Chapter 4

Potential of Anionic Surfactant Modified Alumina in

Removal of Crystal Violet from Aqueous Solution

4.1 Introduction

4.1.1 Crystal Violet

Crystal violet or Gentian violet is triarylmethane dye. The dye is used as a histological stain
and in Gram’s Method of classifying bacteria. Crystal violet has antibacterial, antifungal,
and anthelmintic properties and was formerly important as a topical antiseptic. The medical
use of the dye has been largely superseded by more modern drugs, although it is still listed by
the World Health Organization [1].

The name "gentian violet" was originally used for a mixture of methyl pararosaniline dyes
(methyl violet) but is now often considered a synonym for crystal violet. The name refers to
its colour, being like that of the petals of a gentian flower; it is not made from gentians or
from violets. Table 4.1 shows the general detail of Crystal Violet.

Table 4.1: General Detail of Crystal Violet

IUPAC Name
Tris (4-(dimethylamino) phenyl) methylium chloride

Other Names
 Aniline violet  Basic violet 3  Baszol Violet 57L
 Brilliant Violet 58  Hexamethyl-p-rosaniline  Methylrosanilide chloride
chloride
 Methyl Violet 10B  Methyl Violet 10BNS  Pyoktanin
Properties
 Molecular Formula: C25N3H30Cl & Molar Mass: 407.979 g/mol
 Melting Point: 205 °C, 478 K, 401 °F & Stability: Stable
 Solubility : Soluble in cold & hot water, insoluble in diethyl ether

[187]
 (A) (B)

(C)

Figure 4.1: Solid Phase (A), Aqueous Solution (B) & Chemical Structure (C) of Crystal Violet Dye

4.1.2 Production of Crystal Violet:

A number of possible routes can be used to prepare crystal violet [2, 3]. The original procedure
developed by Kern and Caro involved the reaction of dimethylaniline with phosgene to give
4,4'-bis(dimethylamino)benzophenone (Michler's ketone) as an intermediate [4]. This was then
reacted with additional dimethylaniline in the presence of phosphorus
oxychloride and hydrochloric acid [5].

The dye can also be prepared by the condensation of formaldehyde and dimethylaniline to
give a leuco dye [2, 3, 6].

CH2O + 3 C6H5N(CH3)2 → CH(C6H4N(CH3)2)3 + H2O

[188]
Second, this colourless compound is oxidized to the coloured cationic form: (A typical
oxidizing agent is manganese dioxide).

CH(C6H4N(CH3)2)3 + HCl + 1/2 O2 → [C(C6H4N(CH3)2)3]Cl + H2O

4.1.3 Synthesis of Crystal Violet:

Crystal violet is one of the components of methyl violet, a dye that was first synthesized by
[7]
Charles Lauth in 1861 . From 1866, methyl violet was manufactured by the Saint-
Denisbased firm of Poirrier et Chappat and marketed under the name "Violet de Paris". It was
a mixture of the tetra-, penta- and hexamethylated pararosanilines [8].

Crystal violet itself was first synthesized in 1883 by Alfred Kern (1850–1893) working in
[5]
Basel at the firm of Bindschedler and Busch . To optimize the difficult synthesis which
used the toxic gas phosgene (carbonyl chloride), Kern entered into a collaboration with the
German chemist Heinrich Caro at BASF [4].

4.1.4 Dye Colour:

When dissolved in water the dye has a blue-violet colour with an absorbance maximum at
590 nm and an extinction coefficient of 87,000 M−1cm−1 [7]. The colour of the dye depends on
the acidity of the solution. At a pH of 1.0 the dye is green with absorption maxima at 420 nm
and 620 nm while in a strongly acidic solution, the dye is yellow with an absorption
maximum at 420 nm.

The different colours are a result of the different charged states of the dye molecule. In the
yellow form all three nitrogen atoms carry a positive charge, of which two are protonated,
while the green colour corresponds to a form of the dye with two of the nitrogen atoms
positively charged. At neutral pH both extra protons are lost to the solution leaving only one
of the nitrogen atoms positive charged. The pKa’s for the loss of the two protons are
approximately 1.15 and 1.8 [7].

In alkaline solutions, nucleophilic hydroxyl ions attack the electrophilic central carbon to
produce the colourless triphenylmethanol or carbinol form of the dye. Some
triphenylmethanol is also formed under very acid condition when the positive charges on the
nitrogen atoms lead to an enhancement of the electrophilic character of the central carbon

[189]
which allows the nucleophilic attack by water molecules. This effect produces a slight fading
of the yellow colour.

4.1.5 Toxicological Information:

 Hazardous in case of ingestion or inhalation. Slightly hazardous in case of skin

contact (irritant).

 Chronic Effect on Human Health:

It may affect genetic material (mutagenic) & may cause adverse reproductive effects
and birth defects (teratogenic) based on animal test data. It may cause cancer based on
animal test data.

 Acute Potential Health Effects:

(a) Skin: May cause mild skin irritation. It can stain the area of contacted skin.
(b) Eyes: Causes moderate to severe irritation with immediate severe pain. Eye
contact causes blepharospasm, purple staining of the cornea and conjunctiva cause
permanent corneal/eye damage. Inhalation: May be harmful if inhaled. It may cause
upper respiratory tract and mucous membrane irritration. Ingestion: Harmful if
swallowed. It causes gastrointestinal tract irritation with nausea, vomiting,
hypermotility, diarrhea and abdominal pain. May affect respiration (acute pulmonary
edema), behavior (ataxia) Severe systemic poisonings have not been repeated in
humans, but animal studies have shown blood pressure rise and death from respiratory
paralysis during IV administration. Chronic Potential Health Effects: Ingestion:
Prologned or repeated ingestion may cause peritonitis and may affect metabolism
(weight loss) [8].

4.1.6 Application of Crystal Violet:

A. Non - Medical:

Crystal violet is used to dye paper and as a component of navy blue and black inks for
printing, ball-point pens and ink-jet printers. It is also used to colourize diverse products such
as fertilizers, anti-freezes, detergents, and leather jackets.

The dye is also used as a histological stain, particularly in Gram's method for classifying
bacteria.

[190]
When conducting DNA gel electrophoresis, crystal violet can be used as a non-toxic DNA
stain as an alternative to fluorescent, intercalating dyes such as ethidium bromide. Used in
this manner it may be either incorporated into the agar-rose gel or applied after the
electrophoresis process is finished. Used at a 0.001% concentration and allowed to stain a gel
after electrophoresis for 30 minutes, it can detect as little as 16ng of DNA. Through use of
a methyl orange counterstain and a more complex staining method, sensitivity can be
[6]
improved further to 8 ng of DNA . When crystal violet is used as an alternative to
fluorescent stains, it is not necessary to use ultraviolet illumination; this has made crystal
violet popular as a means of avoiding UV-induced DNA destruction when performing DNA
cloning in vitro.

B. Medical:

[9]
Gentian violet has antibacterial, antifungal, and anthelmintic properties . It is used
medically for these properties, in particular for dentistry, and is also known as "pyoctanin"
(or "pyoctanine") [10].

It is commonly used for:

 Marking the skin for surgery preparation and allergy testing

 Tinea; e.g. Athlete's foot, jock itch, and ringworm

 Candida albicans and related infections; e.g. thrush, yeast infections

 Impetigo, used primarily before the advent of antibiotics, but still useful to persons
who may be allergic to penicillin.

In forensics, gentian violet was used to develop fingerprints. Crystal violet is also used as a
tissue stain in the preparation of light microscopy sections [11].

In laboratory, solutions containing crystal violet and formalin are often used to
simultaneously fix and stain cells grown in tissue culture to preserve them and make them
easily visible, since most cells are colourless. It is also sometimes used as a cheap way to put
identification markings on laboratory mice since many strains of lab mice are albino so the
purple colour stays on their fur for several weeks.

[191]
In body piercing, gentian violet is commonly used to mark the location for placing piercings,
including surface piercings.

4.1.7 Source of Dye & Pollution Caused Due to Dye

Color is an important aspect of human world. We like to wear clothes of all kinds of colors
and hues, eat food decorated with colors, even our medicines are colorful. No wonder then,
that a lot of research has gone into the production of color. Today there are more than ten
thousand dyes available commercially and seven lakh tons of dyes are produced annually.
Dyes are colored organic compounds used to impart color onto cloth. The current process for
dyeing textiles is operative, but inefficient and harmful. The primary function of water in the
dyeing process is to rinse excess dye off from the fabrics that have been colored. All of the
current commercial dyeing methods use a significant amount of water, and pollute most of
that water during the process. Dyes can be of many different structural varieties like acidic,
basic, disperse, azo, anthraquinone based and metal complex dyes among others. The textile
[12]
industry is the largest consumer of dye stuffs . Dyeing is the process of adding colour to
the fibres, which normally requires large volumes of water not only in the dye bath, but also
during the rinsing step. Depending on the dyeing process, many chemicals like metals, salts,
surfactants, organic processing aids, sulphide and formaldehyde, may be added to improve
[13]
dye adsorption onto the fibres . During the coloration process a large percentage of the
synthetic dye does not bind and is lost to the waste stream [12].

