Abstract: Experimental investigation were carried out using acid activated vegetable kitchen

waste as alternative removal of Technethrene Red (insoluble vat dye) from aqueous solutions.
The effect of contact time and initial dye concentration were experimentally studied in batch
mode to evaluate the adsorption capacity, kinetic and equilibrium. The data were described
with Langmuir, Freundlich and Temkin adsorption isotherm models.

The experimental

results revealed that the equilibrium data fitted well to Langmuir isotherm model with a
maximum sorption capacity of

24.82 mg/g.

The kinetic data obtained at different

concentration were analyzed using pseudo first order and pseudo second order kinetic
models. The dye uptake process obeyed the pseudo second order kinetic expression. The
rate controlling steps seem to be chemisorption. The Scatchard plot indicated the presence of
different binding sites in AVKW. The values of Langmuir constants suggested favorable
sorption of Techthrene red on AVKW. In comparison to other biosorbents, AVKW was
appeared to be a suitable low cost sorbent and might have significant potential for the
removal of color from wastewater.

Page 1 of 33

Chapter 1
Introduction
1. Introduction
Today, the increasing use of dyestuff to almost all industrial products and the release of
residual and unspent dyestuff to aquatic environment without any treatment has become a
globally concerning problem . Amongst the different industrial wastewaters with different
types of color causing substances, synthetic textile organic dye wastes occupy a prominent
position.
Discharge of such effluent imparts color to the receiving water and interferes with its
intended beneficial use. These are not only aesthetically displeasing but also inhibits sunlight
penetration , cause allergic dermatitis, skin irritation and some of them have been reported to
be carcinogenic and mutagenic for aquatic organism[1].Dyes may also be absorbed by the
crops and vegetables and come to the regular food chain of human and livestock which may
cause severe problem .
Therefore, it is obligatory for the colored effluent to be given some treatment to remove the
dye pollutions. For this to be done, many methods such as adsorption, chemical oxidation,
reverse osmosis, coagulation and

flocculation, and biological treatments have been

employed. The advantages and disadvantages of each technique have been extensively
reviewed [2]. These methods have given and are still giving place to adsorption, a
physicochemical process, since it produces a high quality treated effluent.
Among the various dye classes (Direct, Reactive, Acid, Vat, Disperse, Sulfur) vat dyes are
most widely used in the denim dyeing industries. As the number of denim industries is very
high in Bangladesh and are still increasing day by day, it is the demand of present day to find
an effective, and eco-friendly way of removing color from colored effluent containing vat
dye. This present investigation reports in detail

the adsorption of

Technethrene red

(Insoluble vat dye ) onto acid activated vegetable kitchen waste(AVKW) .Adsorption of dye
is mainly dependent on the dyes properties and structure and to an equal extent on the
surface chemistry of the adsorbent. Kinetics and equilibrium information of a substance in

Page 2 of 33

different physiochemical environment are extremely essential to evaluate its efficiency as a

sorbent and effective use in effluent treatment plant [3]. The experimental data were
correlated by two generalized adsorption isotherm models namely, the Langmuir and
Freundlich models. Kinetic experiments were also conducted to determine the rate at which
Technethrene red is adsorbed on AVKW.

2. Background Studies
Increasingly stringent legislation on the decontamination of waste water has created interest
concerning the use of activated carbon for this purpose [4]. However , activated carbons are
expensive and therefore their use imply

carrying out regeneration and reactivation

procedures[5] .Therefore it has lost its suitability, especially , for the developing countries
like Bangladesh .Hence, many studies have been undertaken to investigate use of low cost
adsorbents such as clay minerals[3-5] ,fly ash[6-9] ,peat[10,11] ,wood powder
[12,13],bark[14,15],and lignin[16] is more suitable . a large number of low cost adsorbents
have been treated for dye removal . For example, Asfour et al. have studied the adsorption of
basic dye Astrazone blue FRR 69 on hardwood (beech) sawdust [13]. Dogan and Alkan have
investigated the kinetics of methyl violet adsorption onto perlite [2].
Liversidge et al. have studied the removal of Basic blue 41 dye by linseed cake [17].
Annadurai et al. have studied the adsorption of various dyes onto cellulose based wastes
[18].Gupta et al. have studied the removal of Metomega Chrome Orange GL by fly ash [19].

3. Objectives
The objectives of the study are as follows:
To evaluate the suitability of using acid activated vegetable kitchen waste for the
removal of insoluble vat dye from dye-house effluent.
To examine the impact of contact time on the adsorptive capacity of acid activated
vegetable kitchen waste.
To investigate the impact of initial dye concentration on the adsorptive capacity of
acid activated vegetable kitchen waste.
To study the removal mechanism of acid activated vegetable kitchen waste.
To examine the applicability of known adsorption isotherms.

Page 3 of 33

 To evaluate the performance acid activated vegetable kitchen waste as adsorbents in

decoloration of colored effluent.

