Bioresource Technology 97 (2006) 19861993

Thermodynamic and breakthrough column studies for the

selective sorption of chromium from industrial euent on
activated eucalyptus bark
Vikrant Sarin, Tony Sarvinder Singh, K.K. Pant

Department of Chemical Engineering, Indian Institute of Technology, New Delhi 110 016, India
Received 6 August 2005; received in revised form 26 September 2005; accepted 1 October 2005
Available online 28 November 2005

Abstract
Studies were carried out on adsorption of Cr(VI) on an adsorbent made from eucalyptus bark. Results revealed that sorption of chromium on activated eucalyptus bark (AEB) was endothermic in nature. Thermodynamic parameters such as the entropy change, enthalpy
change and Gibbs free energy change were found out to be 100.97 J mol1 K1, 33 kJ mol1 and 0.737 kJ mol1, respectively. Industrial chrome euent of dierent chromium concentration at dierent pH was used as feedstock for the xed bed adsorption studies.
When euent was fed to the column at low pH of 2, the breakthrough volume increased signicantly compared to euent at higher
pH of 4.85. The surface properties of sorbent were characterized by the Scanning electron microscopy, X-ray diraction technique
and Infrared techniques. It was concluded that AEB sorbent column could be used eectively for removal of chromium from industrial
euents by reducing the pH of chrome euent to two and at optimal column conditions.
 2005 Elsevier Ltd. All rights reserved.
Keywords: Fixed bed column; Adsorption; Activated eucalyptus bark; Breakthrough

1. Introduction
Since the start of industrialization in the nineteenth century, the material cycle, amount of heavy metals, which
impact upon water, soil, plants, animals, and people have
increased considerably. Many industries, particularly in
the trade of metal processing operations and reneries represent signicant sources of heavy metal emissions. These
include cement manufacturing units (thallium), battery
manufacturers (lead), electroplating (Cu, Ni, Cr), tanning
(Cr), pigments (Cr, lead), wood preservation (Cr), etc.
Through refuse wastewater, heavy metals like chromium
ions enter especially into fresh water or soil and thereby
into plants, animals and humans. Considering process in
biosphere, the geochemical cycle is connected via metabolic
processes by microorganisms in the ocean oor, in sedi*

Corresponding author. Tel.: +91 11 2659 6172; fax: +91 11 2658 1120.
E-mail address: kkpant@chemical.iitd.ac.in (K.K. Pant).

0960-8524/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2005.10.001

ments or sludge, or in water. Microorganism plants and

small animals serve as food source for sh. By means of
plants and other animals, levels of heavy metals from water
and soil nd their way into our food, however when accumulated to high levels, more than the threshold limits
of the organisms, it can generate serious problems and diseases. Chromium is highly reactive element. It exists in six
oxidation states and the two most stable states are Cr(III)
and Cr(VI). Chromium forms stable complexes as Cr2 O
7,


HCrO
,
CrO
,
HCr
O
and
fraction
of
these
complexes.
2 7
4
4
Fraction of the above complexes varies with pH and at
low pH Cr exists as negatively charged dichromate ions.
Cr(VI) is the most toxic form thus it becomes imperative
to remove Cr(VI) from industrial euents before discharging into the water or on to the land. Chromium compounds
are amphoteric in nature i.e. they exhibit both acidic and
basic properties. These compounds also exhibit point of
minimum solubility. The pH of minimum solubility for
chromium is 7.5. Widespread use of chromium chemicals