The colour of textile wastewater is mainly due to the presence of textile dyes, pigments and
other coloured compounds. A single dyeing operation can use a number of dyes from
different chemical classes resulting in a complex wastewater. Moreover, the textile dyes have
complex structures, synthetic origin and recalcitrant nature, which makes them obligatory to
[13]
remove from industrial effluents before being disposed into hydrological systems .
Approximately 10-15% dyes are released into the environment during dyeing process making
the effluent highly colored and aesthetically unpleasant.

[192]
Figure 4.2: Colored Effluent Discharge from Industry

The effluent from textile industries thus carries a large number of dyes and other additives
[12]
which are added during the colouring process . Many of the dyes are extremely toxic also.
Among various dyes, crystal violet (CV), a well-known dye has been used for various
purposes such as a biological stain, dermatological agent, veterinary medicine, and an
additive to poultry feed to inhibit propagation of mold, intestinal parasites, fungus, etc. It is
also extensively used in textile dying and paper printing. It is a mutagen and mitotic poison
[14]
. These are difficult to remove in conventional water treatment procedures and can be
transported easily through sewers and rivers especially because they are designed to have
high water solubility. They may also undergo degradation to form products that are highly
toxic and carcinogenic. Thus dyes are a potential hazard to living organisms. It is hence
important to safeguard the environment from such contaminants. To prevent contamination of
natural waters by dyes, it is essential to first detect and quantify these chemicals in the waste
waters. Dyes, pigments and heavy metals represent common and dangerous pollutants,
originating in large quantities from dye manufacturing, textile as well as pulp and paper
industries. They are emitted into wastewaters and produce difficult to treat water
contamination, as the colour tends to persist even after the conventional removal processes
[12]
.

The residual dyes from different sources (e.g., textile industries, paper and pulp industries,
dye and dye intermediates industries, pharmaceutical industries, tannery, and bleaching
industries, etc.) are considered a wide variety of organic pollutants introduced into the natural
[193]
water resources or wastewater treatment systems. One of the main sources with severe
pollution problems worldwide is the textile industry and its dye-containing wastewaters. In
particular, the discharge of dye-containing effluents into the water environment is
undesirable, not only because of their colour, but also because many of dyes released and
their breakdown products are toxic, carcinogenic or mutagenic to life forms mainly because
of carcinogens, such as benzidine, naphthalene and other aromatic compounds. Without
adequate treatment these dyes can remain in the environment for a long period of time. In
addition to the aforementioned problems, the textile industry consumes large amounts of
potable and industrial water as processing water (90-94%) and a relatively low percentage as
cooling water (6-10%) (in comparison with the chemical industry where only 20% is used as
process water and the rest for cooling). The recycling of treated wastewater has been
recommended due to the high levels of contamination in dyeing and finishing processes (i.e.
dyes and their breakdown products, pigments, dye intermediates, auxiliary chemicals and
heavy metals, etc.). Table 4.2 provides the details of textile products responsible for water
pollution [15].

Table 4.2: Principal Textile Products Responsible for Water Pollution

g/kg of Textile
Type of Finished Textile Product
Product
Polyester Fibres 18

Fabrics from Synthetic Fibres 52

Fabrics from Cotton 18

Dyed Fabrics from Cellulose Fibres 11

Printed Fabrics from Cellulose Fibres 88

4.1.8 Fate and Behavior of Dye in the Environment

It is usually observed that the excess water from dye, now polluted with chemicals and
additives, is often dumped into lakes, rivers, reservoirs, or other water resources. The
environmental issues associated with residual dye content or residual colour in textile
effluents are always a concern for each textile operator that directly discharges commercial
textile operations. Dye concentrations in watercourses higher of 1 mg/L caused by the direct
[194]
discharges of textile effluents, treated or not, can give rise to public complain. High
concentrations of textile dyes in water bodies may stop the reoxygenation capacity of the
receiving water and cutoff sunlight & thereby upset the biological activity in aquatic life and
also the photosynthesis process of aquatic plants or algae [15].

The colour in watercourses is accepted as an aesthetic problem rather than an environmental

hazard. The public seems to accept blue, green or brown colour of rivers but the ‘non-natural’
colour as red and purple usually cause most concern. The polluting effects of dyes to the
Aqueous Solution may be also the result of toxic effects due to their long time presence in
environment i.e. half-life time of several years, accumulation in sediments but especially in
fishes or other aquatic life forms, decomposition of pollutants in carcinogenic or mutagenic
compounds but also low aerobic biodegradability. Due to their synthetic nature and structure
mainly aromatic, the most of dyes are non-biodegradable, having carcinogenic action or
causing allergies, dermatitis, skin irritation or different tissular changes. Moreover, various
azo dyes, mainly aromatic compounds, show both acute and chronic toxicity. Dyes are not
biodegradable in aerobic wastewater treatment processes and some of them may be intactly
adsorbed by the sludge at wastewater biological treatment (i.e. bio-elimination by adsorptive
removal of dyes) [15].

4.1.9 Toxicity & Carcinogenicity of Dyes

Several dyes cause damage of DNA that can lead to the genesis of malignant tumors.
Electron-donating substituents in ortho and para position can increase the carcinogenic
potential. The toxicity diminished essentially with the protonation of aminic groups (-NH2).
Some of the best known dyes and their breakdown derivatives inducing cancer in humans and
animals are benzidine and its derivatives, and also a large number of anilines. In different
toxicological studies are indicated that 98% of dyes has a lethal concentration value (LC 50)
for fishes higher than 1 mg/L, and 59% have an LC50 value higher than 100 mg/L (i.e. 31% of
100-500 mg/L and 28% higher than 500 mg/L) [15].

The measurement of BOD and COD offers a good indication of the organic pollution of
water. But these procedures alone are not sufficient to get information about the potential
harmful effects of chemicals. The toxic effects of other unknown and undetermined
substances in complex wastewaters can be estimated only through toxicity studies. Toxicity

[195]
study refers to bio-analytical techniques applied to organisms at various levels to ascertain
the harmful effects of chemicals on them [16].

In addition to being toxic, dye effluents also contain chemicals that are carcinogenic,
mutagenic or teratogenic to various organisms. This is especially serious because many
chemicals can cause damage to genetic material without being expressed immediately. Azo
and nitro compounds have been reported to be reduced in sediments of aquatic bodies giving
rise to potentially carcinogenic amines. Many dyes are made from known carcinogens like
benzidine and are also known to accumulate, thus posing a serious threat. Many dyes are also
known to get reduced to toxic substances inside living organisms [16].

4.2 Materials & Methodology

4.2.1 Determination of Crystal Violet in Water

a) Method Used to Determine Crystal Violet:

Direct spectrophotometric determination of Crystal Violet colour in the water at 590 nm.

b) Experiment to Determine Crystal Violet in Water & Wastewater by Calibration

Curve Method
 Prepare 20 mg/L stock solution of Crystal Violet by weighing 20 mg Crystal Violet

powder & dissolving the same in 1000 ml distilled water.

 Prepare standard solutions of 2 mg/L, 4 mg/L, 6 mg/L, 8 mg/L, 10 mg/L & 12 mg/L

from 20 mg/L stock solution. Directly take absorbance at 590 nm.

 Take distilled water as a blank. Note down the absorbance & plot the calibration

curve. [18]

[196]
Table 4.3: Experimental Data to Determine Crystal Violet by Calibration Curve Method

Standard Con.
(mg/L) Absorbance
Calculation:
Blank 0.000
From the calibration curve;
2 0.142
y = 0.10x * Sample Vol. (ml)
4 0.359
Where,
6 0.471
y = Absorbance
8 0.716

10 1.064 x = Concentration of
Monocrotophos in mg/L
12 1.239

Figure 4.3: Calibration Curve for Determination of Crystal Violet in Water & Wastewater

[197]
4.2.2 Preparation of Anionic Surfactant Modified Alumina (ASMA)

 20,000 mg/L SDS in 500 ml standard measuring flask was prepared.

 Volume of the solution was 500 ml.

 100 gm/L Alumina was added in the flask.

 Adjusted pH 4 with 1N HCl & 1N NaOH.

 Flasks were kept on magnetic stirrer for 24 Hrs.

 After completion of shaking period, filtered out contents of the flasks through

ordinary filter paper.

 Then the filtered solid material (100 gm/L Alumina + surfactant), remaining on the

filter paper, was gently washed first with tap water & then with distilled water.

 The washed solid material was then dried in hot air oven at 60 °C for 24 Hrs.

 This oven dried solid powder is Anionic surfactant modified alumina (ASMA).

 ASMA powder was stored in plastic bottle for its further use in the removal of organic

pollutant like Phenol, Crystal Violet Dye etc. from waste water by adsolubilization

method.

