ABSTRACT:

Chromium is commonly found in huge quantities in electroplating industries, and tannery

wastewaters. For this reason, the removal and recovery of the chromium content of tannery
wastewaters is crucial for environmental protection and economic reasons. Removal and
recovery of chromium were carried out by using low-cost potential adsorbents. For this purpose
the use of Jatropha oil cake as an adsorbent was studied. The adsorption process and extent of
adsorption are dependent on the physical and chemical characteristics of the adsorbent, adsorbate
and experimental condition. The effect of pH, temperature, adsorbent dose on the adsorption
isotherm of Cr (VI) was studied in batch system. The sorption data fitted well with Temkin
adsorption model. A pseudo first order model was the most appropriate to describe the kinetic
experimental data.
1. INTRODUCTION

The pollutants from the electroplating industries are invariably hazardous, as the effluents
contaminate air, water and soil. Some of the polluting agents have deleterious effect on human
health, examples being cadmium, lead, nickel etc., The environmental load in electroplating
industry mainly consists of process waste water, hydroxide sludge and sulphuric acid. The
untreated rinsing water has a lot of waste.

TABLE–1.1 CONCENTRATIONS OF METALS IN UNTREATED WATER

Contents Concentration (mg/l)

Iron 150
Chrome 4.4
Cr+6 2
Zinc 240
Suspended Material 620

Various industries produce and discharge wastes containing different heavy

metals into the environment, such as mining and smelting of metalliferous, surface finishing
industry, energy and fuel production, fertilizer and pesticide industry and application,
metallurgy, iron and steel, electroplating, electrolysis, electro-osmosis, leatherworking,
photography, electric appliance manufacturing, metal surface treating, aerospace and atomic
energy installation etc. Thus, metal as a kind of resource is becoming shortage and also brings
about serious environmental pollution, threatening human health and ecosystem. Three kinds of
heavy metals are of concern, including toxic metals (such as Hg, Cr, Pb, Zn, Cu, Ni, Cd, As, Co,
Sn, etc.), precious metals (such as Pd, Pt, Ag, Au, Ru etc.) and radionuclides (such as U, Th, Ra,
Am, etc.) The demand of chromium has been increasing globally due to its extensive use in
various metallurgical, chemical, dye, electroplating and leather tanning industries (Raji and
Anirudhan, 1998) due to its various physico-chemical properties. Apart from industrial uses,
Cr(III) plays an important role in our body (Wang et al., 2004). Without Cr(III) in our diet, the
body loses its ability to use sugar, protein and fat properly, which may result in weight loss or
impaired growth, improper function of nervous system and imbibe diabetic conditions.

The pollution of water resources due to indiscriminate disposal of chromium metals has
been causing worldwide concern for the last few decades (Oguz et al., 2005) Chromium, an
element which has been used by man for years, can be regarded as a longstanding environmental
contaminant Low-level exposure of chromium can irritate the skin and cause ulceration. Overexposure
of chromium workers to chromium dusts and mists has been related to irritation and corrosion of the
respiratory tract, lung carcinoma, kidney and liver damage, and damage to circulatory and nerve tissue.
Heavy metals are dangerous because they tend to bio accumulate. Bioaccumulation means an increase in
the concentration of a chemical in a biological organism over time, compared to the chemical's
concentration in the environment. Chromium, especially in its VI oxidation state, is considered as a very
toxic ion; thus, its elimination from aqueous solutions should be considered an environmental primary
target. The hexavalent chromium compounds are also known to be significantly more toxic than the
trivalent ones. The hexavalent form has been considered to be more hazardous due to its carcinogenic
properties. Due to environmental concern, discharge limits of both Cr(III) and Cr(VI) have been instituted
by most industrial countries. Their concentration in industrial wastewaters ranges from 0.5 to 270 mg/l.
The tolerance limit for Cr(VI) for discharge into inland surface waters is 0.1 mg/l and in potable
water is 0.05 mg/l. These metals are found well above the tolerance limit many a times in aquatic
environment [Tewaria et al., 2005].

Methods for removing metal ions from aqueous solution mainly consist of

• Physical
• Chemical and
• Biological technologies.

These Conventional methods include

• Chemical precipitation (Philipot et al., 1984)

• Ion exchange process (Jorgensen et al., 1979)
• Membrane separation
• Solvent extraction (Patterson et al., 1978)
• Thermal treatment methods

Some of the above conventional technologies are ineffective and unfavourable (Venkata Mohan
et al., 2003) because of the following reasons.
 • The chemical methods such as precipitation require a large excess of chemicals, which
generates volumetric sludge and increases the costs. (Spearot et al., 1984)
• The methods such as evaporation, electroplating, ion exchange and membrane process
are generally expensive and require frequent service attention.
• inefficient to reduce the effluent concentration to the required levels
• In some of the conventional metal removal processes, the chromium(III) can be oxidized
to chromium(VI), thus yielding a more toxic compound.
• Chemical precipitation and electrochemical treatment are ineffective, especially when
metal ion concentration in aqueous solution is among 1 to 100 mg L− 1, and also produce
large quantity of sludge required to treat with great difficulty.
• Ion exchange, membrane technologies and activated carbon adsorption process are
extremely expensive when treating large amount of water and wastewater containing
heavy metal in low concentration, they cannot be used at large scale

BIOSORPTION METHOD-ALTERNATIVE TECHNOLOGY

Biosorption technology has been paid much attention, and gradually becomes hot topic in
the field of metal pollution control in the recent years because of its potential application.
Adsorption is a process in which a single or a group of ions/compounds get accumulated on the
surface of another solid or liquid. The substance on which the adsorption takes place is known as
adsorbent and the substance which gets adsorbed is called adsorbate.