V. Sarin et al. / Bioresource Technology 97 (2006) 19861993

in various industries leads to problem of contamination of

natural waters due to improper disposal methods. Chromium euent is generated by the following industrial uses
of chromium like leather tanning, mining of chrome ore,
production of steel and alloys, metal nishing industries,
pigments manufacturing units, photographic industry,
glass industry, wood preservation, chromium salts being
used as corrosion inhibitor in the cooling water treatment
in the industry, textile industry and many other industrial
applications.
Chromium is non-biodegradable and toxic beyond a
given concentration. Chromium threshold concentration
on inhibitory eect on heterotrophic organisms is 10 mg/
L for Cr(III) and 1 mg/L for Cr(VI). All living organisms
require varying amount of Cr(III) in micro amounts for
proper growth. The same metal becomes toxic when present in elevated concentration. As per studies carried out
Cr(VI) is 500 times more toxic to Cr(III) (Kowalski,
1994). Cr(VI) is considered by International Agency for
Research on Cancer (IARC) 1982 as a powerful carcinogenic agent that modies the DNA transcription process
causing important chromosomic aberration (US Department of Health and Human Services, 1991; CieslakGolonka, 1995). The current BIS (Bureau of Indian
Standards) recommended guideline value for chromium
(as total Cr) in drinking water as 0.05 mg/L (maximum).
Chromium ions are removed from the euent using precipitation technique. This technique is widely practiced by
the industry. The common problem associated with this
process is generation of large volume toxic sludge. Safe
disposal of this toxic sludge is another problem. Further
this method depends on the addition of chemicals to the
euent. Ion exchange (Tiravanti et al., 1997), adsorption
(Dahbi et al., 1999) electrodialysis, membrane process, solvent extraction, freeze separation, bio-separation are some
of the other methods for removal.
The present study aimed at development of suitable
method using low cost bio adsorbent for selective removal
of chromium by adsorption from industrial euent.
2. Methods
2.1. Materials
All the chemicals used in the study were of analytical
grade (Merck, Germany). Industrial euent was obtained
from automobile ancillary unit located at Sahibabad, Uttar
Pradesh (India). Industrial chromium euent was obtained
from the outlet of the chrome plating section of the unit.
Synthetic samples used in the study were prepared using
double distilled/deionised water. Characteristics of dierent chromium euent are given in Table 1. Measurements
were made in triplicates for the analysis of metal concentration and data were recorded when the variations in two
readings were less than 5%. All glass wares and sample bottles were soaked in hot water and rinsed with laboratory
dish soap (Lavolene) for at least two hours and then rinsed

1987

Table 1
Characteristics of chromium euent
Parameters
TDS (mg/L)
pH
Concentration Cr(VI) (mg/L)
Concentration Cr(III) (mg/L)
Hardness Ca (mg/L)
Hardness Mg (mg/L)
a

SS

28
200

IE-1a

IE-2

IE-3

IE-4

70
4.95
12.2
0
16.5
11.5

122
4.45
24.4
0
36
24

900
3.41
200
44.5
134
92

1934
4.2
488.5
14.6
240
184

IEindustrial euent.

with de-ionized water. Hexavalent chromium [Cr(VI)]

stock solution (1000 mg L1) was prepared by dissolving
potassium dichromate (K2Cr2O7) in de-ionized water and
stored in airtight polyethylene terphthalate (PET) bottles
at a temperature less than 2 C. Further working solutions
were freshly prepared from stock solution for each experimental run. Concentration of chromium Cr(VI) stock solution was measured periodically to monitor variations in
concentration. Cr(III) concentration was determined by
measuring the dierence between total chromium concentration and Cr(VI) concentration. Total Cr concentration
was determined by oxidizing Cr(III)Cr(VI) using KMnO4
and then determining nal Cr(VI) content in the sample
(APHA, 1992).
2.2. Thermodynamic studies
The adsorbent activated eucalyptus bark (AEB) used for
the removal of Cr(VI) was prepared in the laboratory. The
details of sorbent preparation, kinetics of adsorption and
comparison of chromium removal eciency with other
adsorbents have been discussed elsewhere (Sarin and Pant,
2006). Adsorption, studies in the temperature range 293
343 K were conducted to determine thermodynamics constants such as Gibbs free energy change (DG0), enthalpy
change (DH0) and entropy change (DS0) for the system
and to ascertain the sorption mechanism. For this study,
adsorbent dosage selected was 5 g/L of chromium Cr(VI)
euent in a conical ask and allowed to equilibrate for
24 h at the dierent temperatures ranging from 293 to
343 K. Residual chromium concentration was determined
in each sample after equilibrium was attained.
2.3. Fixed bed adsorption studies
Fixed bed adsorption studies were conducted to evaluate
dynamic behaviour for Cr(VI) removal on AEB. The
experimental set-up consisted of up ow glass column
(0.025 m ID, 0.4 m length) packed with dierent bed
heights of sorbent. Inuent feed ow rate was varied and
maintained throughout the experiments by the use of variable ow peristaltic pump (Neolab India). At the exit of the
column, ow rate was also measured so as to get steady
state ow conditions in the column. Experiments were conducted with industrial euent (pH 4.85) and at optimum
pH 2, obtained from batch experiments.

