Study the adsorption & its kinetic

behavior
of heavy metal from waste water using
Eco-friendly adsorbent
J.Giriraj, Bhagyamalleswari.G, Irfan khan.P, Pratibha.K & Dr.M.Ventakeswara Rao

Abstract— In recent years water pollution has been the question of the hour due to increased contamination of
water streams by the industrial and domestic operations. From the standpoint of environmental pollution
control, the toxic elements in the industrial waste water should be maintained below the permissible levels.
Presence of heavy metals like Mercury, Nickel, Lead, Chromium etc…in waste water causes severe chronic
disorder. Chromium (VI) when present above the allowable limits causes ulcers and dermatology problems.
There are physical and chemical waste water treatment processes like oxidation, reduction, precipitation, ion-
exchange, and adsorption. However all these processes have some limitations either technical or economical
constraints. Although adsorption is a less expensive process, it converts one form of pollution to the other. An
eco-friendly and economically viable technology is much desirable in the days to come. The basic principle of
the adsorption is that the separation of a substance from one phase accompanied by its accumulation or
concentration at the surface of another. The commonly used adsorbents are activated carbon, saw dust, silica
gel, Zeolites and tea waste. Our present work mainly deals with the tea waste and removal of toxic metals such
as Chromium (VI) from industrial waste water. The results are analyzed and conclusions are made.

Index Terms— waste water, adsorption, teawaste, chromium, heavy metal

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1 INTRODUCTION
The industrial activities generate a large number and 2 MATERIALS & METODS
variety of waste products, which are generally, discharged
2.1 Preparation of Adsorbent
either into water streams or onto land. The nature of the
effluent will depend upon the industrial processes which they Tea waste is washed with water and sun dried for a minimum
originate. The problem of adequate handling industrial waste of 24hours. The dried powder is washed with water to free of
water causes more complex and much more difficult problems color and turbidity and then dried to room temperature in a
than sewage because industrial waste waters are heavily laden shade for at least 2 days. The resulting powder is dried and
with organic or inorganic or mineral matter or toxic heavy sieved to different size fractions using rotor sieve shaker. The
metals or with corrosive, poisonous, inflammable or explosive sieves with BSS no as 85,100,120,150,170,200,240,300 are
substances. arranged in an increasing order and placed in a rotap sieve
The objective of waste water treatment and management shaker ad then sieved for 15 minutes then the sieved tea waste
has widely expanded from simple nuisance control to include is preserved in inter–lock packets the particle size is calculated
public health, environmental, aesthetic and ecological as:
considerations. The potential source of Chromium in waste
water in industrial wastes from textile, leather tanning, metal
finishing, electroplating, ceramics, cooling tower effluents and
animals glue manufacture. Maximum permissible limit of Cr
(VI) by WHO, ICMR is 0.05mg/lit. Injection of Cr (VI) above its
permissible limit causes pain, vomiting, nausea brain
hemorrhage, acute diarrhea and abnormalities related to
genetic cycle mutation. Adsorption is viable method for the
removal of the toxic metals from the effluents due to its easy
handling and less expensiveness.

Table: 1 Sieving is done in rotap sieve saker and sizes

are given in above table
After calculating the size of the adsorbent we have taken the
samples of tea waste with particle size-165μm, 115μm, 58μm
as the adsorbent.

2.2 Preparation of Chromium Stock Solution

The synthetic solution of 1000mg/lit of Cr is prepared
by dissolving 2.8510gms of 99.5% K 2Cr2O7 in lit of distilled
water 90mg/lit synthetic solution in a 1000ml of volumetric
flask and adding distilled water up to the mark. Similarly Cr
solutions of other metal concentration are solutions of 0.1N
H2SO4 or 0.1N NaOH
AS 2.8510 gm of 99.5% K 2Cr2O7 in lit of distilled water and thus
0.05686 gm of 99.5% K2Cr2O7 in 1 lit of distilled water.