Page 4 of 33

Chapter 2
Literature Review
2.1.1 The Physical Basis of Color
The color of most colored materials can be attributed to the presence of substances in them
that absorb light of a specific wavelength range within the visible portion of the
electromagnetic spectrum. This absorption of light is primarily due to electronic transitions
between the different orbitals within the absorbing molecule, and the wavelengths absorbed
are determined by energy differences between the orbitals (Allen, 1971). When an object
absorbs light of a particular wavelength, it reflects all other wavelengths and thereby appears
to have a color complementary to the wavelength absorbed. For example, when an object
absorbs light in the wavelength range of 400 nm 430 nm (which is the violet portion of the
visible spectrum), it actually appears yellow to an observer, since yellow is the color
complementary to violet, in the visible spectrum.

2.1.2 Sources of Color in water

Water by itself is essentially colorless. But in several cases, surface waters are found to be
significantly colored, which might be due to the presence of either natural colorants such as
humic acid, humates, tannins, decaying plankton and aquatic plants or manmade colorants
such as dyes, which are the residuals of several manufacturing processes. Most of the
industries such as textiles, paper, plastics, leather, food and cosmetics use dyes or pigments to
color their final product. Any excess dye after application to the product finds its way into the
effluent stream, and unless properly treated, ultimately ends up in different water bodies. The
three main sources of dyes in the aquatic environment are as follows (Holme, 1984):
dye manufacturers;
dye users (e.g textile industry and paper industry ); and
Household discharges, when dyes leach from manufactured products.

While dye contribution from household discharges are negligible, dye manufacturers and dye
users generate large quantities of colored wastewaters, causing significant problems of color
in receiving waters.
Page 5 of 33

2.1.3 Methods of color removal from water

The two general categories of treatment processes for color removal are biological treatment
and physical/chemical treatment. Both processes have several viable techniques, many of
which are effective for certain specific types of wastewaters or coloring substances only.
Although biological treatment processes have been successfully employed for the effective
removal of BOD and TOC from dyeing wastewaters, their decolorizing capacity seems to be
quite poor, which might be attributable to the essentially non-biodegradable nature of most
commercial dyes. There are a whole range of physical/chemical methods which have been
effectively employed for color removal, namely adsorption, membrane

filtration,

chemical oxidation, dissolved air flotation, coagulation/precipitation and electrochemical

methods. Table 1.1 presents the effectiveness of some of these processes for the several dye
types (Kouba and Zhuang, 1994).
Table 1.Error! No text of specified style in document.-1: Effectiveness of
physical/chemical treatment techniques for various dyes (Kouba and Zhuang, 1994)
Treatment

Acid

Direct

Disperse

Reactive

Sulfur

Vat

methods
Adsorption
Coagulation
Chemical

dyes
Suitable
Suitable
Not

dyes
Suitable
Suitable
Suitable

dyes
Suitable
Suitable
Suitable

dyes
Suitable
Suitable
Suitable

dyes
Suitable
Suitable
Not

dyes
Suitable
Suitable
Suitable

oxidation
Membrane

suitable
Suitable

Suitable
Not

filtration
Electrochemical Suitable

Suitable

Suitable

Suitable

suitable
Suitable

Not

Suitable

Not

Not

suitable
suitable suitable
suitable
Adsorption of the dye molecules onto various adsorbents is an ideal option for decolorization,
evidenced by the effectiveness of adsorption for various dye types (Table 1.1 ).
Coagulation/flocculation methods are quite common and reasonably effective in color
removal

and the common coagulant employed are lime, ferrous and ferric sulfate, ferric

chloride, aluminum sulfate, polyaluminum chloride, organic polymers and polyelectrolytes.

The addition of chemicals for coagulation leads to problems of disposal of these chemicals
along with the sludge. Also, it has been observed

that residual

concentrations of

polyelectrolytes in the effluent have a detrimental effect on the nitrification process in

streams (Cooper, 1993).
Page 6 of 33

Electrochemical treatment is a slight variation of the coagulation process, and involve the use
of a sacrificial iron electrode that generates iron hydroxide. The dye molecules either get coprecipitated along with the iron oxide or get adsorbed on the iron oxide precipitate ( Kouba
and Zhuang, 1994 ).
Many of the coloring dye molecules can be destroyed by powerful oxidizing agents such as
ozone or chlorine, but the main problem besides the high capital cost, lies in the possible
toxicity of the breakdown products (Copper, 1993).
Membrane filtration
containing

is quite effective for the rapid treatment of large effluent volumes

various dye categories, with the only limitation being the high capital costs

involved.
In an actual case, the effluent from a dyeing unit might contain residuals of more than one
dye type and hence, the treatment system may require a combination of more than one of the
aforementioned techniques.

2.1.4 Adsorption
The change in concentration of a given substance at the interface as compared with the
neighboring phases is referred to as adsorption . Depending on the type of phases in contact,
we can consider this process in the following systems: liquid - gas, liquid - liquid, solid liquid, solid -gas.
The major development of adsorption process on a large, industrial scale deals mainly with
the solid gas [20-24] and solid liquid [25-26] interfaces, but in various laboratory
separation techniques all types of interfaces are applied [27-31].