1988

V. Sarin et al. / Bioresource Technology 97 (2006) 19861993

The empty bed contact time (EBCT) varied from 0.061

to 0.31 h during runs by varying the initial feed ow rate
or bed height. Sampling of column euent was done at
specied time intervals in order to investigate the breakthrough point (BTP) and shape of breakthrough curve.
Eects of inlet feed ow rate, initial sorbate concentration (1025 mg/L) and adsorbent bed height (0.10.2 m)
were investigated on the performance of breakthrough
for the adsorption of Cr(VI). Initial chromium Cr(VI)
concentration was also varied in the range of 1224 mg/
L. For the analysis of mass transfer zone, breakthrough
data were analyzed by Bohart and Adams model.
2.4. Characterization of activated eucalyptus bark
X-ray diraction (XRD) pattern, infra-red spectroscopy
(IR) and scanning electron microscopy (SEM) studies were
carried on AEB to determine its adsorption mechanism.
For these IR spectra of fresh and used eucalyptus bark
was carried out on IR spectroscope (PROTEGE 460,
USA) in the range of wave numbers from 4000 to
500 cm1. SEM of the fresh and used sorbents was carried
out to determine the qualitative analysis of surface morphology of the sorbent. The analysis was done on a model
Cambridge Stereo Scan 360, UK.
3. Results and discussion
3.1. Thermodynamic studies
In order to determine thermodynamic parameters,
experiments were carried out at dierent temperatures in
the range of 293343 K for Cr(VI) adsorption. The thermodynamic parameters such as standard Gibbs free energy
change (DG0), enthalpy change (DH0) and entropy change
(DS0) were estimated to evaluate the feasibility and nature
of the adsorption process (Sarin and Pant, 2006). The
Gibbs free energy change, of the process is related to equilibrium constant by the equation
DG0 RT ln K c

where, T is temperature in K, R is ideal gas constant having

value as 8.314, J mol1 K1 and Kc is thermodynamic equilibrium constant.
The thermodynamic equilibrium constant, was determined as
Kc

Ca
Ce

where, Ca is mg of adsorbent adsorbed per liter and Ce is

the equilibrium concentration of solution, mg/L.
According to thermodynamics, the Gibbs free energy
change is also related to the enthalpy change (DH0) and
entropy change (DS0) at constant temperature by the following equation

ln K c

DS 0 DH 0

R
RT

The values of enthalpy change (DH0) and entropy change

(DS0) were calculated from the slope and intercept of the
plot ln Kc versus, 1/T with R2 value of 0.94. For the synthetic sample (C0 200 pm Cr(VI), pH 5.7) at temperatures
333 and 343 K the values of Kc were 1.305 and 1.913
respectively. The corresponding DG0 values were 0.737
and 1.850 kJ mol1 respectively. The values, enthalpy
change (DH0) and entropy change (DS0) were found out
to be as 33 kJ mol1 and 100.97 J mol1 K1 respectively.
The calculated values of these parameters of various other
synthetic and industrial samples are reported in Table 2.
A positive value of DH0 as 33 kJ mol1 for chromium
removal with AEB, indicated the endothermic nature of
the process. A negative value of the free energy (DG0)
(0.737 kJ mol1 at 333 K and 1.85 kJ mol1 at 343 K),
indicated the spontaneous nature of the adsorption process. It was also noted that the change in free energy,
increases with increase in temperature, which exhibits an
increase in adsorption with rise in temperature. This could
be possibly because of activation of more sites on the surface of AEB with increase in temperature. A positive value
of DS0 as 100.97 J mol1 K1 showed increased randomness at solid solution interface during the adsorption of
Cr(VI) on AEB. A value of Freundlich adsorption intensity
(n) higher than 1, obtained from batch indicated that sorption of chromium on AEB is favourable and capacity is
only slightly reduced at lower equilibrium concentration
(Sarin and Pant, 2006). The endothermic nature of adsorption for chromium removal has also been reported on biogas residual slurry (Namasivayam and Yamuna, 1995).
3.2. Up ow xed bed column adsorption studies
on chromium removal
Batch experimental data are often dicult to apply
directly to xed bed column adsorber because isotherms
are unable to give accurate data for scale up since a ow
column is not at equilibrium. Fixed bed column adsorption
experiments were carried out to study the adsorption
dynamics. The xed bed column operation allows more
ecient utilization of the adsorptive capacity than the
batch process. The adsorbent at the inlet end is contacted
continuously by the solution at the initial solute concentra-