Biosorption probably occurs through a combination of the following mechanisms,

chemisorption by ion exchange, complexation, coordination, chelation, physical adsorption and
micro precipitation.

Biosorption involves both active and passive transport mechanisms. The first stage,
usually referred to as passive uptake, is an initial rapid and reversible accumulation step. The
second stage, usually referred to as active uptake, is slower intracellular bioaccumulation, often
irreversible and related to metabolic activity.

PRESENT STUDY
 Keeping in view the importance of treatment of Cr(VI) contaminated water from
industrial and mining establishments, the present study reports the feasibility of Cr(VI)
adsorption by using a low cost, environment friendly adsorbent Jatropha oil cake.

The physico-chemical properties of the adsorbents were analyzed by XRD, FT-IR, SEM
and BET. For all the five adsorbents, adsorption efficiency was studied as a function of contact
time, pH, temperature, adsorbent dose and adsorbate concentration. Different adsorption
isotherms were employed in order to evaluate the optimum adsorption conditions.

2. LITERATURE SURVEY

In the present study we have taken Jatropha Oil Cake

Jatropha curcus is a drought- resistant perennial, Monoecious growing well in

margin/poor soil. It is easy to establish, grows relatively quickly and lives, producing seeds for
50 years. Jatropha the wonder plant produces seeds with an oil content of 37%. The oil can be
combusted as fuel without being refined. It burns with clear smoke-free flame, tested
successfully as fuel for simple diesel engine. The by-products are press cake a good organic
fertilizer, oil contains also insecticide

Medically it is used for diseases like cancer, piles, snakebite, and paralysis. The annual
nut yield ranges from 0.5 to 12 tons. The kernels consist of oil to about 60 percent; this can be
transformed into biodiesel fuel through esterification. It is found to be growing in many parts of
the country, rugged in nature and can survive with minimum inputs and easy to propagate. It
grows on well-drained soils with good aeration and is well adapted to marginal soils with low
nutrient content. The Jatropha can be grown in all countries falling under tropical, subtropical
zones and in certain countries fall in temperate climate. Also in certain areas of Arid and sub-
Arid regions As per Vegetation Classification it grows in the selva, or equatorial rain-forest belt,
the hot tropical belt and in the savanna region perfectly. The seeds become mature when the
capsule changes from green to yellow, after two to four months.

Jatropha oil cake contains nitrogen, phosphorous and potassium, have high nutritive
value and can be used as organic manure. It has Insecticidal and Molluscicidal Properties. It
contains manorial value with 6% N, 2.75% P2O5 and 0.94 K2O.
3.MATERIALS AND METHODS

3.1 ADSORBENT PREPARATION

Jatropha oil cake was collected from the Tamil Nadu Agricultural University and it was
sun dried for 2 days. Then it was crushed and sieved <.25mm in size.

3.2 CHARACTERIZATION OF CHROMIUM(VI) EFFLUENT

The Cr(VI) effluent was collected from the Divya Engineering,

Chinnavedampatti, Coimbatore and the pH, COD, TDS and Cr(VI) content in the were
determined using the pH meter, COD analyzer, TDS analyzer and AAS respectively.

3.3 BATCH EXPERIMENTS

Batch biosorption experiments were performed in a rotary shaker at 150 rpm (Shashi and
Krishna., 2007) using 250 ml,100 ml Erlenmeyer flasks containing different amount of
adsorbents (varying from 0.5-5g) in 50 ml of chromium solution with varying pH ranging from
3-7 (using 0.1 M HCl and 0.1 M NaOH). After 3hr, the reaction mixture was centrifuged at 3000
rpm for 10 min. The chromium content in the supernatant was determined using colorimeteric
method (Goel., 1992).

3.4 BATCH EQUILIBRIUM STUDIES

3.4.1 EFFECT OF pH

To measure the effect of pH in metal adsorption, the experimental setup was carried out
in different range of pH level of the Cr solution as follow.

METHODS

1. Cr solution was prepared in the concentration of 50 mg/l in five 100 ml Erlenmeyer

flasks.

2. pH of the Cr solutions was adjusted ranging from 3 to 7 using 1N NaoH and 1N HCl
solutions.
 3. Then 0.5 g of Jatropha oil cake, Pongamia seed shell, Carbonized date seeds were added
to the flasks respectively.

4. The flasks were kept in isothermal shaker for 3 hrs at 150 rpm.

5. After 3 hrs OD value of the Cr solutions were analyzed using colorimeter ( see
Appendix ) and the adsorption values were calculated. The graph was plotted against
adsorption values versus pH range.

3.4.2 EFFECT OF DOSAGE CONCENTRATION

To measure the effect of adsorbent dosage concentration in metal adsorption, the

experimental setup was carried out in different range of adsorbent dosage concentration level of
the Cr solution as follow.

METHODS

1. Cr solution was prepared in the concentration of 50 mg/l in nine 100 ml Erlenmeyer

flasks.

2. pH of the Cr solution was adjusted according to the above results using

1N NaoH and 1N HCl solutions.

3. Then 0.1-5g of Jatropha oil cake, Pongamia seed shell and Carbonized date seeds were
added to the flasks respectively.

4. The flasks were kept in isothermal shaker for 3 hrs at 150 rpm.

5. After 3 hrs OD value of the Cr solutions were analyzed using colorimeter and the
adsorption values were calculated. The graph was plotted against adsorption values
versus dosage concentration.

3.4.3 EFFECT OF TEMPERATURE

 To measure the effect of temperature in metal adsorption, the experimental setup was
carried out in different range of temperature level of the Cr solution as follow.

