Bonfring International Journal of Industrial Engineering and Management Science, Vol. 2, No.

2, June 2012 14
ISSN 2277 - 5056 | 2012 Bonfring
Abstract--- Water pollution is one of the most
undesirable environmental problems in the world and it
requires solutions. Textile industries produce a lot of
wastewater, which contains a number of contaminants,
including acidic or caustic dissolved solids, toxic compounds
and many different dyes. Many of the heavy metals are
hazardous and may affect aquatic life causing various
diseases and disorders. The aim of the present work is to
explore the possibility of using these carbonaceous
materials as low-cost adsorbents. The removal of heavy
metals from industrial effluents is a major priority before
their discharge on environment. Developed processes require
expensive and in many cases advanced technologies.
Commercially activated carbon is more costly, such that
cost of investment may not permit to use effectively. We
report that the low cost carbon system, which were obtained
from used up commercial batteries Nippo and BPL are used
for the effective adsorption of heavy metal cations, Cu
++
,
Ni
++
and Co
++
, colouring metal ions also adsorb
active low molecular weight organic compounds like
phenols, carboxylic acid and phenyl acetic acid.
Carbon dose required for maximum percentage of
adsorption was found as 55.8, 50.5 and 54.2 in the case of
Cu
++
, Ni
++
and Co
++
ions respectively per gram of
isotherm constants after studying Langmuir and Freundlich
method were determined. Plot of metal ion adsorbed in mg vs.
equilibrium metal concentration are linear at low
concentration and flat at higher concentration. This supports
the Langmuir theory that the intermolecular forces between
the sorbate and sorbent would not be significant beyond the
first sorbed layer and that a portion of the sorbate
molecules adheres, while the remainder renounce into the
liquid phase. Under the kinetics, the plots of the
concentration of metal ions i.e. log [1-u (t)] vs. contact time
are linear, indicates that the sorption could be a first order
reversible kinetics.
Keywords--- Activated Carbon, Adsorption Isotherm,
Sorbate, Cu
++
, Ni
++
and Co
++
Etc.