Table 2
Thermodynamic parameters for the adsorption of Cr(VI) by AEB
Euent

Euent
concentration
Cr(VI), mg/L

pH

Equilibrium
constant, Kc

Gibbs free
energy, kJ mol1

Synthetic euent
Synthetic euent
Synthetic euent
Industrial euent
Industrial euent

200 [Cr(VI)]
200 [Cr(VI)]
200 [Cr(VI)]
200 [Cr(VI)]
44.5 [Cr(III)]

2
3
4.7
3.4
3.4

9.0
4.95
1.36
2.10
4.60

5.57
4.06
0.79
1.88
3.87

V. Sarin et al. / Bioresource Technology 97 (2006) 19861993

3.2.1. Eect of xed bed column height

on the performance of breakthrough
The steepness of the breakthrough curves is a strong
function of bed height. Two dierent industrial chromium
euents were passed through the xed bed column. One
having Cr(VI) concentration as 24 mg/L with pH 4.85
(without changing the pH) and the other euent was treated at optimum pH 2. The breakthrough volume obtained
for euents treated at pH 4.85 were very less compared to
the euent having pH 2. Figs. 1 and 2 represent the performance of breakthrough curves at a bed height of 0.1, 0.15
and 0.20 respectively. As it is evident from these gures, an
increase in column depth increased the throughput volume
25

Ct (mg/L)

20
15
10
Bed height - 0.1 m

Bed height - 0.15 m

Bed height - 0.2 m

0
0

200

400

600

800
1000
Time (min)

1200

1400

Fig. 1. Eect of bed height, 0.10, 0.15 and 0.2 m on adsorption of Cr(VI)
by AEB (ow rate: 3.6 104 m3/h, C0: 24.4 mg/L, pH: 4.85).

25

20

Ct (mg/L)

tion. The most important criterion in the design of xed

bed adsorption systems is the prediction of xed bed column breakthrough or the shape of the adsorption wave
front, which determines the operation life span of the
bed. The design of up ow xed bed column adsorber
includes estimation of shape of breakthrough curves and
the appearance of breakpoint. The dynamics of adsorption
process was studied using bed depth service time (BDST)
method based on a model proposed by Bohart and Adams
(1920).
The eect of xed bed column parameters such as sorbent bed height, ow rate and initial chromium concentration on the performance of breakthrough curves were
investigated. All the xed bed column experiments were carried out at ambient conditions at pH 2 and 4.85 having
Cr(VI) concentration as 24.4 mg/L. Flow rate of the euent
through the column was maintained at 3.6 103 m3/h.
Breakthrough volumes obtained at bed heights of 0.1,
0.15 and 0.2 m for euent having Cr(VI) concentration as
24.4 mg/L and pH 4.85 were found out to be
1.48 104 m3, 3.28 104 m3 and 5.76 104 m3 respectively, the corresponding values at a pH of 2 were
66.96 104 m3, 147.5 104 m3 and 242.0 104 m3
respectively. The total chromium adsorbed in the column
for a given feed concentration is equal to the area under
the breakthrough curve. The steepness of breakthrough
curve was a strong function of xed bed column parameters.

