (kJ/mol)

27
40
50

18.4
20.2
21.3

Fig. 8. Linearised pseudo-second order kinetic plots at different


temperatures. pH2.0; dose of M. hiemalis1 g/l; initial Cr(VI)
concentration100 mg/l; agitator speed120 rpm.

Fig. 10. Plot of ln b vs. 1/T.

sorption of Cr(VI) on M. hiemalis was found to be 19.6 kJ/mol


while S was 0.127 kJ/mol/K. Sag and Kutsal [3] have reported that value of H for Cr(VI) sorption on Zoogloea
ramigera was 16.0 kJ/mol, which is quite comparable to the
results obtained in this study. The value of H was positive,
indicating that the sorption reaction is endothermic. This is
also supported by the increase in value of uptake capacity
of all the sorbent with the rise in temperature. The positive
value of S reflects the affinity of Cr(VI) for sorbent used.
In addition, positive value of S shows the increasing randomness at the solid/liquid interface during the sorption of
Cr(VI) on selected sorbent.

Fig. 9. Arrhenius plot.

from 30.5 to 37.2 mg/g; 0.0055 to 0.0075 g/mg min and 5.12
to 10.6 mg/g min, respectively with the rise in temperature
from 27 to 50 C. The kinetic parameters at different temperatures have been plotted in terms of Arrhenius equation
(Fig. 9). The activation energy for the sorption of Cr(VI) on
M. hiemalis was calculated and its value was found to be
4.0 kJ/mol. From the value of activation energy it appears
that the sorption of Cr(VI) on M. hiemalis is physical adsorption process. This is confirmed from the fact that the activation energy for physical adsorption is usually not more than
46 kJ/mol [22]. This further consolidates the earlier observation of the biosorption data following Langmuir isotherm.
The value of G for the sorption of Cr(VI) on M. hiemalis
at different temperature is given in Table 5. The magnitude
of G increased with the rise in temperature. The negative
value confirms the feasibility of the process and the spontaneous nature of sorption of Cr(VI) on M. hiemalis. The values
of H and S were determined from slope and intercept
of the plot of ln b versus 1/T as shown in Fig. 10. H for the

3.8. Desorption of Cr(VI) by NaOH


The results of desorption study of Cr(VI) by NaOH solution is shown in Table 6. The result shows that even after five
cycles of sorption and desorption, there was no appreciable
decrease in the sorption capacity of M. hiemalis. This indicated that the material could be reused for 45 time for the
sorption of Cr(VI). NaOH has been found to be an effective
eluent as has also been reported by other studies on sorption
of Cr(VI) by other workers [2325].

Table 4
Kinetic parameters for sorption of Cr(VI) on M. hiemalis at different temperature
Temperature ( C)

Pseudo-first order kinetics


k1

27
40
50

(min1 )

0.0845
0.0424
0.0450

Pseudo-second order kinetics

r2

qeq (mg/g)

k2 (g/mg min)

h (mg/g min)

r2

0.8372
0.8567
0.8795

30.5
34.5
37.2

0.0055
0.0061
0.0075

5.12
7.26
10.38

0.9926
0.9928
0.9675

pH2.0; dose of M. hiemalis1 g/l; initial Cr(VI) concentration100 mg/l; agitator speed120 rpm.

192

N. Tewari et al. / Biochemical Engineering Journal 23 (2005) 185192

Table 6
Desorption of Cr(VI) from M. hiemalis
Cycles

Sorption (mg/g)

Desorption (mg/g)

Reduction in sorption capacity (%)

Desorption (%)

I
II
III
IV
V

27.3
27.0
26.8
26.7
26.4

27.1
26.6
26.6
26.2
26.0

1.1
1.8
2.2
3.3

99.3
99.3
99.2
98.1
98.5

4. Conclusions
The experiments conducted with the biosorption showed
that M. hiemalis can remove Cr(VI) by biosorption. It was
also observed that the extant of biosorption increased with
lowering of pH up to 2.0. It was further observed that specific
sorption capacity decreased with increase in sorbent to sorbate ratio. Biosorption process followed Langmuir isotherm
model. The sorption capacity was found to increase with increase of solute concentration and temperature. The maximum sorption capacity was found to be 53.5 mg/g at 50 C
and pH 2.0. The rate of sorption was found to follow pseudosecond order kinetics. From the value of activation energy of
the process it is suggested that biosorption of Cr(VI) by M.
hiemalis is physical sorption. Further from the value of H
it was revealed that the biosorption process is endothermic.
Experiments were also conducted to regenerate the sorbent
by extracting chromium by NaOH. It was observed that even
after five cycles of sorption and regeneration the sorption efficiency remained quite high. Thus, it may be concluded that
M. hiemalis exhibited the potential for application in treatment of water containing Cr(VI). However, further research is
needed to establish the process with specific attention to the
regeneration of the sorbent and the recovery of the sorbed
metal. Therefore, future research will be oriented towards
column studies.

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