[198]
4.2.3 Factors Affecting Removal of Crystal Violet by ASMA from Aqueous
Solution
4.2.3(A) Experimental Set Up to Study Effects of pH

 200 mg/L Crystal Violet stock solution was prepared.

 100 ml quantity solution of high initial concentration i.e. 200 mg/L Crystal Violet was
taken in 250 ml beaker.
 Such 5 numbers of sets were prepared.
 Adsorbent i.e. ASMA dosage was kept 6 gm/L. As here quantity is 100 ml 0.6 gm of
ASMA was added to the previously prepared 200 mg/L Crystal Violet solution.
 pH of the 5 beakers were adjusted 2, 4, 6, 8, 10 respectively by adding the required
amount of 1N HCl and 1N NaOH.
 Beakers were kept on the magnetic stirrer for 1 Hr.
 After completion of shaking, contents in the beakers were allowed to settle down for 5
minutes.
 Supernatant was filtered through ordinary filter paper & filtrate was collected to
measure the final concentration of Crystal Violet by using above mentioned direct
spectrophotometric method.
 Readings were recorded & Graph was plotted to get equilibrium pH value.

pH 2 pH 4 pH 6 pH 8 pH 10
200mg/L CV 200ppm CV 200ppm CV 200ppm CV 200ppm CV
+ 6 gm/L ASMA + 6 gm/L ASMA + 6 gm/L ASMA + 6 gm/L ASMA + 6 gm/L ASMA
Contact Time Contact Time Contact Time Contact Time Contact Time
1 Hr 1 Hr 1 Hr 1 Hr 1 Hr

Figure 4.4: Experimental Set up to Study Effects of pH on Removal of CV by ASMA

[199]
4.2.3(B) Experimental Set up to Study Effects of Contact Time

 100 ml Crystal Violet solution of 500 mg/L high initial concentration was taken in
250 ml beaker.
 Such 3 numbers of sets were prepared.
 Dosage of the adsorbent was adjusted 6 gm/L.
 PH 8 (i.e. equilibrium pH resulted from above experiment 4.2.3(A)) was adjusted for
all the 3 beakers by adding the required amount of 1N HCl & 1N NaOH.
 Beakers were kept on the magnetic stirrer for 30 minutes, 1 Hr. & 1.5 Hr.
 Beakers were allowed to stay for 5 minutes after shaking time.
 Supernatant was filtered through ordinary filter paper & filtrate was collected to
measure the final concentration of Crystal Violet by using above mentioned direct
spectrophotometric method.
 Readings were recorded & Graph was plotted to get equilibrium contact time.

30 min. 1Hr. 1.5 Hr.

200 mg/L CV 200 mg/L CV 200 mg/L CV

+ 6 gm/L ASMA + 6 gm/L ASMA + 6 gm/L ASMA
pH 8 pH 8 pH 8

Figure 4.5: Experimental Set Up to Study Effects of Contact Time in Removal of CV by ASMA

[200]
 4.2.3(C) Experimental Set up to Study Effects of Adsorbent i.e. ASMA Dosage

 100 ml Crystal Violet solution of 200 mg/L high initial concentration was taken in
250 ml beaker.
 Adsorbent dosage was varied in the range 1gm/L, 2gm/L , 3 gm/L , 4 gm/L , 5 gm/L ,
6 gm/L , 7 gm/L , 8 gm/L & 9gm/L.
 PH 8 (i.e. equilibrium pH resulted from above experiment 4.2.3(A)) was adjusted &
kept constant for all the beakers by adding the required amount of 1N HCl & 1N
NaOH.
 Beakers were kept on the magnetic stirrer for 30 mins. (i.e. equilibrium Contact Time
resulted from above experiment 4.2.3(B))
 Beakers were allowed to stay for 5 minutes after shaking time.
 Supernatant was filtered through ordinary filter paper & filtrate was collected to
measure the final concentration of Crystal Violet by using above mentioned direct
spectrophotometric method.
 Readings were recorded & graph was plotted.

1 gm/L ASMA 2 gm/L ASMA 3 gm/L ASMA 4 gm/L ASMA 5 gm/L ASMA

200 mg/L CV + 200 mg/L CV + 200 mg/L CV + 200 mg/L CV + 200 mg/L CV +
30mins. Contact Time 30mins. Contact Time 30mins. Contact Time 30mins. Contact Time 30mins. Contact Time
pH 8 pH 8 pH 8 pH 8 pH 8

6 gm/L ASMA 7 gm/L ASMA 8 gm/L ASMA 9 gm/L ASMA

200 mg/L CV + 200 mg/L CV + 200 mg/L CV + 200 mg/L CV +

30mins. Contact Time 30mins. Contact Time 30mins. Contact Time 30mins. Contact Time
pH 8 pH 8 pH 8 pH 8

Figure 4.6: Experimental Set Up to Study Effects of Adsorbent Dosage in Removal of CV by ASMA

[201]
4.2.3(D) Experimental Set up to Study Effects of Adsorbate i.e. CV
Concentration

 100 ml Crystal Violet solution of various high initial conc. Viz. 100 mg/L, 200 mg/L,
300 mg/L & 400 mg/L were taken in 4 numbers of glass beakers.
 Dosage of the ASMA adsorbent was kept 6 gm/L (i.e. equilibrium dosage from above
experiment 4.2.3(C)).
 PH 8 (i.e. equilibrium pH from above experiment 4.2.3(A)) was kept constant by
adding the required amount of 1N HCl & 1N NaOH to all the beakers.
 Beakers were kept on the magnetic stirrer for 30 mins. (i.e. equilibrium Contact Time
from above experiment 4.2.3(B))
 Beakers were allowed to stay for 5 minutes after shaking time.
 Supernatant was filtered through ordinary filter paper & filtrate was collected to
measure the final concentration of Crystal Violet by using above mentioned direct
spectrophotometric method.
 Readings were recorded & Graph was plotted.

100 mg/L CV 200 mg/L CV 300 mg/L CV 400 mg/L CV

6 gm/L ASMA + 6 gm/L ASMA + 6 gm/L ASMA + 6 gm/L ASMA +

30mins Contact Time 30mins Contact Time 30mins Contact Time 30mins Contact Time
pH 8 pH 8 pH 8 pH 8

Figure 4.7: Experimental Setup to Study Effects of Initial Adsorbate Conc. in Removal of CV by ASMA

[202]
4.2.3(E) Effect of Temperature

 100 ml Crystal Violet solution of 200 mg/L high initial concentration (i.e. Equilibrium
adsorbate concentration resulted from above experiment 4.2.3(D)) was taken in 250
ml beaker.
 Such 3 numbers of sets were prepared to study the effect of temperature (30°C, 40°C
& 50°C) in removal of CV by ASMA.
 ASMA dosage of the adsorbent was kept 6 gm/L (i.e. Equilibrium adsorbent dosage
resulted from above experiment 4.2.3(C)).
 PH 8 (i.e. equilibrium pH resulted from above experiment 4.2.3(A)) kept constant by
adding the required amount of 1N HCl & 1N NaOH to all the beakers.
 Beakers were kept on magnetic stirrer & various range of temperature Viz. 30°C,
40°C & 50°C was adjusted.
 Beakers were kept on the magnetic stirrer for 30 min. (i.e. Equilibrium contact time
obtained from above experiment 4.2.3(B)).
 Beakers were allowed to stay for 5 minutes after shaking time.
 Supernatant was filtered through ordinary filter paper & filtrate was collected to
measure the final concentration of Crystal Violet by using above mentioned direct
spectrophotometric method.
 Readings were recorded & Graph was plotted to get equilibrium temperature.

30 ºC 40 ºC 50 ºC
200mg/L CV 200mg/L CV 200mg/L CV
6 gm/L ASMA + 6 gm/L ASMA + 6 gm/L ASMA +
30mins Contact Time 30mins Contact Time 30mins Contact Time
pH 8 pH 8 pH 8

Figure 4.8: Experimental Setup to Study Effects of Temperature in Removal of CV by ASMA

[203]
4.2.4 Chemical Kinetic Study

 200 ml Crystal Violet dye solution of 200 mg/L high initial concentration was taken
in 250 ml beaker.
 Prepare a single set of 200 ml quantity for the study.
 Dosage of the adsorbent ASMA was kept 6 gm/L (i.e equilibrium dosage resulted
from experiment 4.2.3 (C)).
 PH 8 (i.e. equilibrium pH resulted from above experiment- 4.2.3(A)) kept constant of
all the beakers by adding the required amount of 1N HCl & 1N NaOH.
 Beakers were kept on the magnetic stirrer & 10 ml supernatant was taken after every
5 minute interval for 30 minutes (i.e. equilibrium contact time resulted from
experiment 4.2.3 (B)).
 Supernatant was filtered through ordinary filter paper & filtrate was collected to
measure the final concentration of Crystal Violet by using above mentioned
spectrophotometric method.
 Readings were recorded & Graphs were plotted.
Following Kinetic Models were studied in detail.