1989

15

10

Bed height - 0.1 m

Bed height - 0.15 m
Bed height - 0.2 m

0
0

1000

2000

3000
Time (min)

4000

5000

6000

Fig. 2. Eect of bed height, 0.10, 0.15 and 0.2 m on adsorption of Cr(VI)
by AEB (ow rate: 3.6 104 m3/h, C0: 24.4 mg/L, pH: 2).

treated due to higher contact time. At relatively lower

contact time, the curve was steeper for both the euents
showing the faster exhaustion of the bed. For Cr(VI)
removal the treated volume varied from 1.48 104 m3 to
5.76 104 m3 as the bed height was increased from
0.1 m to 0.2 m (Figs. 1 and 2). The curves followed characteristic S shape prole, which is associated with adsorbate
of smaller molecular diameter and more simple structure.
The increase in the metal uptake capacity at either pH
of 4.85 or 2 with the increase of bed height in the xed
bed column was probably due to increased surface area
of the adsorbent, which provide more binding sites for
the adsorption. The breakthrough time was also increased
with the increase in bed height.
3.2.2. Eect of ow rate on the performance of
breakthrough curves
Studies at dierent ow rates were conducted in the
xed bed of AEB. The ow rate was varied from
3.6 104 m3/h to 1.2 104 m3/h while the inlet Cr(VI)
concentration was kept constant at 12.2 mg/L at pH 4.85.
Euent at optimal pH 2 was also run at a ow rate of
3.6 104 m3/h. The eect of ow rate on breakthrough
performance, at a bed height of 0.10 m has been shown
in Fig. 3. As can be seen from the breakthrough plots,
higher eciency of the process was achieved at lower ow
rate. This can be explained by the fact at low empty bed
contact time (EBCT), the diusion process which controls
the sorption becomes slow, and hence, the sorbent needs
more time to bond the metals eciently. These breakthrough curves demonstrate inuence of sorption kinetics.
The uptake of chromium decreased with increase in ow
rate. It was also observed that sorbents get saturated easily
at higher ow rates. Breakthrough volume obtained at pH
4.85 was signicantly less than at pH 2. As volumetric ow
rate increases, the velocity through the bed decreases,
which results in the decrease in the length of adsorption zone. At higher ow rates breakthrough curves
become steeper and breakpoint time and the adsorbed

1990

V. Sarin et al. / Bioresource Technology 97 (2006) 19861993

14

25

Cr(VI) conc 24.4 mg/L at pH 4.85

Cr(VI) conc 12.2 mg/L at pH 4.85
Cr(VI) conc 24.4 mg/L at pH 2
Cr(VI) conc 12.2 mg/L at pH 2

12

20

Ct (mg/L)

Ct (mg/L)

10

4 ml/min

15

10

6 ml/min
2

2 ml/min
5

0
0

500

1000

1500

2000
2500
Time (min)

3000

3500

4000

Fig. 3. Eect of ow rate on breakthrough curves for adsorption of

Cr(VI) by AEB (C0: 12.2 mg/L, bed height: 0.10 m, pH: 4.85, ow rate
m3/h 104: (j) 6 (r) 4 (m) 2).

0
0

500

1000

1500
Time (min)

2000

2500

Fig. 4. Eect of initial Cr(VI) concentration on breakthrough performance (ow rate: 3.6 104 m3/h, pH: 4.85 and 2, bed height: 0.10 m).