3 RESULTS & DISCUSSION It is observed that the rate of adsorption is fast in the initial
3.1 Effect of Agitation Time stages because adequate surface area available for adsorption
Now the chromium (VI) solution of 50 ml with 18.4 of chromium. As time increases, more amount of chromium
PPM as an initial concentration(Ci) is taken in different gets adsorbed onto the surface of the adsorbent and thus the
conical flasks .To this solution the adsorbent tea waste of size available surface area decreases. The adsorbate normally
165μm of 1 gram is taken and mixed into the chromium forms a thick layer over the surface .when this monomolecule
solution .Then these conical flasks are kept on a rim shaker covers the surface, the capacity of the adsorbent is exhausted
and then for every 15 min interval of time each conical flask is and it is observed that for particle size of 165 and 115μm the
taken out from the rim shaker and the solution is filtered optimum agitation time is found to be 120 min and for particle
using a Whitman filter paper so that to separate the adsorbate size of 58μm agitation time is found to be 90 min.
from that of the aqueous solution .The final concentrations (C 0)
of chromium are analyzed and the % adsorption is calculated
as follows
%Adsorption = (Ci-Co) x 100/Ci
The optimum agitation time is determined by plotting
the % removal of chromium against agitation time. Fig 1 to 3
represents the effect of agitation time. Optimum time is
defined as the time required for heavy metal concentration to
reach a constant value during adsorption.
 weights say 1,2,3,4 gm and allowed to undergo adsorption
process and then filtered and the final concentrations is
determined and tabulated below

It is observed that the rate of adsorption is fast in the initial

stages because adequate surface area available for adsorption
of chromium. As time increases, more amount of chromium
gets adsorbed onto the surface of the adsorbent and thus the
available surface area decreases. The adsorbate normally
forms a thick layer over the surface .when this monomolecule
covers the surface, the capacity of the adsorbent is exhausted
and it is observed that for particle size of 165 and 115μm the
optimum agitation time is found to be 120 min and for particle
size of 58μm agitation time is found to be 90 min.

It is evident from the plots that the %adsorption increases with

3.2 Effect of Particle Size
Chromium solution is mixed with 1 gram of
adsorbent of different particle sizes and kept on rim shaker
.After 90min they are removed from the rim shaker and then
filtered .The final concentrations are analyzed and the %
adsorption is determined and tabulated below
Now a graph is drawn between the values of particle size and
the % adsorption
increase in the adsorbent dosage .The % adsorption of
chromium from the aqueous solution increases from 84.47 to
92.30 as the dosage is increased from 1to 4 gms .such behavior
is obvious because the no of active sites available for metal
removal would be more as the amount of the adsorbent
increases. And thus the remaining experiment is carried out by
using 4gms of adsorbent.

3.4 Effect of Volume of the Aqueous Solution

Considering the adsorbent of particle size 58µm and
the chromium solution of different volumes say 50, 100, 150,
200, 250 ml are mixed with 4 gms of adsorbent and allowed to
undergo adsorption process and then filtered and the final
concentrations are analyzed and tabulated below

Fig 4 represents the % adsorption as a function of particle size.

The % adsorption of chromium is increased as the adsorbent
particle size decreases from 165μm to 58μm.This phenomena
is expected, as the size of the particle decreases, surface area of
the adsorbent increases, thereby the no of active sites on the
adsorbent are better exposed to the adsorbate and from fig-4 it
is observed that adsorbent of small particle size (58μm) has the
highest % adsorption of 84.47. Therefore the remaining
experiment is carried out by using the adsorbent with particle
size of 53μm Change in % adsorption with variation in volume of aqueous
solution from 50 to 150ml is shown in fig-6 From this plots, it
3.3 Effect of Adsorbent Dosage is clear that %adsorption gradually decreases with an increase
Considering the adsorbent with particle size of 58μm in volume of the aqueous solution .The % adsorption is
the chromium solution is mixed with adsorbent of different decreased from 92.3 to 80.89 As the volume of aqueous
solution increases, the amount of chromium present in the
solution also increases .This implies that % metal removal by
unaltered surface area of the adsorbent decreases as the
amount of chromium in the solution is increased.
3.5 Effect of Initial Concentrations of Aqueous
Solution
Considering the adsorbent of particle size 53 μm and
the chromium solutions with different initial concentrations
are mixed with 4gms of the adsorbent and allowed to undergo
adsorption process and then filtered and then the final
concentrations are analyzed and tabulated below
The effect of initial concentration of chromium in the aqueous
solution on the percentage adsorption of chromium is shown
in fig-7. The % adsorption is decreased from 95.83 to 68.292 by
increasing the initial concentration of chromium in the
aqueous solution from 5mg/l to 50 mg/l such behavior can be
attributed to the increase in the amount of adsorbate to the
unchanging no of available active sites on the adsorbent (since
the amount of adsorbent is kept constant).
3.6 Effect of pH:
The adsorption experiment was conducted by varying the
pH of the solution. It is observed that the present adsorption
increases in acidic medium and the decrease in basic medium.
3.7 ADSORPTION ISOTHERMS
3.7.1. Freundlich Isotherm for Adsorption of Chromium:
The Freundlich relationship is an empirical equation. It does
not indicate a finet uptake capacity of the adsorbent and can
thus only be applied in case of low and intermediate
concentration ranges
The Freundlich isotherm is given by
qe= Kf Ce(1/n)
Taking logarithm on both sides, we get
logqe= logKf +(1/n) logCe
Where Kf and n are known as Freundlich constants obtainable
from the plot of log qe versus logCe
The equation is obtained from the plot
3.7.2. Langmuir Isotherm for Adsorption of Chromium
Since the chemical forces fall off very rapidly with
distance it is probable that chemisorptions does not extend
beyond a single layer of adsorbate on the surface of the solid.
it can be anticipated as first pointed out by Langmuir that
chemisorbed adsorbate layers may be only one molecule
thick .The Langmuir isotherm is the most widely used two-
parameter equation . The relationship is a hyperbolic type
form
qe/q m=bCe / (1+ bCe)
Where Ce is the concentration of the adsorbate at equilibrium,
qe is the amount adsorbed at equilibrium per unit mass of the
adsorbent and b is the co-efficient related to affinity on
rearranging the above equation
(Ce/ qe) = 1/b q m+Ce/q m
From the plot between (Ce/ qe) and Ce, we can calculate
the slope (1/ q m) and the intercept (1/b) . Further analysis of
the Langmuir equation is made on the basis of separation
factor .RL defined as
RL= 1 / (1+ bCe)