1) Pseudo First Order Model

The pseudo-first order kinetic model based on the adsorbent for sorption analysis is of the
form:

Log (qe - qt) = log qe – (k1/2.303) t

Where,

qe (mg/gm)is the mass of Monocrotophos adsorbed at equilibrium

qt (mg/gm) the mass of Monocrotophos at any time (t) & K1 (min-1) is the equilibrium rate
constant of pseudo-first order adsorption.

The values of k1 & qe are determined from the slope & intercept of the plot of Log (q e - qt)
versus t, respectively [17].

[204]
 2) Pseudo Second Order Model

A pseudo-second order rate expression based on the sorption equilibrium capacity may be
represented as:

t / qt = 1/ k2qe2 + (1/ qe) t

Where,

k2 is the pseudo-second order rate constant (g mg-1 min-1) [17].

The value of qe is determined from the slope of the plot of t/ qt versus t.

3) Intra-particle Diffusion

In order to understand the mechanism involved in the sorption process the kinetics
experimental results were fitted to the Weber’s intra-particle diffusion (Weber and Morris,
1963) model. It is reported that if intra-particle diffusion is involved in the process then a plot
of adsorbate uptake vs. the square root of time would result in a linear relationship and the
intra-particle diffusion would be the rate limiting step if this line passes through the origin.
Thus the kinetics results were analyzed by the Intraparticle diffusion model which is
expressed as

qt = kid t1/2 + C

Where,

C is the intercept

Kid is the intra-particle diffusion rate constant.

The intra-particle diffusion rate constant was determined from the slope of linear gradients of
the plot qt versus t1/2 [17].

[205]
4.2.5 Batch Isotherm Studies

Isotherm experiments were conducted to investigate the relationship between the solid phase
concentration of an adsorbate & the solution phase concentration of the adsorbate at an
equilibrium condition. The removal percentage (R %) of CV was calculated for each run by
following equation:

R (%) = [(Ci-Ce)/Ci]*100

[15]
Where, Ci and Ce are the initial & final concentration of CV (mg/L) in the solution . The
adsorption capacity of the adsorbent for each concentration of CV at equilibrium was
calculated using following equation:

qe (mg/g) = [(Ci-Ce)/M]*V

Where, Ci & Ce were the initial & final concentration of CV (mg/L) in the test solution
respectively. V is the volume of solution (in Liter) & M is the mass of adsorbent (gm) [15].

4.2.6 Adsorption Isotherm Studies

In the present study, various adsorption isotherm models have been used to study the
adsorption capacity and equilibrium coefficients for adsorption. Four commonly used
isotherms (viz. Langmuir, BET, Freundlich and Temkin isotherm) were studied.

1. The Langmuir Adsorption Isotherm

In the years 1916-1918 Langmuir developed the adsorption theory in its modern form.
Langmuir isotherm equation is derived from simple mass kinetics, assuming chemisorption.
The derivation of the Langmuir adsorption isotherm involves four implicit assumption: a) the
adsorption is at a fixed number of definite, localized sites; b) monolayer adsorption is formed
on the surface of adsorbent; c) the surface is homogenous, that is, the affinity of each binding
site for gas molecules is the same; d) there is no lateral interaction between adsorbate
molecules. Alternatively at higher concentrations, it predicts a monolayer sorption capacity
(Janos et al., 2003). It assumes that the uptake of adsorbate occurs on a homogenous surface
by monolayer adsorption without any interaction between adsorbed ions. The commonly
expressed form is:

[206]
 Ce/qe = [1/Q0b + 1/Q0 × Ce]

Where, Ce is the equilibrium concentration of adsorbate (mg/L) and qe is the amount of

adsorbate adsorbed per gram at equilibrium (mg/g), Q0 (mg/g) and b (L/mg) are Langmuir
constants related to adsorption capacity and rate adsorption, respectively. The values of Q0
and b were calculated from the slop and intercept of the Langmuir plot of Ce versus Ce/qe [19].

The Langmuir adsorption isotherm has the simplest form and shows reasonable agreements
with a large number of experimental isotherms. Therefore, the Langmuir adsorption model is
probably the most useful one among all isotherms describing adsorption, and often serves as
a basis for more detailed developments [20].

2. Freundlich Isotherm

Boedecker proposed in 1895 an empirical adsorption equation known as Freundlich isotherm,

because Freundlich assigned great importance to it and popularized its use. It is frequently
found that data on adsorption from a liquid phase are fitted better by the Freundlich isotherm
equation, provided that the adsorption sites are not identical, and the total adsorbed amount is
the same over all types of sites. The Freundlich isotherm is expressed as:

Log 10 qe = log 10(Kf) + (1/n) log10 (Ce)

Where, qe is the amount of adsorbate adsorbed at equilibrium (mg/g), and Ce is the

equilibrium concentration of adsorbate in solution (mg/L). Kf and n are the constants
incorporating all factors affecting the adsorption process [19].

The Freundlich equation is an empirical expression that encompasses the heterogeneity of the
surface and the exponential distribution of sites and their energies. According to Freundlich
equation, the amount adsorbed increases infinitely with increasing concentration or pressure.
This equation is, therefore, unsatisfactory for high coverage. At low concentration, this
equation does not reduce to the linear isotherm. In general, a large number of the
experimental results in the field of van der Walls adsorption can be expressed by means of
the Freundlich equation in the middle concentration range [19].

[207]
3. Temkin Isotherm

Temkin isotherm model is given by following equation:

X= a + b ln C

Where, C is the equilibrium concentration of solution (mg/L), X is amount of adsorbate

adsorbed per gram weight of adsorbent (mg/g), a and b are constants related to adsorption
capacity and intensity of adsorption and related to the intercept and slope of the plots of ln C
versus X [21].

4. BET Isotherm

BET isotherm was developed by Brunauer, Emmett and Teller as an extension of Langmuir
isotherm, which assumes that first layer of molecules adhere to the surface with energy
comparable to heat of adsorption for monolayer sorption and subsequent layers have equal
energies. Equation in its linearized form expressed as:

Cf/ (Cf-Cs) q = 1/Bqmax – (B-1/Bqmax) (Cf/Cs)

Where, Cs is the saturation concentration (mg/L) of the solute, Cf is solute equilibrium

concentration. B and qmax are two constants and can be evaluated from the slope and intercept
[22]
.

[208]
4.3 Results & Discussion
4.3.1(A) Effect of pH

pH of an aqueous medium has an important role for the uptake of the adsorbate. The
chemical characteristics of both adsorbate and adsorbent vary with pH. Detail Study was
conducted to observe the effect of pH in the range of 2–10. The pH of the solutions was
maintained by adding 1N HCl or 1N NaOH. In this batch study, initial concentration of
crystal violet was fixed at 200 mg/L & the dose of adsorbent at 6 gm/L. It was observed that
with increase in pH, removal of Crystal Violet increased up to certain pH range & again
gradually decreased. At pH > 9.15 SDS molecules are desorbed from the alumina surface and
cause reduction in the Crystal Violet removal. Here in below figure 4.9, it is shown that
maximum removal of Crystal Violet was obtained from experimental data i.e. 99.8 % and
adsorption capacity (qe i.e. 33.27 mg/gm) at pH 8 [17].

Table 4.4 & figure 4.9 show the effect of pH on the removal of Crystal Violet by ASMA
from the Aqueous Solution. Results of % removal of Crystal Violet at various adsorbent
dosages have been given in table 4.5 & it is graphically presented in figure 4.10.

[209]
Table 4.4: Effect of pH on Adsorption of CV by ASMA from Aqueous Solution

High
Adsorbent Contact Final Conc. of CV (mg/L)
initial pH
Dosage Time Absorbance from Calibration Curve
conc. of Range
Gm/L (Hr.) (y=0.10x * Sample Vol.)
CV (mg/L)
2 1.157 16.3
4 0.090 1.0
200 6 1.0 6 0.080 0.8
8 0.045 0.4
10 0.074 0.7

Figure 4.9: Effect of pH on Adsorption of CV by ASMA from Aqueous Solution

[210]
Table 4.5: % Removal of CV & Adsorption Capacity of ASMA at Different pH

High initial Adsorbent Adsorption

Contact Time
conc. of CV Dosage pH Range % Removal Capacity qe
(Hr)
(mg/L) Gm/L (mg/gm)
2 91.9 30.62
4 99.5 33.17
200 6 1.0 6 99.6 33.20
8 99.8 33.27
10 99.7 33.22

Figure 4.10: Effect of pH on % Removal of CV by ASMA

[211]
4.3.1(B) Effect of Contact Time

One of the most effective factors affecting adsorption is agitation time or contact time. In the
present study 3 range of contact time was selected to determine the effect of contact time on
CV removal by ASMA which are 30 minutes, 60 minutes & 90 minutes. Among them 60
minutes was found equilibrium for adsorption of Crystal Violet on ASMA. Almost 99.9%
removal was observed at 6 gm/L ASMA dosage and 8 pH. After that % removal efficiency
was decreasing at 90 minutes. As the % removal is almost same at 30 minute & 60 minute we
can consider 30 minute as equilibrium contact time for further studies. This will save both
time & energy.