G. Revathi Associate Professor, Department of Chemistry, Sri
Subramanya College of Engineering and Technology, Palani - 624 615, India.
I. INTRODUCTION
DSORPTION is a process of binding of molecules or
particles on the surface and is usually weak and
reversible. Compound that contain chromogenic groups are
often strongly adsorbed on activated carbon.
Decolourisation is one of the adsorption processes with
significant loss of required materials from solution mixtures.
The most common industrial adsorbents are activated carbon,
silica gel and alumina, because of higher surface area per
unit weight of the compound. Freshly prepared carbon has a
clean surface which has the capacity of adsorption more.
After the adsorption process is over, when the carbon
surface system is saturated, no further adsorption takes
place. The reuse of carbon system can be achieved by
desorption process which includes roasting, treatment with
steam, oxidizing agents like hydrogen peroxide, acids etc.
Temperature effects are pronounced in the process of
adsorption, some of the carbon system may also be oxidized
and hence material loss is occurred. Hence experimental
studies are conducted at constant temperature, and the
resulted graphs are called isotherms.
Some of the complex metal ions containing dyes are
expected to be retained on adsorbent surface by simple
physical adsorption, mechanical retention and sometimes by
covalent bonds [1]. Dyes containing aromatic amines are
expected to carry heavy metal ions like Cr (III) [2], Cu (II)
[3] and Co (II) [4] are mainly responsible for heavy metal
ion pollution. Colour acquired by water body through the
discharge of effluents inhibits the growth of the desirable
aquatic biota necessary for self purification by reducing
the penetration of sunlight and consequent reduction in the
photosynthetic activity [5]. Kawadkal et al [6] reported that
the fish present in the river had a disagreeable taste
indicating the organoleptic property of the fish is altered.
Even in the low concentrations, phenol impart not only
bad taste but also toxic to fish and other aquatic life [7].
Textile waste water pollution into the river water not only
reduced the vegetative cover of catchments but also
eliminated some of the rare species of flora and fauna of that
area.
Adsorption process is a sludge free operation and hence
produce high quality treated effluents. Activated carbon has
been demonstrated for its high potential power in removing
colour from textile dye effluents [8]. Activated carbon is
Adsorptive Removal of Metal (Cu
++
, Co
++
and
NI
++
) Ions from Aqueou Solution Over Powdered
Activated Carbon: A Kinetic and Equilibrium Study
G. Revathi
A
Bonfring International Journal of Industrial Engineering and Management Science, Vol. 2, No. 2, June 2012 15
ISSN 2277 - 5056 | 2012 Bonfring
effective for removal of organic substances of low
solubility [9] because it provides large interfacial area
at which such substances may accumulate and
differences in adsorption capacity may be explained in
terms of relative pore size and varying surface properties
[10].
Though activated carbon is potential in removing textile
effluents colour, the initial cost of carbon is high and also it
have the problems of regeneration, the scientist are in search
for alternate adsorbents. The removal of colour [11] is
widely studied after using various low cost carbon which was
prepared from natural sources such as wool, silica, clay
minerals, peat, wood and industrial wastes like fly ash, coke,
clay, bagasse pith, orange red, bamboo pulp, cotton waste,
tea dust, coconut husk and shell, rice husk etc., by many
workers. Stack et al [12] observed that higher
concentration biological solids, activated sludge process was
effective in removing colour up to86% only. The high
capacity of charcoal for decolourisation was observed by
Lowitz[13] in 1785.
Activated carbons are known to have a
heterogeneous physical and chemical structure. The former
arises from the existence of micro, meso and macro pores of
different sizes and the later arises from the variety of
functional groups that exist on the surface [14].
The edges of carbon surface are more reactive and
contain a wide variety of functional groups, which are
associated with high concentration of unpaired electron spin
centre. The acidic functional groups present on the surface
include carboxyl groups, phenolic groups and quinine type
carboxylic groups. The effects of surface carbon-oxygen
groups and the sorbate-sorbent - * interaction on the
adsorption mechanism of organic compounds were
enlightened by Hassler [15] in the 1950s. Adsorption
capacity of an activated carbon depends on, the nature of
the adsorbent (pore structure, ash content and functional
groups), the nature of adsorbate (pKa, functional group
present, polarity, molecular weight & size) and the
solution conditions (pH, ionic strength and concentration).
The adsorption capacity of any adsorbent is generally
proportional to the surface area and adsorbent pores. Gupta
et al [16] investigated removal of chrome ions using
activated carbon and reported that uptake of chrome ion is
mainly due to inter particle diffusion leading to the
formation of a mono layer on the sorbent indicating
chemisorption type of interaction.
Commercially activated carbon is most costly, hence to
overcome this, low cost carbon system, which were
obtained from used up commercial batteries like Nippo,
BPL etc., are used. The carbon systems are also
recommended for effective adsorption of heavy metal
cations like Hg
++
, Cd
++
, Zn
++
, Cr
+++
on one hand and F
-
,CrO
4
-
and other anions on the other hand which leads to
Green Chemistry.
In our preliminary investigation the adsorption of
metal ions like Co(II), Cr(V), Fe(II), Pt(II),Cu(II) on the
carbons have been attempted. Out of the metal ions studied
Cu(II), Co(II) and Ni(II) are found to adsorbed more on the
carbon and hence detailed study is undertaken on Cu
+2
, Ni
+2
and Co
+2
ions.
II. OBJECTIVES OF THE PRESENT STUDY
1. Procurement of carbon from waste batteries(Nippo, BPL
brands)
2. Characterization of carbon systems for parameters such as
surface area (PNPmethod), pH determination,
decolourization power on methylene blue.
3. Selection of metal ions for detailed study.
4. Optimization of conditions for maximum adsorption.
5. Adsorption isotherm studies (Langmuir and Freundlich)
and
6. Kinetic parameters of the adsorption
III. EXPERIMENTAL STUDIES
A. Procurement of Carbon
Used up commercial batteries BPL Company was
collected and broken after taking care to protect the carbon
rods. The carbon rods were powdered and washed well with
water for several times. The carbon powder was dried under
sunlight of about 48 hours. The powder was grinded in a
mortar and sieved for particle size 40 American Standard
Mesh (ASTM).
B. Determination of pH
About 10 g of carbon sample was taken into a 500 ml
beaker. 300 ml of cooled water of pH=7 was added and
heated to boil. After 10 minutes the solution was filtered and
the first fraction of 20 ml was discarded and the remaining
filtrate was cooled and pH was measured using Elico pH
meter.
The pH of the carbon sample observed is 6.5.
C. Determination of Decolorizing Power
About 0.1 g of carbon sample was taken in a 50 ml
glass stoppered flask; 1 ml of methylene blue solution
(0.15%) was added from a burette and shaken for 5 minutes.
Addition of methylene blue solution and shaking was
continued till the blue colour persists at least for 5 minutes.
Decolourizing power (mg/g) = (1.5 x V)/M
where
V - volume of methylene blue solution consumed for carbon
sample in ml.
M - weight of the carbon sample taken for analysis in grams.
Our result is 135 mg/g (V=9ml,M=0.1g).
D. Determination of Surface Area (Adsorption of P-
Nitrophenol (PNP) Method)
0.1molar PNP solution was prepared. Aliquots ranging
from 0.5-5 ml solutions were transferred to a series of 100
ml standard measuring flask. To each 2 ml of 0.1N NaOH
Bonfring International Journal of Industrial Engineering and Management Science, Vol. 2, No. 2, June 2012 16
ISSN 2277 - 5056 | 2012 Bonfring
solution was added and made up to 100 ml with water. The
absorbances of these solutions were measured
photometrically.
About 0.5 g of carbon were accurately weighed and
taken into a series of 150 ml stoppered reagent bottles. In
the range of 0.1 to 0.9 ppm PNP solutions were prepared
separately and 100 ml of these solutions were added to each
of these reagent bottles and kept for shaking in a rotary
mechanical shaker for about 24 hours. At the end of
equilibration period, 60ml of the supernatant solution was
transferred into a 100 ml standard measuring flask. 2ml of
0.1N NaOH solution was added and made up to 100 ml. The
absorbances of these solutions were measured
photometrically. The concentration of PNP solution (C),
remaining in each case was established by reference to
the calibration graph. The number of millimoles of PNP
solutions absorbed by 1 g of carbon was calculated using
the difference between initial and final concentration of
PNP solution and it was designated as N. C/N was
plotted against C (figure 1) and a straight line was obtained.