2.1.5 Adsorption Techniques in Color Removal

Adsorption has evolved into one of the most effective and feasible physical processes for
decolorization of textile and dyeing wastewaters (Yea and Thomas, 1995). The three different
modes of contacting the adsorbent and wastewater are as follows:
batch contact;
fixed bed contact; and

Page 7 of 33

 Fluidized bed contact.

Batch contact systems are highly effective on a smaller scale of operation, while the fixed
bed contact systems have the advantage of a constant dye concentration in contact with the
adsorbent at all times. Though the fluidized bed systems have a high rate of mass transfer, the
operating conditions are highly critical in terms of flow rates and loading volumes and hence
call for careful control (Mckay, 1980).
The various factors that influence the rate of adsorption in any system are as follows:
dye concentration;
adsorbent particle size;
extent of agitation ( for batch systems);
temperature;
adsorbent/solution ratio;
pH of the solution;
Equilibrium capacity of the adsorbent.

2.1.6 Adsorption kinetics

In order to investigate the mechanism of adsorption and potential rate controlling steps such
as mass transfer and chemical reaction, processes are used to test experimental data. Many
models such as homogeneous surface diffusion model (also known as pore and diffusion
model) have been extensively utilized for batch reactors to describe the transport of solutes
inside adsorbent particles; however, the mathematical complexity of this model makes it
inconvenient for practical use. [14, 19, 21, 34-36].

2.1.7 Pseudo First Order Equation

The Lagergrens equation , pseudo first order equation ,is given as [36] :
dQt/dt =k1 ( Qe - Qt )
After integration by applying the boundary conditions Qt = 0 at t = 0 and Qt= Qt at t = t, the
equation becomes:
ln(Qe/(Qe-Qt) = k1t
The equation can be rearranged to obtain a linear form:
ln(Qe-Qt)=ln Qe k1t
Where (Qe) and (Qt) are the amount of dye adsorbed at equilibrium and at time (t)
respectively, and (k1) is the equilibrium rate constant of pseudo first order sorption.

Page 8 of 33

The equilibrium adsorption capacity, Qe , is required to fit the data , but in many cases Q e
remains unknown due to slow adsorption processes . For this reason it is necessary to obtain
the real equilibrium adsorption capacity, qe , by extrapolating the experimental data to t=
or by using trial and error method . Also, in many cases, the first order equation of
Lagergren does not fit well for the whole range of contact time and is generally applicable
over the initial stage of adsorption processes [32-34].

2.1.8 Pseudo SecondOrder Equation

Pseudo second-order equation based on equilibrium adsorption [19, 21, 35, 37 and 38] is
expressed as:
d Qt/dt=k2(Qe- Qt)
Integrating the above equation for the boundary conditions t = 0 to t = t and qt = 0 to Q t = Qt
the equation becomes [39]:

1/( Qe- Qt )=1/ Qt +k2t

Where k2 (g/mg min) is the rate constant of second-order adsorption. If second-order kinetics
are applicable, the plot of t/ Qt versus t should show a linear relationship. There is no need to
know any parameter beforehand and Qe and k2 can be determined from the slope and
intercept of the plot. Also, this procedure is more likely to predict the behavior over the whole
range of adsorption and is in agreement with chemical sorption being the rate-controlling step
[21, 37], which may involve valency forces through sharing or exchange of electrons between
dye anions and adsorbent.

2.1.9 Adsorption Isotherm

An adsorption isotherm is a curve relating the equilibrium concentration of a solute on the
surface of an adsorbent, qe, to the concentration of the solute in the liquid, Ce, with which it
is in contact. The adsorption isotherm is also an equation relating the amount of solute
adsorbed onto the solid and the equilibrium concentration of the solute in solution at a given
temperature.(1)
In the endeavor to explore novel adsorbents in accessing an ideal adsorption system, it is
essential to establish the most appropriate adsorption equilibrium correlation ,which is
indispensable for reliable prediction of adsorption parameters and quantitative comparison of

Page 9 of 33

adsorbent behavior for different adsorbent systems(or for varied experimental conditions) . In
the perspective, equilibrium relationships, generally known as adsorption isotherms, describe
how pollutants interact with the adsorbent materials, and thus are critical for optimization of
the adsorption mechanism pathways, expression of the surface properties and capacities of
adsorbents, and effective design of the adsorption systems. (2)

2.1.10Adsorption Isotherm Models

Over the years, a wide variety of equilibrium isotherm models (Langmuir, Freundlich,
BrunauerEmmettTeller, RedlichPeterson, DubininRadushkevich, Temkin, Toth, Koble
Corrigan, Sips, Khan, Hill, FloryHuggins and RadkePrausnitz isotherm), have been
formulated in terms of three fundamental approaches. Kinetic consideration is the first
approach to be referred. Hereby, adsorption equilibrium is defined being a state of dynamic
equilibrium, with both adsorption and desorption rates are equal . Whereas, thermodynamics,
being a base of the second approach, can provide a framework of deriving numerous forms of
adsorption isotherm models , and potential theory, as the third approach, usually conveys the
main idea in the generation of characteristic curve [41]. However, an interesting trend in the
isotherm modeling is the derivation in more than one approach, thus directing to the
difference in the physical interpretation of the model parameters.