METHODS

1. Cr solution was prepared in the concentration of 50 mg/l in three 100 ml Erlenmeyer

flasks.

2. pH of the Cr solutions were adjusted using 1N NaoH and 1N HCl solutions and the
amount of adsorbent added according to the above results.

3. Then the temperature of the shaker was adjusted to 30°C, 40°C, 50°C respectively.

4. The flasks were kept in isothermal shaker for 3 hrs at 150 rpm.

5. After 3 hrs OD value of the Cr solutions were analyzed using colorimeter and the
adsorption values were calculated. The graph was plotted against adsorption values
versus temperature.

3.4.4 EFFECT OF CONTACT TIME:

To measure the effect of contact time in metal adsorption, the experimental setup was
carried out in different time interval level as follow.

METHODS

1. Cr solution was prepared in the concentration range of 10-50 mg/l in 100 ml Erlenmeyer
flasks.

2. pH of the Cr solutions were adjusted using 1N NaoH and 1N HCl solutions and the
amount of adsorbent added according to the above results.

3. The flasks were kept in isothermal shaker for different time interval of 10-300 mins at
150 rpm.

4. After 3 hrs OD value of the metal solutions were analyzed using colorimeter and the
adsorption values were calculated. The graph was plotted against adsorption values
versus temperature.
3.5 THEORITICAL CONSIDERATIONS

The amount of chromium biosorbed was calculated from the differences between the
chromium quantity added to the adsorbents and the chromium content of the supernatant using
the following equation:

…………………………………………………………………...(3.1)

Where,

qe is the chromium uptake (mg/g), C0 and Ce the initial and equilibrium chromium
concentrations in the solution (mg/L), respectively, V the solution volume (L) and M is
the mass of biosorbent (g).

For adsorption models and kinetic experiments, samples were taken at regular
time intervals and analyzed for chromium concentration. To evaluate the differences in
the biosorption rates and uptakes, the adsorption models and kinetic data were described
by the following equations.

3.5.1.1 FREUNDLICH ISOTHERM

Freundlich adsorsption isotherm was proposed by Boedecker in 1895 (Dabrowski,A.,

2001) as an empirical equation. Later Freundlich (Freundlich, H., 1926) made some useful
modifications as a result of which, it assumed great importance. The Freundlich adsorption
equation can be written as:
 1
x
= q e = kc n ……………………………………………………………………..(3.2)
m

Taking the logarithm of both sides,

1` 1
log q e = log k + log ce = K f + log c e ……………………………………………...(3.3)
n n

Where,

‘qe’ is equilibrium adsorption capacity (mg/g), ‘Ce’ is the equilibrium

concentration of the adsorbate in solution, ‘Kf’, and ‘n’ are constants related to the
adsorption process such as adsorption capacity and intensity respectively.

3.5.1.2 LANGMUIR ADSORPTION ISOTHERM

The Langmuir adsorption isotherm (Langmuir, I., 1918) was based on the

following assumptions:

 Fixed number of adsorption sites: at equilibrium, at any temperature, a fraction of the

adsorbent surface sites (θ) is occupied by adsorbed molecules and the rest (1-θ) is free.

 All sorption processes are homogeneous.

 There is only one sorbate

 One sorbate molecule reacts with only one active site.

 No interaction between the sorbate species.

 A monolayer surface phase is formed.

The equation proposed by Langmuir was universally applicable to chemisorption with

some restrictions involving physical adsorption. This equation is applicable to the physical or
chemical adsorption on solid surface with one type of adsorption active center. As long as its
restrictions and limitations are clearly recognized, the Langmuir equation can be used for
describing equilibrium conditions for sorption behavior in different sorbate-sorbent systems or
for varied conditions within any given system. The Langmuir equation is given by:

Ce 1 C
= + e …………………………………………………………………...(3.4)
qe Qo b Qe

Where,

‘Ce’ is the equilibrium concentration and ‘qe’ is the amount of adsorbate adsorbed
per gram of adsorbent at equilibrium (mg/g); ‘Q0’ and ‘b’ are Langmuir constants related
to the sorption capacity and intensity respectively.

3.5.1.3 TEMKIN ADSORPTION ISOTHERM

Temkin and Pyzhev suggested that due to the indirect adsorbate/adsorbent interaction, the
heat of adsorption of all the molecules in the layer would decrease linearly with coverage (Aksu,
Z., 2005). The linear form of Temkin isotherm can be written as:

q eq = B ln A + B ln C eq …………………………………………………………...…(3.5)

Where,

B=RT/b………………………………………………………………..…(3.6)

‘T’ is absolute temperature in Kelvin and ‘R’ is the universal gas constant ( 8.31 J/mol
K ). The constant ‘b’ is related to heat of adsorption. Ceq = equilibrium concentration of the
adsorbate.

3.5.2. ADSORPTION KINETIC MODELS

The study of adsorption kinetics in wastewater is significant as it provides valuable

insight into the reaction pathways and into the mechanism of the reaction.

Further, it is important to predict the time at which the adsorbate is removed from
aqueous solution in order to design an appropriate sorption treatment plant. Any adsorption
process is normally controlled by three diffusive transport processes for the adsorbate:
  From bulk solution to the film surrounding the adsorbent.

 From the film to the adsorbent surface

 From the surface to the internal sites followed by binding of the metal ions onto
the active sites.