This decrease in the adsorption rate may be due to a distribution of surface sites that cause
[23]
decrease in adsorbent - adsorbate interaction with increasing surface density . It may be
explained by the fact that optimum adsorption occurs at a particular pH, dose and time.
Gradually adsorption process got slowed because initially a number of vacant surface sites
may be available for adsorption and after some time, the remaining vacant surface site may
be exhausted due to repulsive forces between the adsorbent and counter ion binding at the
surface of the adsorbate [17].

Table 4.6 & figure 4.11 show the effect of contact time on the removal of Crystal Violet by
ASMA from the Aqueous Solution. Results of % removal of Crystal Violet at various
adsorbent dosages have been given in table 4.7 & it is graphically presented in figure 4.12.

[212]
Table 4.6: Effect of Contact Time on Adsorption of CV by ASMA from Aqueous Solution

Final Conc. of CV
High initial Adsorbent Contact (mg/L)
Equilibrium
conc. of CV Dosage Time Absorbance from Calibration
pH
(mg/L) Gm/L (Min.) Curve
y=0.10x * Sample vol.

30 0.057 0.6

200 6 8 60 0.045 0.4

90 0.136 1.6

Figure 4.11: Effect of Contact Time on Adsorption of CV by ASMA from Aqueous Solution

[213]
Table 4.7: % Removal of CV & Adsorption Capacity of ASMA at Different Contact Time

High initial
Adsorbent Adsorption
conc. of CV Equilibrium Contact Time
Dosage % Removal Capacity qe
(mg/L) pH (Min.)
Gm/L (mg/gm)
30 99.7 33.23
200 6 8 60 99.8 33.27
90 99.2 33.07

Figure 4.12: Effect of Contact Time on % Removal of CV by ASMA

[214]
4.3.1(C) Effect of Adsorbent Dosages

To observe the effect of adsorbent dosage i.e. ASMA dosage various range of the adsorbent
dosage was selected which were between 1 – 9 gm/L. From the experiments it was observed
that adsorption increases with the increase of ASMA dosage. % Removal of crystal violet
increases from 97.6 % to 99.9 % as the ASMA dosage increases from 1 gm/L to 7 gm/L.
Maximum % removal i.e. 99.9% was observed at 7 gm/L ASMA dosage. pH was adjusted 8
& 30 minutes Contact Time was given. But it was also observed that almost 99.8% removal
was observed at 6 gm/L dosage of ASMA. So we can consider 6 gm/L as equilibrium dosage
& can keep that dosage in further studies to save chemical.

After completion of reaction time supernatant was collected & final conc. of crystal violet
was measured spectrophotometrically. After 7 gm/L i.e. at 8 & 9 gm/L, it was observed that
the % removal efficiency decrease slightly & remain almost constant. Higher the dose of
adsorbent in the solution, greater is the availability of exchangeable sites for metal ions and
greater is the surface area [24]. From the results, the equilibrium adsorbent ASMA dosage is 7
gm/L. Adsorption capacity qe decreases with increase in adsorption dosage due to increase in
dosage surface area will increase & per gram adsorption will decrease [24].

Table 4.8 & figure 4.13 show the effect of adsorbent dosage on the removal of Crystal Violet
by ASMA from the Aqueous Solution. Results of % removal of Crystal Violet at various
adsorbent dosages have been given in table 4.9 & it is graphically presented in figure 4.14.

[215]
Table 4.8: Effect of Adsorbent Dosage on Adsorption of CV by ASMA from Aqueous Solution

High
Final Conc. of CV
initial
Equilibrium Adsorbent (mg/L)
conc. of Equilibrium
Contact Dosage Absorbance from Calibration
CV pH
Time (Min.) Gm/L Curve
(mg/L)
y=0.10x * Sample vol.
2 0.472 4.7
3 0.334 3.3
4 0.142 1.4
5 0.077 0.8
200 30 8
6 0.045 0.4
7 0.026 0.3
8 0.039 0.4
9 0.033 0.3

Figure 4.13: Effect of Adsorbent Dosage on Removal of CV by ASMA from Aqueous Solution

[216]
Table 4.9: %Removal of CV & Adsorption Capacity of ASMA at Different Adsorbent Dosage

High initial Equilibrium Adsorbent Adsorption

Equilibrium %
conc. of CV Contact Time Dosage Capacity qe
pH Removal
(mg/L) (Min.) (Gm/L) (mg/gm)
2 97.6 97.6
3 98.3 65.6
4 99.3 49.7
5 99.6 39.8
200 30 8
6 99.8 33.3
7 99.9 28.5
8 99.8 25.0
9 99.8 22.2

Figure 4.14: Effect of Adsorbent Dosage on %Removal of CV by ASMA

[217]
4.3.1(D) Effect of Initial Adsorbate (Crystal Violet) Concentration

The effect of initial concentration of adsorbate Crystal Violet on the adsorption process was
studied. Here, adsorbent dose was kept 6 gm/L, pH 8 was adjusted and contact time was
given 30 minutes. Initial concentration of Crystal Violet was adjusted 100 mg/L, 200 mg/L,
300 mg/L & 400 mg/L. Final conc. of CV was observed 0.3 mg/L, 0.4 mg/L, 1.3 mg/L & 2.2
mg/L respectively for 100 mg/L, 200 mg/L, 300 mg/L & 400 mg/L high initial concentration.
The % removal of CV was observed 99.7%, 99.8%, 99.6% & 99.5% respectively for 100
mg/L, 200 mg/L, 300 mg/L & 400 mg/L high initial concentration. Here, in the present study
% removal efficiency was almost same or near the same for all the high initial concentartion
ranges. Therefore the adsolubilization technique used in present study can be applied to the
waste water or aqueous solution containing higher concentration of Crystal Violet dye. From
the experiment, optimum dosage is 200 mg/L with 99.8% Crystal Violet removal but here
adsorption capacity (qe) increases with increase in concentration of Crystal Violet, due to
availability of higher amount of adsorbate, while in rest of the variables experiments, Crystal
Violet dose was constant.

Table 4.10 & figure 4.15 show the effect of adsorbate concentration on the removal of
Crystal Violet by ASMA from the Aqueous Solution. Results of % removal of Crystal Violet
at various adsorbent dosages have been given in table 4.11 & it is graphically presented in
figure 4.16.

[218]
Table 4.10: Effect of Initial Adsorbate Concentration on Adsorption of Crystal Violet by ASMA from
Aqueous Solution

Equilibrium Equilibrium High initial Final Conc. of

Adsorbent Contact Equilibrium conc. of CV
pH
Absorbance
Dosage Time Crystal Violet from Calibration
(Gm/L) (Min.) (mg/L) Curve (mg/L)
100 0.030 0.3

200 0.045 0.4

6 30 8
300 0.125 1.3

400 0.217 2.2

Figure 4.15: Effect of Adsorbate Conc. on Adsorption of CV by ASMA from Aqueous Solution

[219]
Table 4.11: %Removal of CV & Adsorption Capacity of ASMA at Different Initial Adsorbate Conc.

High
Equilibrium Final Conc. of CV
Equilibrium initial Adsorption
Adsorbent Equilibrium (mg/L) %
Contact Time conc. of Capacity qe
Dosage pH from Calibration Removal
(Min.) CV (mg/gm)
(Gm/L) Curve
(mg/L)
100 0.3 99.7 16.6
200 0.4 99.8 33.3
6 30 8
300 1.3 99.6 49.8
400 2.2 99.5 66.3

Figure 4.16: Effect of Initial Adsorbate Conc. on %Removal of CV by ASMA

[220]
4.3.1(E) Effect of Temperature

To observe the effect of temperature on removal of CV from aqueous solution three different
temperature ranges was selected viz. 30 °C, 40 °C & 50 °C. For the study purpose, 3 sets
were prepared. Temperature range was adjusted by the knob of magnetic stirrer. Here
adsorbent dosage & pH were kept 6 gm/L & 8 respectively for all the sets. 30 minutes contact
time was provided. But no change in % removal efficiency was observed at different
temperature. As shown in graph 99.8 % CV removal was observed for all the temperature
range. Thus it can be concluded that temperature has no effect on the CV removal.

Table 4.12 & figure 4.17 show the effect of temperature on the removal of Crystal Violet by
ASMA from the aqueous solution. Results of % removal of Crystal Violet at various
adsorbent dosages have been given in table 4.13 & it is graphically presented in figure 4.18.