2.1.11 Langmuir isotherm model

Langmuir adsorption isotherm, originally developed to describe gassolid-phase adsorption
onto activated carbon, has traditionally been used to quantify and contrast the performance of
different bio-sorbents [38]. In its formulation, this empirical model assumes monolayer
adsorption (the adsorbed layer is one molecule in thickness), with adsorption can only occur
at a finite (fixed) number of definite localized sites, that are identical and equivalent, with no
lateral interaction and steric hindrance between the adsorbed molecules, even on adjacent
sites . In its derivation, Langmuir isotherm refers to homogeneous adsorption, which each
molecule possess constant enthalpies and sorption activation energy (all sites possess equal
affinity for the adsorbate), with no transmigration of the adsorbate in the plane of the surface.
Graphically, it is characterized by a plateau, an equilibrium saturation point where once a
molecule occupies a site, no further adsorption can take place. Moreover, Langmuir theory
has related rapid decrease of the intermolecular attractive forces to the rise of distance. The
mathematical expression of Langmuir isotherm models are illustrated in Table 1. Hereby, a
dimensionless constant, commonly known as separation factor (RL) defined by Webber and
Page 10 of 33

Chakkravorti can be represented as: RL = 1/(1 + KLCo) ,where KL (L/mg) refers to the
Langmuir constant and Co is devoted to the adsorbate initial concentration (mg/L). In this
context, lower RL value reflects that adsorption is more favourable. In a deeper explanation,
RL value indicates the adsorption nature to be either unfavourable (RL > 1), linear (RL = 1),
favorable (0 < RL < 1) or irreversible. (RL = 0).

2.1.12Freundlich Isotherm Model

Freundlich isotherm is the earliest known relationship describing the non-ideal and reversible
adsorption, not restricted to the formation of monolayer. This empirical model can be applied
to multilayer adsorption, with non-uniform distribution of adsorption heat and affinities over
the heterogeneous surface historically, it is developed for the adsorption of animal charcoal,
demonstrating that the ratio of the adsorbate onto a given mass of adsorbent to the solute was
not a constant at different solution concentrations. In this perspective, the amount adsorbed is
the summation of adsorption on all sites (each having bond energy), with the stronger binding
sites are occupied first, until adsorption energy are exponentially decreased upon the
completion of adsorption process .At present, Freundlich isotherm is widely applied in
heterogeneous systems especially for organic compounds or highly interactive species on
activated carbon and molecular sieves. The slope ranges between 0 and 1 is a measure of
adsorption intensity or surface heterogeneity, becoming more heterogeneous as its value gets
closer to zero. It is empirical and very widely used.

K is an indicator of adsorption capacity. Higher the maximum capacity, higher the K. 1/n is a
measure of intensity of adsorption. Higher the 1/n value, more favorable is the adsorption.
Generally, n < 1,

>1 n and KF are system specific constants

Page 11 of 33

2.1.13Temkin Isotherm model

Temkin isotherm is the early model describing the adsorption of hydrogen onto platinum
electrodes within the acidic solutions. The isotherm [57] contains a factor that explicitly
taking into the account of adsorbentadsorbate interactions. By ignoring the extremely low
and large value of concentrations, the model assumes that heat of adsorption (function of
temperature) of all molecules in the layer would decrease linearly rather than logarithmic
with coverage [58]. As implied in the equation, its derivation is characterized by a uniform
distribution of binding energies (up to some maximum binding energy). Temkin equation is
excellent for predicting the gas phase equilibrium (when organization in a tightly packed
structure with identical orientation is not necessary), conversely complex adsorption systems
including the liquid-phase adsorption isotherms are usually not appropriate to be represented.

Page 12 of 33

Chapter 3
Materials & Method
1.1.1.1

Materials for adsorber

3.1.2

Vegetable waste

Normal vegetable waste from kitchen was used. Vegetable waste was collected randomly.
Then they were separated as Gourd, Radish, Garlic, and were used for our experiment.

3.1.3

Chemical

HCl (35%), supplied by AUST ***Wet processing laboratory*** was used. Treatment with
HCL assists in reducing the natural colors of the vegetable waste.

3.1.4

Material for dye solution

Techthrene / vat red 6B supplied by DYSIN-CHEM LIMITED, which is a micro dispersion

of vat dye, and distilled water was used to make dye solution.

1.1.4.1

Dye specification

3.1.5

Electrical balance machine:

Balance weight supplied by ***AUST wet processing laboratory*** was used to weight out
our necessary amount of dye and absorber.