ion concentration decreases. A higher uptake of chromium

was observed at the beginning of xed bed column operation but as solution continued to ow, the concentration of
chromium in the euent rapidly increased; the bed
becomes saturated with chromium and the concentration
of the solute in the euent rise sharply.
An increase in ow rate from 1.2 104 m3/h to
3.6 104 m3/h reduced the volume of euent treated from
0.456 m3 to 0.162 m3 for Cr(VI) removal over AEB. There
was a corresponding decrease in sorption capacity from
662 mg/kg to 617 mg/kg for euent having Cr(VI) concentration as 12.2 mg/L and pH 4.85. Whereas sorption capacity for euent having Cr(VI) concentration as 12.2 mg/L at
pH 2 was 8748 mg/kg. As Cr(VI) ions moves from bulk
solution to the surface of the lm surrounding the sorbent
particle, concentration gradient develops at the interface,
which allows the solute particle to penetrate through the
lm, and reaches the surface of the particle where the positively active sites attract the negatively charged dichromate
ions. At higher ow velocities, lm surrounding the particle
breaks thereby reducing the adhesion of sorbate to the sorbent particle. As can be seen from Fig. 3 the uptake of
Cr(VI) decreased with the increase in ow rate. The breakthrough capacity of the sorbent decreased with increase in
ow rate. As the velocity through the bed decreased, the
depth of the adsorption zone decreased because there was
more time for adsorption to occur.
At low pH, the surface of AEB becomes positively
charged because many more positive sites are created and
amide functional groups become positively charged due
to electromeric eect. This results in many more positive
charges being created on the surface of the adsorbent,
resulting in many folds increase in adsorption capacity of
AEB at low pH.
3.2.3. Eect of initial chromium concentration
on breakthrough curve
Eect of initial chromium concentration on the performance of breakthrough curve is shown in Fig. 4. Break-

through volume obtained at bed height of 0.1 m, euents

having ow rate as 3.6 104 m3/h through the bed and
having Cr(VI) concentration as 24.4 and 12.2 Cr(VI) both
at pH 4.85 was 1.35 104 m3 and 3.6 104 m3 respectively. On optimising the pH to 2 of the above two euents
and keeping all the other experimental conditions same,
breakthrough volume increased and was obtained as
66.96 104 m3 and 101.7 104 m3 respectively. A
change in the inlet sorbate concentration aected the operating characteristics of the xed bed column. At low initial
concentration, breakthrough occurred late and the treated
volume were higher since the lower concentration gradient
caused a slower transport due to decreased diusion coecient or mass transfer coecient (Aksu and Ferda, 2004). It
was observed that at low pH the adsorption increased
many folds. This could be due to increase in the number
of binding sites. The sorbent gets saturated early at high
initial concentration because binding sites become more
quickly saturated in the system. These results indicated that
increase in chromium concentration reduced the metal to
sorbent ratio and the metal uptake as long as the sorbent
was not saturated. Initial sorbate concentration aected
the performance of xed bed for adsorption of chromium
(Fig. 4). Breakpoint time decreased with increasing inlet
Cr(VI) concentration as the binding sites saturated faster.
These results showed that performance of breakthrough
curves for chromium removal by AEB was strongly
aected by initial concentration and pH of solution and
thus aected the treatment of euent.
3.3. Modelling of breakthrough curves
Many mathematical models have been developed to
describe contaminant sorption over dierent adsorbents
in many of the diverse applications for which it is used
(Weber and Smith, 1987; Tien, 1994). The design of the
adsorption process is based on the accurate generation of

V. Sarin et al. / Bioresource Technology 97 (2006) 19861993

breakthrough curves. The uid velocity, concentration of

solute in feed and the bed height aect the shape of the
curve. Steep slopes of breakthrough curves were obtained
for systems that exhibit high lm transfer coecients, high
internal diusion coecients or at adsorption isotherm
that is smaller value of 1/n (Faust and Aly, 1987). The
dynamic behaviour of the xed bed column was predicted
with the AdamBohart model in the present investigation.
3.3.1. AdamBohart model
Bohart and Adams (1920) established the fundamental
equations describing the relationship between Ct/C0 and t
in a continuous system for the adsorption of chlorine on
charcoal, known as bed depth service time (BDST) model.
Although the original work by AdamsBohart was done
for the gascharcoal adsorption system, its overall approach
has been applied successfully in quantitative description of
other systems (McKay, 1982; Singh and Pant, 2004). This
model assumes that the adsorption rate is proportional to
both the residual capacity of the sorbent and the concentration of the sorbing species. The AdamsBohart model is used
only for the description of the initial part of the breakthrough curve i.e. up to the breakpoint or 1050% of the saturation points.
The main objective of the xed bed adsorption is to
reduce concentration in the euent so that it does not
exceed permissible limit (breakthrough concentration Cb).
This approach was focused on the estimation of characteristic parameters such as maximum adsorption capacity (N0)
and kinetic constant (ka) from AdamBohart model using
a quassi chemical kinetic rate expression. The mass balance
obeys the following equation
oq
k a qC
ot
oC
ka
 qC
oz
v

4
5

The following equation can be obtained to relate the process conditions and operating parameters with service time.