Table 4.12: Effect of Temperature on Adsorption of CV by ASMA from Aqueous Solution

Final Conc.
High Equilibrium
Adsorbent of CV
initial Contact Equilibrium Temp
Dosage Absorbance (mg/L)
conc. of Time pH (°C)
Gm/L from
CV (mg/L) (min.)
Graph
30 0.045 0.40
200 30 8 6 40 0.039 0.39
50 0.042 0.42

Figure 4.17: Effect of Temperature on Removal of CV by ASMA

[221]
Table 4.13: %Removal of CV & Adsorption Capacity of ASMA at Different Temperature

High
initial Equilibrium
Equilibrium Adsorption
conc. of Equilibrium Adsorbent Temp %
Contact Time Capacity qe
CV pH Dosage (°C) Removal
(Min.) (mg/gm)
(mg/L) (Gm/L)

30 99.8 33.3
200 30 8 6 40 99.8 33.3
50 99.8 33.3

Figure 4.18: Effect of Temperature on %Removal of CV by ASMA

[222]
4.3.2 Chemical Kinetic Study

Chemical kinetics is also known as reaction kinetics. It is the study of rates of chemical
processes. It includes investigations of how different experimental conditions can influence
the speed of a chemical reaction. In order to investigate the controlling mechanism of
adsorption process such as mass transfer & chemical reaction, a suitable kinetic model is
needed to analyze the data. In the present study, three kinetic models have been tested in
order to predict the adsorption data of ASMA as a function of time using a Pseudo-First
Order, Pseudo-Second Order Kinetic Models & Intra-Particle Diffusion Model. Table 4.14
shows experimental data of chemical kinetic study.

Table 4.14: Experimental Data of Chemical Kinetic Study

High initial
Adsorbent Time Final Conc. of CV
conc. of Equilibrium Adsorption
Dosage Interval (mg/L) from
CV (mg/L) pH Capacity qt (mg/gm)
(Gm/L) (min.) Graph
5 8.5 31.91
10 1.7 33.05
15 0.8 33.20
200 8 6
20 0.6 33.24
25 0.5 33.25
30 0.4 33.27 = qe

1) Pseudo-First Order Model

Log (qe - qt) = log qe – (k1/2.303) t

Where, qe (mg/gm)is the mass of CV adsorbed at equilibrium, qt (mg/gm) the mass of CV at

any time (t) & K1 (min-1) is the equilibrium rate constant of pseudo-first order adsorption. The
values of k1 & qe are determined from the slope & intercept of the plot of Log (qe - qt) versus
t, respectively [23]. Data required for Pseudo First Order Kinetic Model is given in table 4.15.

[223]
Table 4.15: Data Required for Pseudo First Order Kinetic Model Calculation

Time Interval Final Conc. of CV

Log (qe – qt) qt (mg/gm)
(min.) (mg/L) from Graph

5 8.5 0.1335 31.91

10 1.7 -0.6576 33.05
15 0.8 -1.1549 33.20
20 0.6 -1.6990 33.24
25 0.5 -1.6990 33.25
30 0.4 0.0 33.27 = qe

Where, qe (mg/gm) = Mass of CV Adsorbed, qt (mg/gm) = Mass of CV at particular time

qe = [(Initial Conc. of CV – Final Conc. of CV)/M) * V

Where, V is the volume of solution (in Liter) & M is the mass of adsorbent (gm) [15].

Plot of time interval Vs. Log (qe – qt) is represented in figure 4.19. Calculated values of
constant K1 & correlation coefficient r2 is given in table 4.17.

Table 4.16: Pseudo First Order Kinetic Study

Time Interval (min.) Log (qe – qt)

5 0.1335
10 -0.6576
15 -1.1549
20 -1.6990
25 -1.6990
30 0.0000

[224]
Figure 4.19: Graphical Presentation of Pseudo First Order Kinetic Study

 Calculation from Graph

K1/2.303 = Slope

Where, Slope from Graph = -0.024; i.e. K1 = -0.024 * 2.303 = -0.055272

qe (calculated) = Antilog (intercept from graph) = Antilog (-0.412) = 0.3873

Table 4.17: Pseudo-First Order Kinetic Parameters for CV adsorption on ASMA

qe (mg/gm) qe (mg/gm)
Adsorbent K1 (min-1) R2
(Exp.) (Cal.)
ASMA 33.27 0.3873 -0.055272 0.082

From the above study it was observed that the present adsolubilization process does not
follow pseudo first order kinetic model. The experimental qe is 33.27 mg/gm & qe value
calculated from graph is 0.3873 mg/gm. As given in the Table 4.17 the experimental &
calculated values of adsorption capacity i.e. qe are not at all in good agreement. From the
figure 4.19, correlation coefficient value i.e. R2 was obtained 0.082 (which is very less)
indicates very poor rate of reaction. From all the above experimental as well calculated data it
was observed that the CV removal by ASMA does not follow pseudo first order kinetic
model.

[225]
2) Pseudo-Second Order Kinetic Model

t / qt = 1/ k2qe2 + (1/ qe) t

Where, k2 is the pseudo-second order rate constant (g mg-1 min-1) [17]

. The value of qe is

determined from the slope of the plot of t/ qt versus t (figure 4.20). The calculated value of qe

(34.49 mg/gm) from the pseudo second order kinetic model & it is in good agreement with

experimental qe value (33.27 mg/gm). The obtained correlation coefficient value i.e. R2 =

0.99 indicates very good rate of reaction. This suggests that the sorption system followed the

pseudo second order kinetic model. The value of kinetic constants and qe values of CV

sorption onto ASMA are given in table 4.19.

Table 4.18: Data Required for Pseudo Second Order Kinetic Model Calculation

Time Interval (min.) qt (mg/gm) t/qt

5 31.91 i.e. 5/31.91 = 0.16

10 33.05 i.e. 10/33.05 = 0.30
15 33.20 i.e. 15/33.2 = 0.45
20 33.24 i.e. 20/33.24 = 0.60
25 33.25 i.e. 25/33.25 = 0.75
30 33.27 i.e. 30/33.27 = 0.90

Figure 4.20: Pseudo-Second Order Kinetic Model Study

[226]
 Calculation from Graph
qe (Calculated) = 1/Slope from graph = 1/0.029 = 34.49
Intercept = 0.006 = 1/K2qe2

i.e. K2 = 1/ [0.006*(34.49)2] = 1/7.1374 = 0.1401 gm/mg/minute

Table 4.19: Pseudo-Second Order Kinetic Parameters for CV Adsorption on ASMA

qe (mg/gm) qe (mg/gm) Kinetic Constant

Adsorbent -1 -1
R2
(Exp.) (Cal.) K2 (g mg min )

ASMA 33.27 34.49 0.1401 0.99

3) Intra-Particle Diffusion Model

qt = kid t1/2 + C

Where, C is the intercept & Kid is the intra-particle diffusion rate constant. The intra-particle
diffusion rate constant was determined from the slope of linear gradients of the plot qt versus
t1/2 [17] as shown in the figure 4.21. Table 4.20 shows parameters of intra-particle diffusion.

Table 4.20: Parameters of Intra-Particle Diffusion

Time Interval (min.) qt (mg/gm) √Time

5 31.91 2.2361
10 33.05 3.1623

15 33.20 3.8730

20 33.24 4.4721

25 33.25 5.0000

30 33.27 5.4772

[227]
Figure 4.21: Intra-Particle Diffusion Study

Table 4.21: Intra-Particle Diffusion Parameters from Graph

C (Graph) qe (Exp.)
Adsorbent Kid R2
(mg/gm) (mg/gm)

ASMA 0.36 31.52 32.27 0.67

According to this model, the plot of uptake, qt, versus the square root of time (t1/2) should be

linear if intra-particle diffusion is involved in the adsorption process & if this line pass
[25]
through the origin then intra-particle diffusion is the rate controlling step . When the plot
does not pass through the origin, this is indicative of some degree of boundary layer control
& this further show that intra-particle diffusion is not only rate-limiting step, but also other
kinetic models may control the rate of adsorption, all of which may be operating
simultaneously [26].

The values of rate constant of intra-particle diffusion are given in table 4.21. The values of
the intercept C provide information about the thickness of boundary later i.e. larger the
intercept, larger is the boundary layer effect. Here, intercept C is 31.52 & experimental value
of Adsorption Cpacity (qe) is 33.27 mg/g. Both of them are in good agreement. Calculated
value of adsorption capacity supports the practically obtained adsorption capacity.

[228]
4.3.3 Adsorption Isotherm Studies

1. Langmuir Isotherm

The experimental result of Langmuir isotherm for uptake of CV (Ini. Conc. 200 mg/L) on
ASMA from Aqueous Solution is shown in table 4.22 & Langmuir constant calculated from
graph is shown in table 4.23. Graphical representation of the same is shown in figure 4.22.

Table 4.22: Langmuir Isotherm Data for Uptake of CV (Ini. Conc. 200 mg/L) on ASMA from Aqueous
Solution.