Electric balance machine specification:

Page 13 of 33

3.1.6

Magnetic stirrer:

Magnetic stirrer supplied by ******, was used to stir the dye solution, and to
provide continuous agitation in the dye solution containing absorber.

Specification of Magnetic stirrer ***. ***

3.1.7

Spectrophotometer: *** ***

Specification of Spectrophotometer:
Specification

Description

Model
Instrument Type
Measurement Geometry

Datacolor 650 TM
Dual-Beam Spectrophotometer
Diffuse Illumination and 8 viewing
Pulsed Xenon filtered to approximate

Illumination Source
Sphere Diameter
Range
Photometric Range
Power Requirements
Absolute Operating Range

illuminant D65
152 mm / 6.0 inches
360 nm to 700 nm
0 to 200%
85 to 264V, 47 to 63 Hz
5 to 40, 5% to 85% non condensing
relative humidity
Datacolor
USA

Manufacturer
Origin

Page 14 of 33

Figure 3.Error! No text of specified style in document.-1: Spectrophotometer (Datacolor

650 TM)

1.1.7.1

Metholodogy

3.1.8

Dye preparation

At first powder dye (i.e. 0.1g or, 0.15g or, 0.2g) was weighted, and mixed with 1 liter distilled
water to make it (0.1g/L or, 0.15g/L or, 0.2g/L). The mixture of dye and water was made with
the help of magnetic stirrer. Then 250 ml solution was collected.

3.1.9

Absorber preparation

Vegetable waste was collected from the kitchen randomly. Then they were separated as
Gourd, Garlic, and Radish, washed thoroughly and dried under heavy sun light. They were
collected when they became crispy, blended them into as fine particle/powder. After the
powder was prepared, it was activated by using HCl acid (35%). [ 5g absorber and 5g HCl
were taken along with 1 liter water followed by mixing the HCl and water and then introduce
to the absorber. The solution was heated to 70*C for 20 minutes. Water was drained out].
Then the absorber was dried and collected and was ready for use.

1.1.9.1

Calibration of Color

The dye solution was initially calibrated for color concentration in terms of absorbance units.
The solution was diluted to a concentration range of 10, 20, 30, 40, 50, 60, and 100 mg/l and
Page 15 of 33

each concentration was measured for its absorbance value. The absorbance values were then
plotted against the concentrations. Figure 2.1 shows the calibration curve of the dye solution.
The value of the extinction coefficient of Technethrene red was determined from the
calibration curve and found to be 10.5.
Table: Absorbance value of Technethrene Red solution of different concentration.
Concentration (g/l)
0.01
0.02
0.03
0.04
0.05
0.06
0.1

Absorbance
0.0783
0.1872
0.2867
0.4034
0.5003
0.6214
1.0204

Figure 2.1 Calibration curve of the Technethrene Red solution

Figure 2-Error! No text of specified style in document.-2: Calibration curve of the Technethrene Red solution

Page 16 of 33

1.1.9.2

Batch sorption experiments

The effects of initial concentration and contact time were performed at room temperature
(300K). The kinetic study was carried out at three initial concentrations of Techthrene red.
For the measurement of sorption capacity, 250 ml dye solution of initial concentration (C 0) of
100 mg/L was taken and 1 g of AVKW was added to it. This mixture was agitated at room
temperature on a magnetic stirrer and the liquor was sampled at the time intervals of 0, 3, 5,
7, 10, 15, 20, 30, 45, 60, 90, and 120 minutes. After desired time the absorbance of sampled
solutions were measured in a spectrophotometer (Datacolor 600, USA). Similar procedure
was followed to determine absorbance value for other three initial concentrations (C 0) such as
150 mg/L, and 200 mg/L. The concentrations of dye solution for each time interval were
determined using the calibration curves established earlier.
The amount of Techthrene red adsorbed onto AVKW was calculated by following the Eq. 1:

Qe = ( C0 - Ce )* V / W ..(1)
where, Qe (mg/g) is sorption capacity, C0 (mg/L) and Ce (mg/L) are the initial and final
concentrations of Techthrene red, respectively; V (L) is volume of dye solution and W (g) is
the weight of sorbent.

Page 17 of 33

The percentage removal of dye (R) was calculated following the Eq. (2):
R={(

C0 - Ce ) / C0 } * 100 % (2)

1.1.9.3

Kinetic models

The sorption mechanism of Techthrene red onto AVKW was studied using pseudo first-order,
pseudo second-order kinetic and intraparticle diffusion equations. The pseudo first-order
kinetic equation given by Lagergren (Lagergren, 1898) is expressed as Eq. (3):

Log10 ( Qe Qt ) = Log10 ( Qe ) ( KL / 2.303 ) * t

.(3)
where, Qe and Qt (mg/g) are the amount of dye adsorbed at equilibrium and at time t (min.)
respectively and KL (min-1) is the equilibrium rate constant of pseudo first-order sorption.
The pseudo second-order kinetic equation (Ho and McKay, 2000) is expressed as Eq. (4):

t / Qt = ( 1 / Ks Qe2 ) + t / Qe .( 4 )
where, KS (g/mg min.) is the rate constant
The intraparticle diffusion model (Karagz et al., 2008) is expressed as Eq. (5):

Qt

= Kdif t1/2 + C ( 5 )

where, Kdif is the rate constant and C is a constant.