C0
ln
 1 ln eka N 0 Z=v  1  k a C 0 t
6
C
A linear relationship between bed depth and service time
given by Eq. (7) (Hutchins, 1973)


N 0Z
1
C0
t

1
7
ln
C0v kaC0
C
were C is the euent concentration of adsorbate in the liquid
phase (mg/L); C0 is initial concentration of sorbate in the
liquid phase (mg/L); v is the linear ow velocity (m/h); N0
is adsorption capacity (mg solute/kg adsorbent); ka is rate
constant in BDST model (m3/kg h); t is time (h) and Z is
bed depth of xed bed column (m). Eq. (7) enables the service
time, t, of an adsorption bed to be determined for a specied
bed depth, Z, of adsorbent. The service time and bed depth
were correlated with the process parameter such as initial
arsenic concentration, ow rate and adsorption capacity.

1991

BDST plots for Cr(VI) adsorption onto AEB were

made. The slope of the BDST curves represents the time
required for the adsorption zone to travel a unit length
through the adsorbent under the selected experimental conditions at a given concentration. This is used to predict the
performance of the bed, if there is a change in the initial
solute concentration, C0, to a new value of solute
concentration.
The critical bed depth Z0 is obtained for t = 0 and for a
xed outlet concentration Ct = Cb, where Cb is the concentration at the breakthrough dened as a limit concentration
or a xed percent of initial concentration.


v
C0
Z0
ln
1
8
kaN 0
Cb
The critical bed depth (Z0) represents the theoretical depth
of adsorbent, which is necessary to prevent the sorbate concentration to exceed the limit concentration Cb. The critical
bed depth is the theoretical depth of the sorbent sucient
to prevent the adsorbate concentration from exceeding
Cb (breakthrough concentration) at t = 0.
After applying Eq. (7) to the experimental data at the
breakthrough point, a linear relationship was found while
plotting service time (t) against bed height, Z for Ct
0.1 mg/L (breakthrough point).
As could be seen from the Table 3, the values of kinetic
constants were inuenced by ow rate and increased with
increase in ow rate indicating that overall system kinetics
was dominated by external mass transfer in the initial part
of the adsorption in the xed bed column. Calculated
values of adsorption capacity (N0) showed a marginal
decrease with increase in ow rate. These results correlate
well with the observed sorption capacity and showed poor
adsorber performance at high ow rate. Time required to
pass a unit length of primary adsorption zone (td) also
decreased with increase in ow rate.
3.4. Study of adsorption mechanism of chromium on AEB
Maximum Cr(VI) adsorption over AEB is 99.9% at initial solution pH 2.0 (Sarin and Pant, 2006). To determine
the behaviour of AEB towards adsorption of Cr(VI),
X-ray diraction (XRD), scanning electron microscopy
(SEM) and infra red spectroscopy (IR) on fresh AEB and
exhausted AEB (with chromium) were carried out. The
results obtained explain the mechanism for uptake of
Cr(VI) exhibited by AEB at low pH. From SEM of adsorbent (AEB) it was observed that adsorbent was brous in
nature whereas SEM of adsorbent (AEB) saturated with
chromium Cr(VI) clearly indicated the adsorption of
Cr(VI) on the surface of the adsorbent did not aect the
crystallinity of the surface.
XRD of both adsorbent (AEB) before and after saturation with Cr(VI) was also carried out to identify the phase
present on sorbent. The structure of AEB remained the
same before and after saturation with Cr(VI). There was
no change in the structure, indicating that the structure

1992

V. Sarin et al. / Bioresource Technology 97 (2006) 19861993

Table 3
BDST parameters for sorption of Cr(VI) over AEB
Adsorbate

Bed depth,
m 102

Flow rate,
m3/h 104

Linear velocity,
m/h

td, H/m

pH

Feed concentration,
mg/L

N0,
mg/kg

ka,
m3/kg H 102

Z0 critical bed
depth, m

Cr(VI)