But in kinetic modeling, all these three steps are grouped together and it is assumed that
the difference between the average solid phase concentration and equilibrium concentration is
the driving force for adsorption. Further, it is establishedfrom the experimental observations that
at optimum agitation speed, the external boundaries have hardly any effect. So application of the
kinetic model depends only on the initial and final concentrations of the solution at different time
intervals. It is incorrect to apply simple kinetic model such as first and second order rate
equations to a sorption process with solid surface, which is rarely homogenous. Secondly, the
effects of transport and chemical reaction are often experimentally inseparable.

Several kinetic models have been proposed to clarify the mechanism of a solute sorption
from aqueous solution onto an adsorbent:

 Pseudo first order/Lagergren kinetic model

 Pseudo second order kinetic model

3.5.2.1 PSEUDO FIRST ORDER OR LAGERGEN KINETIC MODEL

The Pseudo first order or Lagergen kinetic rate equation for the sorption of liquid-solid
system was derived based on solid adsorption capacity. It is one of the most widely used sorption
rate equations for sorption of a solute from a liquid solution (Taqvi., 2006, Sudhodan., 2006,
Ho., 1999, Lagergren., 1898). According to the authors, the overall adsorption rate is directly
proportional to the driving force, i.e., the difference between initial and equilibrium
concentrations of the adsorbate (qe-q).

dq e
Therefore, the pseudo first order kinetic equation can be expressed as: = k (q e − qt )
dt
………………………………………………………………..…(3.7)
 Where,

‘qe’ is the amount of solute adsorbed at equilibrium per unit mass of adsorbent
(mg/g), ‘q’ is the amount of solute adsorbed at any given time ‘t’ and ‘k’ are the rate
constant. By using the boundary conditions and simplifying, the equation:

k
log( q e − q ) = log q e − t ……………………………………………………....(3.8)
2.303

Where,

‘k’ can be calculated from the slope of the linear plot between log(qe-qt) vs. ‘t’
for different adsorption parameters such as pH, temperature, adsorbate concentration,
adsorbent dose, particle size and agitation speed.

3.5.2.2 PSEUDO SECOND ORDER KINETIC MODEL

A pseudo second order reaction model (Ho, Y. S., 1998, Ho, Y. S., 1999) can also be
applicable to kinetics of sorption and the equation for this reaction can be shown as:

dq
= k ( q e − q ) 2 ………………………………………………………………….(3.9)
dt

On integration for boundary conditions when t=0 to t>0 and q=0 to q>0 and further
simplifications, equation:

t 1 1 1 1
= 2 + t = + t ………………………………………………………...(3.10)
q kq e q e h qe

Where,

h = kq e2 is known as initial sorption rate where ‘k’ is rate constant.The plot of t/qt vs. ‘t’ at

different adsorption parameters will give a linear relationship, which allows for computation of
‘qe’, ‘k’ and ‘h’.
4. RESULTS AND DISCUSSIONS

4.1 EFFECT OF pH

Among all other parameters, pH of solution has been found to be the most important one.
It not only influences the speciation of metal ions but also the charges on the sorption sites of
biomass type (Gao and Wang, 2007; Lee et al., 1998; Marques et al., 2000). Biosorbents,
generally Jatropha oil cake, is considered to contain various functional groups like hydroxyl,
carboxyl, sulphydryl etc. (Lawther et al., 1995; Wang, 2002). With the change in pH of solution,
the behavior of these functional group changes. For example, the ionization constants of various
carboxyl groups have been reported to be around 3–4 (Eccles and Hunt, 1986). In highly acidic
pH, these are protonated and act as positively charged species (Gardea-Torresdey et al., 1990).
Deprotonation of these functional groups occur on increasing pH and these behave as negatively
charged moieties. As the pH is increased from highly acidic to slightly acidic region, the positive
character of biomass is converted to negative one.
It can be said that sorbed positive metal ions can be removed by decreasing the pH of the
system and the biosorbent can be regenerated, re-used and thus, pH contributes directly to the
economics of the biosorption process. In acidic pHs, metal ions are generally positively charged
and are attracted by negatively charged biomass. When the pH is increased, the amount of OH-
ions is increased in the solution. Metal ions react with these OH- ions and are precipitated as
metal hydroxide at some pH value, depending upon the Ksp values of the metal hydroxides. In
general, metal ions are precipitated out in alkaline pH range and do not contribute towards the
biosorption. This gives the upper limit of pH to be studied. Moreover, the chemical speciation of
metal is decided by solution pH. Generally, when the pH of solution exceeds 8, metal ions are
precipitated out. It gives the upper limit of pH range to be studied.Most of the studies performed
for positively charged metal ion are carried out in this pH range.

Fig.4.1.1 Effect of pH in Jatropha oil cake on the removal of Cr (VI) ( initial metal solution
concentration = 50 mg/l, dosage = 0.5 g, temperature = 30°C ).
The above figure clearly represent the adsorption capacity is maximum for Jatropha oil cake at
pH 5.

4.2 EFFECT OF TEMPERATURE

Temperature is found to be an important parameter for the sorption of metal ions dealing
with the thermodynamics of the biosorption process. It is directly related to the kinetic energy of
the metal ions. Thus, it can account for the diffusion process. An increase or decrease in
temperature should cause a change in the amount of metal removed or sorbed by the biomass. As
the biomass is porous in nature, possibilities of diffusion along with adsorption cannot be ruled
out as a mechanism for metal removal. If the process is exothermic and increase in temperature
causes a decrease in the sorption capacity ( Tan et al., 2007 ) and also if the process is
endothermic and increase in temperature causes a increase in the sorption capacity( Asma Saeed
et al., 2009 ).
Fig.4.2.1 Effect of temperature in Jatropha oil cake on the removal of Cr (VI)

( pH 5, initial metal solution concentration = 50 mg/l, dosage = 2.5 g ).