1.1.9.4

Isotherm models

The data were analyzed with Langmuir (Langmuir, 1918), Freundlich (Freundlich, 1906) and
Temkin
(Temkin and Pyzher, 1940) sorption isotherm equations as expressed in equation 6 8,
respectively.

Ce /

Qe

= ( 1 / Q0 * b ) + (Ce / Q0 ) ( 6 )

Log10 ( x / m ) = log10 KF + ( 1/ n) * log10 Ce ( 7 )

Page 18 of 33

Qe = BT lnAT +

BT lnCe ( 8 )

where, Ce (mg/L) is the equilibrium concentration, Q e (mg/g) is the amount of dye adsorbed
at equilibrium, Q0 and b are the Langmuir constants related to sorption capacity and energy
respectively, x (mg) is the amount of dye removed, m (g) is the weight of the sorbent used,
KF (L/g) and n (dimensionless) are Freundlich constants, AT and BT are model constants for
Temkin isotherm.
The parameters of all kinetic and isotherm models were obtained by linear regression analysis
of concerned plot, for example, the value of KL were obtained from the linear best fit plot of
Log10 ( Qe Qt ) against agitation time, t. The Origin pro 8.0 and Teraplot software package
was used to linear regression analysis for all models.

Page 19 of 33

Chapter 4
Results and Discussion
4.1

Effect of Contact Time and Initial Dye Concentration:

Effect of contact time and initial dye concentration on adsorption of Techthrene red by acid
activated vegetable kitchen waste are presented in Figure 1. The amount of dye adsorbed
increased with an increase in contact time and reached equilibrium after 60 minute for initial
dye concentration of 100 mg/l, 150 mg/l and 200 mg/l used in this study (Table 7-9 ).

Figure 3-3: Effect of agitation time on adsorption capacity of Technethrene Red by AVKW.

Page 20 of 33

Figure 2 Effect of agitation time on removal of Techthrene red by AVKW.

The equilibrium time is independent of initial dye concentration. However, in the first 20
minute, the initial rate of adsorption was greater for higher initial dye concentrations, because
the diffusion of dye molecules through the solution to the surface of adsorbents is affected by
an increase in the dye concentration. An increase in dye concentration accelerates the
diffusion of dyes from the dye solution onto adsorbents due to the increase in the driving
force of the concentration gradients (Sun and Xu, 1997; Ozacar, 2003). Hence the amount of
dye adsorbed at equilibrium increased from 13.55 mg/g to 19.075 mg/g as the initial dye
concentration was increased from 100 mg/l to 200 mg/l.
The removal percentage of Techthrene red by AVKW are presented in Figure 2. It is clear
from the figure that although the maximum adsorption capacity increase with increase in
initial dye concentration, the percentage removal of dye decrease with increase in the initial
dye concentration for the same amount of adsorbent.

Table 7 Adsorption parameters of Technethrene Red onto AVKW for 100 mg/l

Page 21 of 33

Time

Absorbance Initial

(min)

Volume

of Concentration Equilibrium

Adsorption Equilibri

concentration dye solution

Ct

Concentration Capacity

adsorptio

C0

(mg/l)

Ce

(Qt )

capacity

( mg/l )

( mg/g )

Qe

V (L)

(mg/l)
Ct = ( A / l )*

( mg/g )

1000

Qt = ( C0 Ct )* V /
W

1.05

100

0.9376

89.2

2.7

0.8129

77.4

5.65

0.7225

68.8

7.8

10

0.6507

61.9

9.525

15

0.6019

20

0.5429

51.7

12.075

30

0.5116

48.7

12.825

45

0.4965

47.2

13.2

60

0.4809

45.8

13.55

90

0.4818

45.8

13.55

120

0.5016

47.7

13.075

100

0.25

57.3

45.8

10.675

Table 8 Adsorption parameters of Technethrene Red onto AVKW for 150

mg/l

Page 22 of 33

13.55

Time

Absorbance Initial

(mi

Volume

concentration of dye

n)

Concentration Equilibrium
Ct

Adsorption Equilibrium

Concentration Capacity

adsorption

C0

solution (mg/l)

Ce

(Qt )

capacity

(mg/l)

V (L)

( mg/l )

( mg/g )

Qe

Ct = ( A / l )*

( mg/g )

1000

Qt = ( C0 Ct )* V /

1.575

150

W
0

1.4275

135.9

3.52

1.2991

123.7

6.57

1.2006

114.3

8.925

10

1.1393

108.5

10.375

15

1.0467

20

0.9907

94.3

13.92

30

0.9221

87.8

15.55

45

0.8597

81.8

17.05

60

0.8446

80.4

17.4

90

0.8512

81

17.25

120

0.8191

82.7

16.825

200

0.25

99.6

80.4

12.6

Table 9 Adsorption parameters of Technethrene Red onto AVKW for 200 mg/l
Tim

Absorban

Initial

Volum

ce

concentrati

on

dye

C0
(mg/l)