Langmuir Isotherm

Adsorbent Ce qe
Dosage (gm) (Final Conc. of Adsorbate) Ce/qe
(Adsorption Capacity)
(mg/L) (mg/gm)

2 4.72 97.6 0.048

3 3.34 65.6 0.051
4 1.42 49.7 0.029
5 0.77 39.8 0.019
6 0.4 33.3 0.012
7 0.26 28.5 0.009
8 0.39 25.0 0.016
9 0.33 22.2 0.015

Figure 4.22: Langmuir Isotherm Plot for Uptake of CV on ASMA from Aqueous Solution

[229]
Calculation from Graph:

Langmuir Equation: Ce/qe = [1/Qo b + 1 / Qo × Ce]

Q0 = 1/Slope = 1/0.01 = 100 mg/gm; b = Intercept * Q0 = 0.01 * 100 = 1 (L/mg)

Table 4.23: Langmuir Constants for Uptake of CV on ASMA from Aqueous Solution

Q0 (mg/gm) b (L/mg) R2

100 1 0.91

The values of coefficient of correlation (R2) for uptake of CV on ASMA obtained is in good
agreement. The value of R2 is 0.91, which is nearer to 1, indicates favorable adsorption. It
indicates first layer of molecules adhere to the surface with energy comparable to heat of
adsorption for monolayer sorption and subsequent layers have equal energies [22, 27]. Here we
[27, 28]
can say that Langmuir isotherm applies to each layer . The higher values of Q0 i.e. 100
mg/gm & b i.e. 1 L/mg obtained for uptake of CV on ASMA for Langmuir isotherm suggest
better applicability of it. Thus uptake of CV on ASMA has good fit for Langmuir isotherm.

2. Freundlich Isotherm

Results of modeling of the isotherms of CV adsorption by ASMA according to Freundlich

isotherm model is summarized in table 4.24. Graphical presentation of the Freundlich
isotherm is represented in figure 4.23. Table 4.25 shows the Freundlich constants calculated
from graph.

[230]
Table 4.24: Freundlich Isotherm Values for Uptake of CV (Ini. Conc. 200 mg/L) on ASMA from Aqueous
Solution.

Freundlich Isotherm
Adsorbent Ce
Dosage (gm) Ce / qe Log Ce Log Ce/qe
(Final Conc. Of Adsorbate)
(mg/L)
2 4.72 0.048 0.6739 -1.3188
3 3.34 0.051 0.5237 -1.2924
4 1.42 0.029 0.1523 -1.5376
5 0.77 0.019 -0.1135 -1.7212
6 0.4 0.012 -0.3979 -1.9208
7 0.26 0.009 -0.585 -2.04576
8 0.39 0.016 -0.4089 -1.7959
9 0.33 0.015 -0.4815 -1.8239

Figure 4.23: Freundlich Isotherm Plot for Uptake of CV on ASMA from Aqueous Solution

Calculation from Graph:

Freundlich Equation: Log10 qe = log 10(Kf) + (1/n) log10 (Ce)

n = 1/Slope = 1/0.56 = 1.8 L/mg

Kf = Antilog (Intercept) = Antilog (-1.64) = 0.023

[231]
Table 4.25: Freundlich Constants for Uptake of CV (Ini. Conc. 200 mg/L) on ASMA from Aqueous
Solution.

Kf (mg/gm) n (L/gm) R2

0.023 1.8 0.95

Here the value of Kf i.e. adsorption capacity 0.023 mg/gm & adsorption intensity n (rate of
adsorption) & i.e. 1.8 L/gm is obtained from Freundlich isotherm. The value of n fulfills the
condition (0 < n < 1) of Freundlich isotherm[17, 19, 27]
. The value of n in the range 2-10
[29]
represent good, 1-2 moderately difficult and less than 1 poor adsorption characteristics .
Here the value of intensity i.e. is 1.8 which is almost 2 represents moderately difficult
adsorption characteristics. The values of coefficient of correlation (R2) for uptake of CV on
ASMA obtained is in good agreement. The value of R2 is 0.95 indicates very good
adsorption.

The data obtained from the Freundlich plot indicates that the adsorption sites are not
identical; the total adsorbed amount is the same over all types of sites. It encompasses the
heterogeneity of the surface, exponential distribution of sites and their energies. It reflects
van der walls adsorption in the middle concentration range [30].

3. Temkin Isotherm
Results of modeling of the isotherms of CV adsorption by ASMA according to Temkin
isotherm model is summarized in table 4.26. Graphical presentation of the Temkin isotherm
is represented in figure 4.24. Table 4.27 shows the Temkin constants calculated from graph.

[232]
Table 4.26: Temkin Isotherm Values for Uptake of CV (Ini. Conc. 200 mg/L) on ASMA from Aqueous
Solution.

Temkin Isotherm
Adsorbent
Dosage (gm) Ce
ln C X (mg/gm)
(Final Conc. Of Adsorbate) (mg/L)

2 4.72 1.5518 97.6

3 3.34 1.206 65.6
4 1.42 0.3507 49.7
5 0.77 -0.2614 39.8
6 0.4 -0.9163 33.3
7 0.26 -1.3471 28.5
8 0.39 -0.9416 25.0
9 0.33 -1.1087 22.2

Figure 4.24: Temkin Isotherm Plot for Uptake of CV on ASMA from Aqueous Solution

Calculation from Graph:

Temkin Equation: X = a + b ln C

b = Slope = 21.8 L/mg & a = Intercept = 49.2 mg/gm

[233]
Table 4.27: Temkin Constants for Uptake of CV on ASMA from Aqueous Solution

a (mg/gm) b (L/mg) R2

49.2 21.8 0.9

The value of correlation coefficient R2 is 0.9 indicates vary good adsorption characteristic
with Temkin isotherm. The uptake of CV on ASMA follows Temkin isotherm as the value of
b is 21.8 which is very high [21] & value of a i.e. adsorption capacity calculated from graph is nearer
to experimental average qe i.e. 45.2 mg/gm. The Temkin isotherm fits the present data because it
[31]
takes into account for the occupation of the more energetic adsorption sites at first . Value
of the Temkin isotherm fits best for the uptake of CV on ASMA in the present study.

4. BET Isotherm

Result of modeling of the isotherms of CV adsorption by ASMA according to BET isotherm

model is summarized in table 4.28. Graphical presentation of the BET isotherm is represented
in figure 4.25. Table 4.29 shows the BET constants calculated from graph.

Table 4.28: BET Isotherm Values for Uptake of CV (Ini. Conc. 200 mg/L) on ASMA from Aqueous
Solution.

BET Isotherm
Adsorbent Cf
Dosage (gm) q
(Final Conc. of Cf / Cs Cf/(Cs - Cf)*q
(mg/gm)
Adsorbate) (mg/L)
2 4.72 97.6 0.0236 2.360
3 3.34 65.6 0.0167 1.114
4 1.42 49.7 0.0071 0.355
5 0.77 39.8 0.0039 0.154
6 0.4 33.3 0.0020 0.067
7 0.26 28.5 0.0013 0.037
8 0.39 25.0 0.0020 0.049
9 0.33 22.2 0.0017 0.037

[234]
Figure 4.25: BET Isotherm Plot for Uptake of CV on ASMA from Aqueous Solution

Calculation from Graph:

BET Equation: Cf / (Cs-Cf)q = 1/Bqmax – (B – 1/ Bqmax) (Cf/Cs)

1/B*qmax = Intercept i.e. B*qmax = -5.56

i.e. qmax = -5.59 /-538.4 = 0.01 mg/gm

((B – 1)/B*qmax) = Slope = 96.65

i.e. B – 1 = 96.65 * -5.56

i.e. B = -538.4 (L/mg)

Table 4.29: BET Constants for Uptake of CV on ASMA from Aqueous Solution

qmax (mg/gm) B (L/mg) R2

0.01 -538.4 0.96

[235]
The experimental data for uptake of CV on ASMA have best fit for BET isotherms of
adsorption isotherm. The value of R2 obtained 0.96 for BET isotherm indicates the same.
Here we can say that BET isotherm as an extension of the Langmuir isotherm to account for
multilayer adsorption and Langmuir isotherm applies to each layer [28].

4.4 Regeneration Study

After removal of CV from Waste Water, ASMA can be regenerated using Acetone by
following method.

 2 gm of exhausted ASMA (i.e. ASMA after CV removal) was taken in a beaker.

 8 ml of Acetone was added to it.
 The beaker was kept on the magnetic stirrer for 1 Hr at 24°C. The mixture was stirred
well.
 Arrange the distillation assembly.
 Then after collect the mixture of Acetone & CV in a distillation flask.
 Here, boiling points of Acetone & CV are 56°C & 205°C respectively.
 Therefore, conduct distillation process at 56°C & distilled out the Acetone in a
collection beaker.
 Collect the distillate of Acetone & store it in a glass bottle.
 This Acetone can be used further in various processes.
 The remaining CV, in a distillation flask, was tested to measure the concentration of
CV desorbed from the ASMA & extracted in Acetone.
 After completion of distillation, CV as a solid matter was observed in the distillation
flask.
 The final concentration of CV was measured by using above mentioned direct
spectrophotometric method.
 From the result we found 160 mg/L concentration of extracted CV. The initial high
concentration of CV was 200 mg/L & after adsolubilization by 6 gm/L ASMA it was
0.4 mg/L.
 That means 199.6 mg/L of CV was adsolubilized on ASMA.
 During Acetone treatment almost 160 mg/L of CV desorbed from the ASMA &
extracted in the Acetone.