The above figures show the adsorption capacity of Jatropha oil cake at 30°C, 40°C and
50°C. It is clear that adsorption capacity of the the adsorbent is higher in low temperature. It
indicates the exothermic nature of the adsorption reaction. It was explained that as temperature
increased, the physical bonding between the organic compounds and the active sites of the
adsorbent weakened.

4.3 EFFECT OF DOSAGE CONCENTRATION

If the adsorbent concentration is increased the percentage of Cr(VI) adsorption also

increased. This is evident from the Fig.6.1, where the percentage adsorption was plotted against
adsorbent dose. The percentage adsorption increased with increase in adsorbent dose. The
percentage adsorption increased from 5.4 at lower adsorbent dose (0.1 g/50 ml) to 70.82 at
higher adsorbent dose ( 3g/50 ml ) for Jatropha oil cake
Fig.4.3.1 Effect of dosage concentration in Jatropha oil cake on the removal of

Cr (VI) ( pH 5, initial metal solution concentration = 50 mg/l, temperature = 30°C).

However, the Cr(VI) uptake capacity of the Jatropha oil cake 5.4 mg/g at low adsorbent
dose ( 0.1 g/50 ml ) to 0.218 mg/g at high adsorbent dose. Other investigators on Cr(VI) sorption
( Donmez., 1999 ) have also reported similar trend. The decrease in Cr(VI) uptake at higher
adsorbent dose may be due to competition of the Cr(VI) ions for the sites available.

4.3.1 CHARACTREIZATION OF THE CHROMIUM(VI) EFFLUENT

TABLE 4.3.1 Determined values of the Cr(VI) effluent

Trial 1 Trial 2 Trial 3 Average

pH 1.23 1.21 1.21 1.22

TDS 7378 7370 7356 7368

(ppm)

COD 191.5 193.4 192.6 192.5

(ppm)

CONC(VI) 266 265 270 267.2

(mg/L)
 The tolerance limit for Cr(VI) for discharge into inland surface waters is 0.1 mg/l and in
potable water is 0.05 mg/l but the concentration of Cr(VI) in the effluent we have taken is 267.2
and the other characteristics of the effluent such as pH, TDS and COD are 1.22, 7368 ppm and
192.5 ppm respectively which is acidic and harmful to the environment. So we tried to reduce the
Cr(VI) level in the effluent by the adsorption process.

4.4 ADSORPTION ISOTHERM

Adsorption properties and equilibrium data, commonly known as adsorption isotherms,

describe how pollutants interact with adsorbent materials and so they are critical to optimize the
use of adsorbents. In order to optimize the design of an adsorption system to remove Cr(VI) from
solutions, it is important to establish
the most appropriate correlation for the equilibrium curve. An accurate mathematical description
of equilibrium adsorption capacity is indispensable for reliable prediction of adsorption
parameters and quantitative comparison of adsorption behavior for different adsorbent systems.
Several models have been intensively used in the literature to describe experimental data of
adsorption isotherms. The most famous ones are Langmuir, Freundlich and Temkin.

4.4.1 LANGMUIR ADSORPTION ISOTHERM

The Langmuir model suggests that pollutant removal from the aqueous phase occurs on
homogeneous surfaces by monolayer sorption without interactions between sorbed molecules.
This adsorption model is given by:
Ce 1 C
= + e
q e Qo b Qe ……………(4.1)

Where,

‘Ce’ is the equilibrium concentration, ‘qe’ is the amount of adsorbate adsorbed per
gram of adsorbent at equilibrium (mg/g), ‘Q0’ and ‘b’ are Langmuir constants related to
the sorption capacity and intensity respectively.
 Fig.4.4.1.1 Langmuir adsorption isotherm of Cr(VI) on Jatropha oil cake at 30 C.

4.4.1.1 LANGMUIR PARAMETERS

Table.4.4.1.1 Langmuir isotherm model parameters and correlation coefficients for adsorption of
Cr(VI) on Jatropha oil cake, Pongamia seed shell, and Activated date seeds.

ADSORBENTS Q0 (mg/l) b (l/mg) R2

Jatropha oil cake 6.21 0.0951 0.0941
For the Langmuir isotherm, when Ce/qe is plotted against Ce, a straight line with slope of
1/Qe is obtained. The correlation coefficient, R2 in table( 4.4.1.1) indicated that the adsorption
data of Cr(VI) on the Jatropha oil cake.

4.4.2 FREUNDLICH ISOTHERM

Concerning the Freundlich isotherm, it can be expressed by the

following equation:

1` 1
log q e = log k + log ce = K f + log c e
n n ...................................................(4.2)

Where,
 ‘qe’ is equilibrium adsorption capacity (mg/g), ‘Ce’ is the equilibrium concentration of the
adsorbate in solution, ‘Kf’, and ‘n’ are constants related to the adsorption process such as
adsorption capacity and intensity respectively.

0.3 y = 0.979x - 0.268

0.2 R² = 0.844
0.1
0
-0.1
-0.4 -0.2 -0.2 0 0.2 0.4 0.6
-0.3
-0.4
-0.5
-0.6
)/(m
g o
q
e
l

-0.7

log ce (mg/l)

Fig.4.4.2.1 Freundlich adsorption isotherm of Cr(VI) on Jatropha oil cake at 30 C.

The constants ( Kf & n ) can be calculated from the intercept and the slope of linear plot
of the above diagrams of log qe versus log Ce.

4.4.2.1 FREUNDLICH PARAMETERS

Table.4.4.2.1 Freundlich isotherm model parameters and correlation coefficients for adsorption
of Cr(VI) on Jatropha oil cake, Pongamia seed shell, and Carbonized date seeds.