10

3.6

0.71

15

3.6

0.71

Cr(VI)

20

3.6

0.71

Cr(VI)

10

3.6

0.71

Cr(VI)

10

2.4

0.473

Cr(VI)

10

1.2

0.237

2
4.85
2
4.85
2
4.85
2
4.85
2
4.85
2
4.85

24.4

Cr(VI)

485
10
485
10
485
10

8407
173.24
8407
173.24
8407
173.24
8407
173.24
8401
173.12
8418
173.48

0.423
0.2215
0.423
0.2215
0.423
0.2215
0.65
0.2244
0.65
0.2244
0.65
0.2244

0.063
0.0583
0.063
0.0583
0.063
0.0583
0.0482
0.0441
0.0321
0.0075
0.016
0.0037

24.4
24.4
12.2
12.2
12.2

of AEB remains intact after Cr(VI) adsorption (Fig. 5). IR

of the adsorbent (AEB) before and after saturation with
Cr(VI) was carried out to identify the functional group
eective for adsorption. IR wavelength used was in the
range of 2.515 lm. Functional groups involved in the
removal of chromium were identied from analysis of IR
spectrum of AEB before and after saturation with Cr(VI)
shown in the Fig. 6. The IR bands observed at wave numbers 2360.15, 889.36 and 667.31 cm1 with fresh sorbent
were found missing with AEB saturated with Cr(VI) ions.
These results indicated that these bonds were involved with
sorption of Cr ions. The bond involved in adsorption at the
wave numbers 2360.15 cm1 is triple or cumulative bond

of ammonium salts (R2 NH

2 or R3 NH2 ) attached to
polyphenols or straight organic chains of bark. Where as
the bonds found missing at wave number 889.36 and
667.31 cm1 are of CH bonds of unsaturated groups particularly aromatic rings and cis alkenes respectively. At low
pH (pH 6 2) all the chromium complexes exist as negatively charged dichromate ions (HCr2 O
7 ). Further the concentration of hydronium ion is large at low pH. This result
in electromeric eect on the ammonium salts attached to
aromatic rings or straight chains of bark. Thus due to electromeric eect the sites becomes positively charged and the

Fig. 6. IR of fresh AEB and used, saturated with chromium, AEB.

Fig. 5. Plots of XRD of fresh AEB (a) and used (saturated with Cr)
AEB (b).

number of sites increases, thereby attracting negatively

charged dichromate ions. This phenomenon results in high
and selective removal of Cr(VI) at low pH. Removal of poisonous hexavalent form of chromium from solutions was
possible using selected adsorbents.
The cost of preparation of AEB is low since the raw
material required for its preparation is cheaply and abundantly available. AEB saturated with chromium, after drying, can be used as fuel. The ash obtained after burning of

V. Sarin et al. / Bioresource Technology 97 (2006) 19861993

this AEB shall contain chromium metal. This ash would be

of very low volume compared to conventional chromium
sludge, thus can be disposed o easily.
4. Conclusions
Activated eucalyptus bark was found to be an eective
biosorbent for removal of Cr(VI) from industrial euent.
The adsorption of Cr(VI) by AEB is endothermic spontaneous in nature. The adsorption capacity increases with
increase in temperature range of 293343 K. Gibbs free
energy change has been observed as 5.572 kJ mol1 and
negative value indicates the feasibility of adsorption for
system. Up ow xed bed column adsorption studies have
shown that chromium removal was a strong function of initial ow rate, bed height and initial sorbate concentration.
Mutual eects of the adsorption capacities and adsorption
rate satisfactorily explain the dependence of shape of the
breakthrough curves on experimental parameters. Higher
bed volume of wastewater could be treated at low chromium concentration and lower ow rate. Relatively higher
sorption capacities were observed in xed bed column
operation compared to batch operation. The kinetic constants were inuenced by ow rates and increased with
increase in ow rate. It was concluded that at low pH concentration of hydronium ion is large which results in electromeric eect on the ammonium salts attached to the
aromatic rings or straight chain of bark.
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