0< RL<1 indicates favorable adsorption

RL>1 indicates unfavorable adsorption
RL=1 indicates linear adsorption
RL=0 indicates irreversible adsorption

Different kinetic models with correlation

coefficient and lalgergren kinetic model is
favourable

3.8.2. Intra particle diffusion model

Metal ions of chromium are transferred from solute to solid

adsorbent trough intra particle diffusion. For this model there
3.8 Adsorption kinetics is an equation for knowing whether tea waste is suitable or not
3.8.1. Pseudo first order rate equation of lagergren for adsoption of heavy metal such as chromium is given
The Lagergren rate equation (Lagergren, 1898) was the below.
®rst rate equation for the sorption of liquid/solid system
based on solid capacity. The Lagergren rate equation is qt =Kp.t (1/2) +C
one of the most widely used sorption rate equations for Where qt is amount of heavy metal adsorbed on adsorbent
the sorption of a solute from a liquid solution. The order (mg/g), Kp is intra particle rate constant, and C is constant.
of adsorbate interaction with adsorbent has been
described using various kinetic models. Psuedo first-
order model derived by Lagergren and sven is widely
applicable. Psuedo-second-order can also very well
describe these interactions in certain specific cases.

Log (qe-qt) =logqe – (k/2.303)*t

Where qe and qt (mg/lit) are amount adsorbed at

equilibrium and at time t respectively and k (min-1) is
the pseudo first-order rate constant. A plot of log (qe-
qt) vs. t gives a straight line which allows computing
the adsorption rate constant
K (min-1)

Fig: 11 Intra particle diffusion model

Fig: 10 peudo first order graph of lagergren

4 CONCLUSION
In this study it is observed that the tea waste is an efficient adsorbent
for removal of Cr (VI) from aqueous solutions.It is observed that as
the contact time increases percentage adsorption increases until it
reaches equilibrium. The optimum contact time for Cr (VI) is
90min.It is also observed that as the adsorbent dosage increases
percentage adsorption increases. The optimum adsorbent dosage is
4gms.It is observed that as the adsorbent size increases percentage
adsorption decreases because surface area decreases.It is observed
that as the initial adsorbate concentration increases percentage
adsorption decreases.In the study of volume of aqueous solution as
the volume increases percentage adsorption decreases.Freundlich
Isotherm and Langumiar Isotherms are studied at room temperature
and adsorption process is favourable. Kinetics has studied and it is
confirm that adsoption ofcromium metal through tea waste is favours
first order kinetics and intra particle diffucion model is also studied,
it is observed that tea waste is aving good boundary layer effect. Tea
waste is founf to be good low cost adsorbent for heavy metals like
chromium.

Acknowledgment

The authors’ greatfullly acknowledge the support of R.V.R&JC

COLLEGE OF ENGINEERING (Chemical Engineering
department) through out the project.

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