ADSORBENTS Kf (mg/g(l/mg)1/n) N R2
Jatropha oil cake 0.54 1.02 0.8446
For the Freundlich isotherm, when log qe is plotted against log Ce, a straight line
with slope of 1/n is obtained. The correlation coefficient, R2 in table( 4.4.2.1) indicated that the
adsorption data of Cr(VI) on the Jatropha oil cake was not fitted to the Freundlich isotherm.

4.4.3 TEMKIN ISOTHERM

Temkin (1941) considered the effects of some indirect adsorbate-adsorbate interactions

on adsorption isotherms and suggested that, because of these interactions, the heat of adsorption
of all the molecules in the layer would decrease linearly with coverage. The Temkin isotherm has
been used in the following form:
q eq = B ln A + B ln C eq
……………………...………(4.3)

where,

‘T’ is absolute temperature in Kelvin and ‘R’ is the universal gas constant ( 8.31 J/mol K ). The
constant ‘b’ is related to heat of adsorption. Ceq = equilibrium concentration of the adsorbate.

y = 0.601x + 0.626
1.4 R² = 0.912
1.2
1
0.8
0.6
(m

0.4
gq
e

0.2
/)

0
-1 -0.5 0 0.5 1 1.5
ln ce (mg/l)

Fig.4.4.3.1 Temkin adsorption isotherm of Cr(VI) on Jatropha oil cake

at 30 C.

The constants ( b & A ) can be calculated from the intercept and the slope of linear plot
of the above diagrams of qe versus ln Ce.

4.4.3.1 TEMKIN PARAMETERS

Table.4.4.3.1 Temkin isotherm model parameters and correlation coefficients for adsorption of
Cr(VI) on Jatropha oil cake, Pongamia seed shell, and Activated date seeds.

ADSORBENTS B A (l/g) R2
Jatropha oil cake 6,967.39 1.042 0.9125

For the Temkin isotherm, when qe is plotted against ln Ce, a straight line with slope of B
is obtained. The correlation coefficient, R2 in table( 4.4.3.1) indicated that the adsorption data of
Cr(VI) on the Jatropha oil cake fitted to the Temkin isotherm. Among three adsorption isotherms
Temkin isotherm only fitted to the Cr(VI) adsorption equilibrium data.

4.5 ADSORPTION KINETIC MODELING

Adsorption of a given solute on a solid is a fairly complex mechanism. Indeed, the speed
of adsorption is strongly influenced by several parameters such as the status of the solid matrix
that has generally heterogeneous reactive sites, and the physicochemical conditions under which
the adsorption takes place. The study of adsorption kinetics is very useful for understanding the
mechanisms that are involved and also for the design of future facilities adsorption on a large
scale. In order to predict the mechanism involved during the present biosorption process and the
potential rate controlling steps such as mass transport, pore diffusion and chemical reaction
processes, two kinetic models were used to fit the experimental data, namely, pseudo-first-order,
pseudo-second-order models. The best-fit model was selected based on linear regression
correlation coefficient (R2) value.

4.5.1. PSEUDO-FIRST-ORDER KINETIC MODEL

The pseudo-first-order kinetic model (Lagergren, 1898) can be

defined as:

k1 ………………………………………………….…(4.4)
log( q e − q ) = log q e − t
2.303

Where,

‘k1’is the pseudo-first order rate constant of adsorption (min-1). It can be calculated from
the slope of the linear plot between log(qe-qt) vs. ‘t’ for different adsorption parameters such as
pH, temperature, adsorbate concentration, adsorbent dose, particle size and agitation speed.
 The constants ( K1& qe ) can be calculated from the intercept and the slope of linear plot
of the above diagrams of ln (qe-qt ) versus time.

Fig.4.5.1.1 Pseudo-first order kinetics for adsorption of Cr(VI) on Jatropha oil cake at 30 C.

4.5.1.1 PSEUDO-FIRST ORDER KINETIC MODEL PARAMETERS FOR JATROPHA

OIL CAKE

Table.4.5.1.1 Pseudo-first order kinetic model parameters and correlation coefficients for
adsorption of Cr(VI) on Jatropha oil cake.

C0 (mg/l) qe, exp qe, cal K1 R2

10 0.24 0.11 0.016 0.8455
20 0.48 0.20 0.0257 0.9912
30 0.72 0.24 0.0292 0.9011
40 0.97 0.28 0.0244 0.8961
50 1.18 0.31 0.025 0.8792

4.5.2 PSEUDO-SECOND-ORDER

The pseudo-second-order kinetic model can be defined as:

t 1 1 1 1
= 2
+ t= + t
q k 2 qe qe h q e ……………………………………(4.5)

Where,

h = k 2 q e2 is known as initial sorption rate where ‘k’ is rate constant.The plot of

t/qt vs. ‘t’ at different adsorption parameters will give a linear relationship, which allows
for computation of ‘qe’ and ‘K2’.

The constants ( K2& qe ) can be calculated from the intercept and the slope of linear plot
of the above diagrams of t/qt versus time.

Fig.4.5.2.1 Pseudo-second-order kinetics for adsorption of Cr(VI) on Jatropha oil cake at 30 C.

4.5.2.1 PSEUDO-SECOND-ORDER KINETIC MODEL PARAMETERS FOR

JATROPHA OIL CAKE

Table.4.5.2.1 Pseudo-second-order kinetic model parameters and correlation coefficients for

adsorption of Cr(VI) on Jatropha oil cake.