(mi
n)

Concentrati

Equilibrium Adsorpti

Equilibriu

Concentrati

on

on

Capacity

adsorptio

solutio (mg/l)

Ce

(Qt )

n capacity

( mg/l )

( mg/g )

Qe

of on
Ct

Page 23 of 33

17.4

V (L)

Ct = ( A /

( mg/g )

l )* 1000

Qt = ( C0
- Ct

2.1

200

V/W
0

1.7580

167.4

8.15

1.6206

154.3

11.42

1.5371

146.3

13.425

10

1.4552

138.5

15.375

15

1.4116

20

1.3771

131.1

17.22

30

1.3109

124.8

18.8

45

1.3096

124.7

18.825

60

1.2995

123.7

19.075

90

1.3061

124.3

18.925

120

1.3196

125.6

18.6

4.2
4.2.1

200

0.25

134.4

123.7

16.4

)*

19.075

Isotherms for the Sorption Process:

Langmuir Isotherm:

Linear fit of Langmuir equation for the adsorption of Technethrene Red onto AVKW at room
temperature is shown in Figure 2. The value of Q0, b, R2 are presented in Table 2. The
results indicated that linear form of Langmuir model shows the minimal deviation from the
fitted equation as indicated by the high value of

R2 as 0.9986. It was proposed that when the

value of R2 is greater than 0.89, the adsorption data would follow the Langmuir model [2].
Furthermore, the value of Q0 which is the measure of the maximum adsorption capacity of
AVKW for Technethrene Red was calculated as 24.82 mg/g

as shown in Table 2.

Representing the experimental data by Langmuir isotherm indicates both the homogeneous
nature of AVKW surface and the formation of monolayer coverage of Technethrene Red
dye molecule at its outer surface [23]. Other researchers reported similar observations for the
Page 24 of 33

adsorption of different dyes onto activated carbon prepared from various sources. Adsorption
of acid orange 10 dye [34], direct dyes [35] and Congo red dye [36] onto activated carbon
prepared from bagasse, sawdust and coir pith respectively.

Figure 2 Langmuir isotherm for the adsorption of Technetrene Red on AVKW.

Separation factor (RL), is a dimensionless constant [21, 23], and it is a good characteristic of
the Langmuir isotherm. RL, can be expressed in the following equation:
RL = 1/ (1+bC0)
Where C0 (mg/L) is the highest initial concentration of Technethrene Red and b (L/mg) is
Langmuir constant. The value of RL indicates the shape of the isotherm to be linear (R L = 1 ),
unfavourable

(RL > 1), favourable (0 < R L < 1 ), or irreversible (RL = 0) . Thus the RL

values between 0 and

1 indicate favourable adsorption. Plot of

R L versus

C0

of

Technethrene Red at room temperature is shown in Figure 5. The RL values were in the
range of

0.157

to

0.271, which is less than unity, indicating that the adsorption of

Technethrene Red onto AVKW is a favourable process, and the data fits Langmuir isotherm
model.

Page 25 of 33

Figure 5 plot of saperation factor versus initial concentration

4.2.2

Freundlich Isotherm:

Equilibrium adsorption data of Technethrene Red dye onto AVKW was tested with
Freundlich isotherm model. The linear plot of Freundlich isotherm at room temperature is
employed to determine intercept value of KF and the slope 1/n along with R2 (Table 2) .
Although, the value of R2 (0.9986) of Freundlich is slightly lower than the value of R 2
(0.9782) of Langmuir isotherm. Treybal has shown that the value of Freundlich constant, n
between 1 and 10 represents beneficial sorption process (Treybal, 1980). In the

present

investigation the value of n was found to be 2.8686 indicating the beneficial sorption of
Technethrene Red onto AVKW.
Figure 3 Freundlich isotherm for the adsorption of Technethrene Red on AVKW.

Page 26 of 33

4.2.3

Temkin Isotherm:

In addition, Temkin adsorption isotherm was chosen to fit with the equilibrium adsorption
data. The linear plot of the Temkin isotherm is illustrated in Figure 4. The parameters, A T and
BT of the Temkin equation have been calculated for Technethrene Red dye (Table 2). Due
to low value of both adsorption capacity, AT (0.2507 L/g) and the value of R2 (0.9883), the
data of equilibrium isotherms of Technethrene Red onto AVKW is poorly described by
Temkin model.
Figure 4 Temkin isotherm for thr adsorption of Remazol G Yellow RGB on AVKW.