Figure 1: Surface Area (PNP Method)
The reciprocal of the slope of the straight line gave the
number of milli moles of PNP required per gram of carbon
to form a monolayer which was designated as N
m
. By
assuming that the molecular cross sectional area of PNP
as 52.5
0
A
2
, the area available in square meters per gram
of carbon (A) was calculated using the equation A=N
m
N
0

10
-20

where
A - specific area in square meters per gram.
N
m
- the number of moles per gram required to form a
monolayer (reciprocal of the slope of the straight line).
N
0
- Avagadro number
- molecular cross sectional area of PNP solution given in
square angstroms.
Our result is 344 m
2
/g.
E. Effect of Carbon Dose on Cu (II), Ni (II) and Co (II)
A series of 0.1 to 0.9 mole metal ion solutions were
taken in stoppered reagent glass bottles and varied quantities
(0.1 to 0.9 g) of carbon were added and equilibrated for 5
hours and from the supernatant liquid, the percentage of
metal ion removed was calculated.
F. Adsorption Isotherm Studies of Cu, Ni and Co Ions
Adsorption isotherm experiments were conducted by
taking varying amount of adsorbents ranging from 100 mg
to 500 mg and each case 0.1 to o.9 moles of 100 ml metal
ion solution were added and equilibrated. After
equilibration period, the concentration of supernatant liquid
was measured and the amounts of metal adsorbed were
calculated.
IV. RESULTS AND DISCUSSION
Plot of metal adsorbed in mg (x/m) Vs equilibrium metal
concentration (C
e
) (figure 2) are linear at low concentration
and steady at higher concentration. This supports the
Langmuir theory that the intermolecular forces between
the sorbate and sorbent would not be significant beyond the
first sorbed layer and that a portion of the sorbate molecules
adheres, while the remainder renounce into the liquid phase.
The plot of log(x/m) Vs log (C
e
) (figures 3 & 4) results
only one straight line which indicates the mono layer
formation of metal ions on the adsorbed surface.(where x-
Amount of metal ion adsorbed at equilibrium state, m-
weight of adsorbent used, C
e
- The equilibrium concentration
of metal ions remaining). Fit of the experimental data into
Freundlich model is an indication of heterogeneity of the
adsorbent surface.