C0 (mg/l) qe, exp qe, cal K1 R2

10 0.24 0.25 0.016 0.9993
20 0.48 0.49 0.0257 0.9999
30 0.72 0.73 0.0292 0.9993
40 0.97 0.99 0.0244 0.9999
50 1.18 1.2 0.025 0.9993
 Fig.4.5.2.2 Pseudo-
second-order
kinetics for
adsorption of
Cr(VI) on
Pongamia seed

shell at 30 C.

The slope and intercept of plot of t/qt versus time were used to determine the Pseudo-
first-order rate constant K2. In many cases, the second order equation does not fit well the whole
range of contact time except for Jatropha oil cake and is generally applicable over the initial
stage of the adsorption process.

Also the calculated ( qe,cal ) and experimental ( qexp ) values of adsorption capacity for all
substrates clearly showed ( Table 4.5.2.1,4.5.2.2 and 4.5.2.3 ) that the adsorption process of all
substrates are not followed the second order kinetic models except Jatropha oil cake. Because the
calculated ( qe,cal ) values and the experimental values of the adsorption ( qexp ) is not correlated
with each except Jatropha oil cake.

Also the Correlation coefficient R2 is suited for this kinetic model. The values varies is
supportive to the substrate adsorption. So we concluded that the overall rate of the Cr(VI)
adsorption process is being controlled by this first order adsorption mechanism but for Jatropha
oil cake Pseudo-second-order values are supportive.

4.6 SEM ANALYSIS

Scanning electron microscopy (SEM) has been a primary tool for characterizing the
surface morphology and fundamental physical properties of the adsorbent. It is useful for
determining the particle shape, porosity and appropriate size distribution of the adsorbent.
Scanning electron micrographs of Jatropha Oil cake for before adsorption and after adsorption of
chromium are shown in Fig. 2. From Fig. 2, it is clear that, Jatropha Oil cale (JOC) has
considerable numbers pf pores where, there is a good possibility for Cr(VI) to be trapped and
adsorbed into these pores.(Arami, et al., 2006).

Fig.4.6 Scanning electron microscope of JOC (a) before adsorption with Cr (VI) (b) After
adsorption with Cr (VI).

5. CONCLUSION

The results presented here shown only an approach to metal removal from large volumes
of electroplating effluents using cheap agricultural residues. These initial studies have shown that
Cr(VI) adsorption on Jatropha oil cake may represent a cheap and efficient method of adsorbing
metal containing electroplating effluent.

This may be a practical economic and cleaner technique for treating large volumes of
metal containing effluent, in contrast, most physio-chemical techniques described earlier have
several shortcomings which include excess amounts of chemical usage or sludge generation with
obvious disposal problems, costly plant requirements or operating expenses. Biological treatment
systems are unsuitable for direct use with large volumes of effluent.

After removal through adsorption as described above, the treated effluent could be
acceptable by the municipal waste water network for treatment, or may be recycled for reuse
within the electroplating plant. The metal-adsorbed substrate , on the other hand, can be
biodegraded in solid-state with the possibility of using the fermented residue as a soil
conditioner.

6. REFERENCES

1. Aggarwal, D., Goyal, M., Bansal, R. C (1999) ‘Adsorption of chromium by activated

carbon from aqueous solution’ Carbon 37, 1989–1997.

2. Aksu, Z., Tezer, S (2005) ‘Biosorption of reactive dyes on the green alga Chlorella
vulgaris’ Proc. Biochem. 40,1347–1361.
3. Aoki, T., Munemori, M (1982) ‘Recovery of chromium(VI) from wastewaters with
iron(III) hydroxide—I. Adsorption mechanism of chromium(VI) on iron(III) hydroxide’
Water Res. 16, 793–796.

4. Arami, M., Limaee, N.Y., Mahmoodi, N.M., Tabrizi, N.S (2006) ‘Equilibrium and
kinetics studies fort he adsorption of direct and acid dyes from aqueous solution by soy
meal hull’ J. Hazard. Mater. B 135, 171–179.

5. Asma Saeed, Muhammad Iqbal, Saeed Iqbal Zafar ‘Immobilization of Trichoderma

viride for enhanced methylene blue biosorption: Batch and column studies’ J. Hazard.
Mater. 168, 406-415.
6. Attia, A. A., Girgis, B. S., Fathy, N. A (2008) ‘Removal of methylene blue by carbons
derived from peach stones by H3 PO4 activation: batch and column studies’ Dyes
Pigments 76, 282–289.

7. Bailey, S. E.,Olin, T. J., Bricka, R. M., Adrian, D. D (1999) ‘A review of potentially low-
cost sorbents for heavy metals’ Water Res 33:2469–79.

8. Cardoso, S.M., Coimbra, M.A., Da Silva, J.A.L (2003) ‘Temperature dependence of the
formation and melting of pectin-Ca2+ networks: a rheological study’ Food Hydrocol. 17,
801–807.
9. Crini, G ( 2005) ‘Recent developments in polysaccharide-based materials used as
adsorbents in wastewater treatment’ Prog. Polym. Sci. 30, 38–70.
10. D. D., Meng, X (2003) ‘Utilization of fly ash for stabilization/ solidification of heavy
metal contaminated soils’ Eng. Geol. 70, 377–394.

11. Daneshvar, N., Salari, D., Aber, S (2002) ‘Chromium adsorption and Cr(VI) reduction to
trivalent chromium in aqueous solutions by soya cake’ J. Hazard. Mater. 94, 49–61.

12. Das C.P and Patnaik L.N (2001) ‘Use of industrial waste for reduction of COD from
paper mill effluent’ Indian Journal Environmental Health. 43(1), 21-27.