Page 27 of 33

Table 2: Langmuir, Freundlich and Temkin isotherm model constants and correlation
coefficients for sorption of Technethrene Red onto AVKW.
Isotherms

Parameters

Langmuir
Q0 (mg/g)

24.82

b (L/mg)
R2

0.02689
0.9986

Freundlich
KF (mg/g(L/mg)1/n)
N
R2

3.6182
2.8686
0.9782

Temkin
BT
AT(L/g)
R2

5.613
0.2507
0.9883

In order to characterize the sorption of Techthrene red onto AVKW, Scatchard equation, Q e
/Ce = (Qm- Qe) Ksc, where Ksc and Qm are biosorption binding constant and maximum
biosorption capacity (Lin et al., 2011), respectively, has been investigated. Scatchard plot is
one of the most effective techniques for characterizing sorption process and is used to obtain
more compact information about the binding data (Akar et al., 2008). The shape of a
Scatchard plot is related to the interaction type between biosorbate and biosorbent. If a
straight line can be obtained by ploting , Q e /Ce versus , Qe, the biosorbent presents only one
type of binding sites; if Scatchard plot displays a deviation from linearity biosorbent presents
more than one type of binding sites (Lin et al., 2011). The Scatchard plot obtained in the
present investigation has been presented in Figure 10. The dash line in the figure represents
the linear regression fit line. This badly fitted Scatchard plot indicates the presence of more
than one type of binding sites on AVKW.
Figure 10 Scatchard plot for the adsorption of Techthrene red on AVKW.

Page 28 of 33

Scatchard curve
Linear fitting of Scatchard curve

Qe/Ce ( L/g )

0.28

0.21

0.14
14

16

18

20

Qe

4.3

Adsorption Kinetics:

Adsorption kinetics largely depend on the physical and chemical characteristics of the
adsorbent material and in turn influence the adsorption mechanism. In order to design an
effective adsorber having the knowledge of the rate at which the adsorption takes place by the
adsorbent, is an important factor. In order to study the adsorption of Technethrene Red onto
AVKW and to interpret the results, experimental data obtained were fitted into different
kinetic models such as the pseudo-first-order and the pseudo-second-order.
Figure 6 : Pseudo first-order (Lagergren) adsorption kinetics of Techthrene Red on AKVW.

Page 29 of 33

100 mg/l
150 mg/l
200 mg/l
Linear Fit of 100 mg/l
Linear Fit of 150 mg/l
Linear Fit of 200 mg/l

1.4
1.2

log ( Qe - Qt )

1.0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
0

10

20

30

40

50

Agitation time (minute)

Figure 7 : Pseudo second-order adsorption kinetics of Techthrene Red on AKVW.

100 mg/l
150 mg/l
200 mg/l
Linear Fit of 100 mg/l
Linear Fit of 150 mg/l
Linear Fit of 200 mg/l

10

t/Qt

20

40

60

80

100

120

Agitation time

Table 3: Pseudo first-order (Lagergren), pseudo second-order models rate constants and
calculated amount of dye adsorbed at equilibrium from experimental data
Initial
concentration

Kinetic Models
Pseudo first order

Page 30 of 33

Pseudo second order

C0

KL

Qe

(mg/L)

(1/min.)

(mg/g)

100

0.0802

11.015

150

0.0889

200

0.1863

R2

R2

KS

Qe

(g/mg

(mg/g)

0.9669

min.)
0.1616

14.0154

0.9923

18.155

0.9778

0.0087

18.24

0.9923

24.04

0.8971

0.0246

19.21

0.9987

Figures 6 7 show the fitted curves of these models. The values of rate constants, amount of
the dye adsorbed at equilibrium and correlation coefficients calculated from these curves
have been presented in Table 3. The pseudo first-order model assumes that the rate of
sorption is proportional to the number of free sorption sites (Hanafiah et al., 2012). According
to Taty-Costodes et al. (Taty-Costodes et al. 2003), in most cases, the pseudo first-order
equation did not apply well throughout the whole range of contact times and is generally
applicable to the initial 20-30 min. of the sorption process.
In the present investigation, the best fit plots for pseudo first-order model showed good
linearity (Table 3) up to 20 min. contact time (Figure 6) but the calculated amount of dye
adsorbed at equilibrium, Qe,cal showed a considerable difference with the experimental values,
Qe,exp (Figure 9). Therefore, the sorption process did not fit very well to the pseudo-first order
model. The correlation coefficient (R2) for pseudo second-order equation was found to be
0.9923, 0.9923 and 0.9987 at the initial concentrations of 100, 150 and 200 mg/L,
respectively (Table 3) and the difference between Qe,cal and Qe,exp is reasonably small (Figure
9) which indicates that sorption of Technethrene red on AVKW follows second order kinetics
mechanism. The pseudo second-order model is built based on the assumption that the rate
controlling step is a chemical sorption involving valence force by sharing or exchange of
electrons between sorbent and sorbate (Kula et al, 2008). Therefore, a satisfactory fitting of
this model suggested that chemisorption was the rate controlling step (Lin et al., 2011; Ho
and McKay, 2000).
Figure 9 Variation of Qe,cal for the adsorption of Technethrene Red on AVKW.

Page 31 of 33

Page 32 of 33

Chapter 5
Conclusion

Page 33 of 33