[236]
  From the results shown in Table 4.30 almost 80% CV can be recovered. Then both
CV as well as ASMA can be reuse for further production or treatment respectively.
But % removal efficiency of ASMA may decrease after regeneration.
 % recovery may be extended by using sophisticated instruments & more precise
experimental work.
 Then both Crystal Violet as well as ASMA can be reused for further production or
treatment respectively.

Table 4.30: Recovery of Crystal Violet

Quantity Conc. of
Initial Final Quantity Contact Conc. of CV
of CV %
Conc. Conc. of Time for Temp. Adsolubilized
Exhausted Extracted Recovery
of CV of CV Acetone Recovery (°C) on ASMA
ASMA by Acetone of CV
(mg/L) (mg/L) (ml) (Hr.) (mg/L)
(gm) (mg/L)

=Ini. Conc.
– Final
200 0.4 2 8 1 24 Conc. 160 80
i.e.
200 – 0.4
= 199.6

4.5 Removal of Mixed Dye from Actual Sample of Textile Industry by ASMA &
DTAC Modified Silica Gel:

The removal of dye from actual textile sample by using anionic surfactant SDS modified
Alumina (i.e. ASMA) & cationic surfactant Dodecyl Trimethyl Ammonium Chloride
(DTAC) Modified Silica Gel (i.e. CSMSG) was also carried out. The sample was containing
mixed dye & its color was brownish red so absorbance was taken at 460 nm. Textile sample
was separately treated with ASMA (Anionic Surfactant Modified Alumina) & CSMSG
(Cationic Surfactant Modified Silica Gel) each. pH 8, contact time 30 min., adsorbent dosage
6 gm/L were adjusted to observe the % removal with ASMA. pH 4, contact time 20 min.,
adsorbent dosage 8 gm/L were adjusted to observe the % removal with CSMSG. Maximum
60% removal was observed with CSMSG for the actual sample & 41% removal was observed
with ASMA.

[237]
The results of % removal have been mentioned in Table 4.31. From the results it was
observed that the CSMSG is an effective adsorbent to remove dyes from industrial waste
water. It may remove more than 60 % of Dyes from the aqueous solution if the sample would
be treated again with fresh adsorbent CSMSG. ASMA showed very less removal efficiency
for actual sample.

Table 4.31: %Removal of Mixed Dyes from Actual Sample

Final Conc. of
Adsorbent Contact High Initial Dye (mg/L)
Adsorbent
Dosage Time pH conc. of Dye from % Removal
Used
(Gm/L) (Min.) (mg/L) Calibration
Curve

CSMSG 8 20 4 3338 60
8168
ASMA 6 30 8 4850 41

4.6 Conclusion

In the present study batch experiments were carried out to observe their effect on CV removal
by ASMA. It was observed that the Anionic Surfactant Modified Alumina can be used as an
effective adsorbent in the waste water treatment for the removal of Crystal Violet Dye.
Various factors affecting CV removal were also studied. The variables for pH were decided
2, 4, 6, 8 & 10 to find out optimum pH for further treatment. While studying pH variables;
other parameters such as high initial concentration of Crystal Violet (200 ppm), Contact Time
(1 Hr), & Adsorbent ASMA Dosage (6 gm/L) were kept constant. The variables for contact
time were decided as 1/2 Hr, 1 Hr & 1.5 Hr to find out optimum contact time for further
treatment. While studying Contact Time variables; other parameters such as high initial
concentration of Crystal Violet (200 ppm), pH (8 – optimum pH obtained from previous
study), & Adsorbent ASMA Dosage (6 gm/L) were kept constant. The variables for
Adsorbent ASMA Dosage were decided as 2 gm/L, 3 gm/L, 4 gm/L, 5 gm/L, 6 gm/L, 7
gm/L, 8 gm/L & 9 gm/L to find out optimum adsorbent dosage for further study. While
studying Adsorbent ASMA Dosage variables; other parameters such as high initial
concentration of Crystal Violet (200 ppm), pH (8 – optimum pH obtained from previous
study) & Contact Time (1/2 Hr – optimum contact time obtained from Previous study) were

[238]
kept constant. The variables for adsorbate concentration were decided as 100 ppm, 200 ppm,
300 ppm & 400 ppm to find out optimum adsorbate concentration for further study. While
studying high intial Adsorbate Concentration variables; other parameters such as pH (8 –
optimum pH obtained from previous study) & Contact Time (1/2 Hr – optimum contact time
obtained from Previous study) & Adsorbent ASMA Dosage (6 gm/L) from previous study)
were kept constant. From the batch study pH 8, contact time 30 minutes & ASMA adsorbent
dosage 7 gm/L were found optimum experimental conditions to get maximum 99.9 %
removal of Crystal Violet from aqueous solution. From the adsorbate variable study it was
observed that different adsorbate concentration did not affect Crystal Violet removal by
ASMA from aqueous solution. It shows that the ASMA can be used to remove Crystal Violet
of any high range. From the batch study; pH 8 (99.8% removal of CV), contact time 30 min
(99.7% removal of CV) & adsorbent dosage 7 gm/L (99.9% removal of CV) was found
optimum experimental conditions for maximum % removal of Crystal Violet from aqueous
solution. From the adsorbate variable study it was observed that different adsorbate
concentration did not affect Crystal Violet removal by ASMA from aqueous solution. It
shows that the ASMA can be used to remove Crystal Violet of any high range. The variables
for temperature were decided as 30 ˚C, 40 ˚C & 50 ˚C to find out optimum temperature
range. From the study it was observed that temperature had no effect on % removal efficiency
of ASMA. It was found same i.e. 99.8% for all the temperature range. By maintaining
optimum experimental conditions maximum 99.8% removal of CV was achieved.

The removal efficiency was also checked on actual textile sample & it was found that
CSMSG removed maximum 60% of mixed dye where as ASMA removed 41% of mixed
dye. From the study it is confirmed that CSMSG & ASMA are very good adsorbents & they
can be efficiently used in industries to remove dyes from the effluent.

For the regeneration of ASMA, Acetone was used. In this study it was found that only CV
was desorbed from the ASMA & not surfactant. This is due to pH is less than Zpc of Alumina
i.e. 9.15. During recovery, 2 gm of exhausted ASMA was treated with 8 ml of Acetone for 1
Hr. at 24 °C. Almost 80% recovery of Phenol was observed during extraction.

[239]
4.7 Recommendation

The present study suggested that ASMA can be effectively useful in the treatment plant for
removal of Crystal Violet. These data can be used in designing and fabrication of an
economic treatment plant for the removal of dye from wastewaters generated from textile,
dye manufacturing industries, paint & varnish industries, etc. By implementing this
technology we can prevent the introduction of dye or coloured water into adjacent water
resources. Colored dye effluents pose a major threat to the surrounding ecosystem. Many of
the dyes are extremely toxic. Among various dyes, crystal violet (CV) is a wellknown
cationic dye and has been used as a biological stain, a dermatological agent, a veterinary
medicine, and as an additive to poultry feed to inhibit propagation of mold, intestinal
parasites, and fungus etc. It is also extensively used in textile dying and paper printing. Thus
dyes and surfactants are the two contaminants occurring in many industrial wastes, and in
many cases at a high concentration level. It is thus very important to find ways for the
removal of surfactants and dyes from the water environment when present at high
concentration.

Dyes are very dangerous constituents of waste water of many industries. As they are easily
soluble in water, they can damage public health by running to the drinking water discharge
point. Anionic surfactant modified alumina can adsolubilize basic dyes efficiently from
aqueous media without consuming much energy. Again the CV can be regenerated by using
Acetone – an organic solvent & both can be separated by distillation. Thus separated Acetone
& CV can be re-used as raw materials again in the industries.

[240]
Here in the figure 4.26 probable plant lay out for the treatment of industrial effluent by
ASMA has been given.

Agitation Tank, pH 8 shall be

Waste Water Maintained by
Where ASMA
Containing Equalization
Dosage of 6 gm/L Adding 1N HCl or
Dye Tank
can be given 1N NaOH

30 min. Retention
Time is Provided for
the Reaction

Recycle & Reuse Treated Water

Regeneration of ASMA & (supernatant) & Regenerate
recovery of CV to recycle exhausted ASMA (sludge) by
& reuse Acetone to Recycle & Reuse

Figure 4.26: Treatment Layout for the Industrial Effluent by using Anionic Surfactant Modified
Alumina.

[241]
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