Figure 2: Equilibrium Sorption Curve
From the Langmuir and Freundlich isotherm studies,
the order of adsorption capacities of various carbon system
for metal ions are Co (NO
3
)
2
system > CuSO
4
system >
NiCl
2
system.
The plots of log (1-u(t)) Vs contact time (figure 5, 6 & 7)
are linear [u(t)=x/x
e
where x- amount of metal ions
transported from liquid phase to solid phase, x
e

concentration of metal ions adsorbed at equilibrium.]
indicates that the sorption could be approximated to first
order reversible kinetic. The overall rate constant K = k
1
+k
-1
where k
1
is the rate constant of forward reaction, k
-1
is the
Bonfring International Journal of Industrial Engineering and Management Science, Vol. 2, No. 2, June 2012 17
ISSN 2277 - 5056 | 2012 Bonfring
rate constant of backward reaction.

Figure 3: Freundlich Plot of Copper Ion

Figure 4: Langmuir Plot of Copper Ion
Table 1: Isotherm Constants

S.No.

System
Freundlich

constant 1/n
Langmuir constant
a mg/l
b 10
-4
mg/l
1 CuSO
4 0.2562 158 5.01
2 NiCl
2 0.2159 156 4.75
3 Co(NO
3
)
2 0.3072 141 5.42

From the Bhatacharya Vencobhachar plots (figures 5, 6 &
7) of Cu ion, Co ion and Ni ion, it is obvious that the system
undergoes first order rate mechanism and form a monolayer.
Desorption also takes place and confirms that it undergoes
physisorption mechanism.
Carbon characteristics like pH (6.5), surface area 344
m
2
/ g and decolourization power 135 mg/g were
determined. Carbon dose required for maximum percentage
of adsorption was found as 55.8, 50.5 and 54.2 in the case
of Cu
++
, Ni
++
and Co
++
ions respectively per gram of
carbon.

Figure 5: Bhatacharya Vencobhachar Plot of Copper

Figure 6: Bhatacharya Vencobhachar Plot of Cobalt

Figure 7: Bhatacharya Vencobhachar Plot of Nickel
The regression co-efficient r and correlation co-
efficient r
2
values show that this system fitted very well to
Bonfring International Journal of Industrial Engineering and Management Science, Vol. 2, No. 2, June 2012 18
ISSN 2277 - 5056 | 2012 Bonfring
first order mechanism. For Cu, r values ranges from 0.9844 to
0.9998 and r
2
ranges from 0.9690 to 0.9996 and for Co and
Ni the corresponding r and r
2
values are 0.9844 to 0.9999
and 0.9625 to 0.9999 & 0.9484 to 0.9821 and 0.8994 to
0.9768 respectively.
V. CONCLUSION
The carbon prepared from locally available cheap
material (used up BPL battery carbon rod) showing
activity very similar to commercial activated carbon.
The maximum removal of metal ions is happening with
equilibrium periods of about 1 hour. Adsorption isotherm
constants after studying Langmuir and Freundlich were
determined. Under the kinetics a first order kinetic
mechanism is operating. The carbon can be reused at least
5 times without much reduction in the adsorption
capacity. Application of the carbon to the removal of
heavy metal ions and decolourization studies gives
significant results.
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