13. Das, D. D., Mahapatra, R., Pradhan, J., Das, S. N., Thakur, R. S (2000) ‘Removal of
Cr(VI) from aqueous solution using activated cow dung carbon’ J. Colloid Interf. Sci.
232, 235–240.

14. Davis, T. A, Volesky, B., Mucci, A (2003c) ‘A review of the biochemistry of heavy
metal biosorption by brown algae’ Water Res 37:4311–30.

15. Davis, T. A., Llanes, F., Volesky, B., Diaz-Pulido, G., McCook, L., Mucci, A (2003a)
‘1H-NMR study of Na alginates extracted from Sargassum spp. in relation to metal
biosorption’ Appl Environ Microbiol 110:75–90.

16. Davis, T. A., Llanes, F., Volesky, B., Mucci, A (2003b) ‘Metal selectivity of Sargassum
spp. and their alginates in relation to their alpha-L-guluronic acid content and
conformation’ Environ Sci Technol 37:261–7.
17. De, A.K and De, A.K (1994) ‘Heavy metals removal from waste water using fly ash and
agricultural wastes- a review’ Journal IAEM, 21, 36-39.

18. Deans, J. R., Dixon, B. G (1992) ‘Uptake of Pb2+ and Cu2+ by novel biopolymers’ Water
Res. 26, 469–472.

19. Donmez, G.C., Aksu, Z., Ozturk,A., Kutsal, T (1999) ‘A comparative study on heavy
metal biosorption characteristics of some algae’ Process Biochem. 34, 885–892.
20. Dupont, L., Guillon, E (2003) ‘Removal of hexavalent chromium with a lignocellulosic
substrate extracted from wheat bran’ Environ. Sci. Technol. 37, 4235–4241.
21. Farinella, N.V., Matos, G.D., Arruda, M.A.Z (2007) ‘Grape bagasse as a potential
biosorbent of metals in effluent treatments’ Bioresour. Technol. 98, 1940–1946.
22. Freundlich, H (1907) ‘Ueber die adsorption in loesungen’ Z. Phys. Chem. 57, 385–470.
23. Gao, R., Wang, J., (2007) ‘Effects of pH and temperature on isotherm parameters of
chlorophenols biosorption to anaerobic granular sludge’ J. Hazard. Mater. 145, 398–
403.
24. Gardea-Torresdey, J.L., Becker-Hapak, M.K., Hosea, J.M., Darnall, D.W (1990) ‘Effect
of chemical modification of algal carboxyl groups on metal ion binding’ Environ. Sci.
Technol. 24, 1372–1378.
25. Gnanasambandam, R., Protor, A (2000) ‘Determination of pectin degree of esterification
by diffuse reflectance Fourier transform infrared spectroscopy’ Food Chem. 68, 327–332.
26. Goel (1992) ‘Determination of chrome content’ Industries and pollution control. 64-89.
27. Goyal, M., Rattan, V. K., Bansal (1999) ‘Adsorption of nickel from aqeous solutions by
activated carbons’ Indian Journal of Chemical Technology, 6, 305-312.

28. Guo,Y., Qi, J., Yang, S., Yu, K., Wang, Z., Xu, X (2003) ‘Adsorption of Cr(VI) on
micro- and mesoporous rice husk-based active carbon’ Mater. Chem. Phys.78, 132–137.

29. Gupta, R., Ahuja, P., Khan, S., Saxena, R. K., Mohapatra, H (2000) ‘Microbial
biosorbents: meeting challenges of heavy metal pollution in aqueous solutions’ Curr Sci
78:967–73.

30. Gupta, V.K., Shrivastava, A.K., Jain, N (2001) ‘ Biosorption of chromium (VI) from
aqueous solutions by green algae Spirogyra species’ Water Res. 35 (17), 4079–4090.
31. Hamadi, N. K., Chen, X. D., Farid, M. M., Lu, M. G. Q (2001) ‘Adsorption kinetics for
the removal of chromium(VI) from aqueous solution by adsorbents derived from used
tyres and sawdust’ Chem. Eng. J. 84, 95–105.

32. Hameed, B. H., Din, A.T. M., Ahmad, A. L (2007) Adsorption of methylene blue onto
bamboo-based activated carbon: kinetics and equilibrium studies, J. Hazard. Mater. 141
(2007) 819–825.

33. Ho, Y.S., McKay, G (1998) ‘Sorption of dye from aqueous solution by peat’ Chem. Eng.
J. 72 (2), 115–124.

34. Howlader, M.M., Hossain Q.S., Chowdhury, A.M.S., Mustapha, A.I., Motallib M.A
(1999) ‘Activated carbon from krishnachura fruit (Delonix regia) and caste seed (Ricinus
communis L)’ Ind.J. Chem. Technol 6, 146- 151.

35. Kadirvel, K., Kavipriya, M., Karthika, C., Radhika, M., Vennilamani. W., Pattabhi, S
(2003) ‘Utilization of various agricultural wastes for activated carbon preparation and
application for the removal of dyes and metal ions from aqueous solutions’ Biores.
Techn. 87, 129-132

36. Kalavathy, M. H., Karthikeyan, T., Rajgopal, S., Miranda, L. R (2005) ‘Kinetic and
isotherm studies of Cu(II) adsorption onto H3 PO4 -activated rubber wood sawdust’ J.
Colloid Interface Sci. 292, 354–362.

37. Kalavathy, M.H., Karthikeyan, T., Rajgopal, S., Miranda, L.R (2005) ‘Kinetic and
isotherm studies of Cu(II) adsorption onto H3PO4-activated rubber wood sawdust’ J.
Colloid Interface Sci. 292, 354–362.