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Chapter - 2

Materials and methods



Adsorption method is considered to be the best and cheap

method for the removal of textile dye effluents from wastewater. This

method is superior when compared with other traditional treatment

methods due to its low-cost, easy availability, simplicity of design,

high efficiency, ease of operation and ability to treat dyes. Activated

carbon is the most efficient adsorbent used widely, but its high cost

limits its applicability.

Formaldehyde and concentrated sulphuric acid treated saw

dust and dilute acid hydrolyzed charred saw dust were successfully

used as adsorbents176 for a variety of dyes. Many chemicals (NaOH,

NH 4 OH, FeCl 3 ) and physical treatments (steam, milling) have been

used to break down the lignin complex in order to improve the

adsorption performance of many lignocellulosic materials182.

2.1 Selection of sorbents

In this study, the Athi tree, Jack fruit tree and Kattamanakku

tree leaves was procured after plucking in wet condition to about

2 kg. The plucked wet plant leaves were dried under sunlight after

measuring average longitudinal length and weight of the leaves. Six

hours sunlight exposure yield dry leaves which were shrinked to

about two per cent in longitudinal length and four percent in weight.

The dried leaves were repeatedly washed with distilled water to

remove dirt, dust and other surface impurities. The washed leaves

were dried in the sunlight for 48 h, cut into small pieces, soaked in

18 N sulphuric acid and heated separately for 24 h at 80qC in a

muffle furnace. After treatment, all the treated samples were cooled to

room temperature and washed with distilled water until the filtrate is

free from acid and attained neutral pH. The resulting activated

carbon materials were dried in a hot air oven at 105qC, powdered and

sieved through a 0.25 mm sieve.

2.2 Botanical characteristics of plant leaves

The botanical characteristics of plant leaves are presented in

Table - 2.1.

Table 2.1: Botanical properties of dry leave

Plant Botanical name content Remarks
Athi tree Ficus recemosa L. Stable and
1 (ATC) (family: 12.20 non-
Moraceae) hygroscopic

Jack fruit tree Artocarpus Stable and

2 (JTC) 11.64 non-
Urticaceae) hygroscopic

Kattamanakku (Jatropha curcus L.) Stable and

3 (KTC) (family: 10.70 non-

Euphorbiaceae) hygroscopic

2.3 Selection of dyes

In the present study, removal of different dyes viz., Direct

Yellow–12 (DY-12), Acid Red-114 (AR-114) and Direct Navy Blue-106

(DNB-106) by adsorption have been investigated on a low cost

adsorbent made from plant species. The physical and chemical

characteristics of dyes are given below.

i) Direct Yellow-12 (DY-12)

Fig. 2.1: Structure of DY-12 dye

Molecular formula : C 38 H 28 N 4 S 2 O 8 Na 2

Molecular weight : 680.66

Chemical name (IUPAC) : Benzenesulphonic, 2,2’-(1,2ethenediyl)

bis[5-[(ethoxyphenyl)azo]disodium] salt

Generic name : Direct Yellow-12

Commercial name : Direct Yellow-12

Abbreviation : DY-12

Colour index number : 24,895

Purity : 98%

Chromophore : Diazo

nj max : 420 nm

Appearance : Yellow powder

ii) Acid Red -114 dye (AR-114)

Fig. 2.2 : Structure of AR - 114 dye

Molecular formula : C 37 H 28 N 4 O 10 S 3 Na 2

Molecular weight : 830

Chemical name (IUPAC) : Disodium-8(3,3’-dimethyl-4-(4-((4-


Generic name : C.I. Acid Red -114

Commercial name : Acid Red-114

Abbreviation : AR-114

Colour index number : 23,635

Purity : 98%

Chromophore : Diazo

nj max : 540 nm

Appearance : Dark red powder

iii) Direct Navy Blue -106 dye (DNB -106)

Fig. 2.3 : Structure of DNB –106 dye

Molecular formula : C 30 H 16 N 4 Cl 2 Na 2 O 8 S 2

Molecular weight : 741.49

Chemical name (IUPAC) : Disodium 6,13-dichloro-3,10-

bisphenyl aminobenzo [5,6]-[1,4]-

Generic name : Direct Navy Blue -106

Commercial name : Direct Navy Blue-106

Abbreviation : DNB-106

Colour index number : 51,300

Purity : 99%

Chromophore : sulphonic

nj max : 600 nm

Appearance : Navy Blue powder

2.4 Preparation of solutions

A stock solution of 1000 ppm was prepared by dissolving the

appropriate amount of dyes obtained from Sigma Aldrich in 1000 ml

of distilled water. Concentrations ranged between 5 and 150 ppm

were prepared from the stock solution. All the chemicals used

throughout this study were of analytical grade reagents. Double-

distilled water was used for preparing all solutions and reagents. The

initial pH is adjusted with 0.1 M HCl or 0.1 M NaOH. All adsorption

experiments were carried out at room temperature (30 r 2qC).

2.5 Preparation of reagents

2.5.1 Hydrochloric acid solution (0.25 M)

Appropriate volume of concentrated hydrochloric acid (sp.

gravity 1.190) was mixed with water and strength of the acid was

determined using standard solution of sodium carbonate.

2.5.2 Methylene blue solution

About 0.15 g of methylene blue was dissolved in 100 ml of

water and used as it is.

2.5.3 Ammonium acetate buffer solution (pH – 4)

About 250 g of ammonium acetate was dissolved in 150 ml of

water. To this 700 ml of glacial acetic acid was added and pH was

adjusted to 4 using dilute acetic acid before diluting to 1 litre.

2.5.4 Sodium acetate solution (31.25%)

About 250 g of sodium acetate trihydrate (CH 3 COONa.3H 2 O)

was dissolved in 800 ml of water and kept as stock solution.

2.5.5 Standard potassium dichromate solution (0.025 N)

About 1.226 g of potassium dichromate was dissolved in water

and made up to one litre.

2.5.6 Sodium thiosulphate solution (0.025 N)

About 6 g of sodium thiosulphate was dissolved in water and

diluted to one litre. The strength of sodium thiosulphate was

established by iodometry.

2.5.7 Starch solution

About 1.25 g of soluble starch was boiled with 200 ml of water.

The solution was prepared fresh on the day of use.

2.5.8 Potassium iodide solution (10%)

About 10 g of potassium iodide was dissolved in 100 ml of


2.5.9 Brominating mixture

About 2.784 g of potassium bromate and 10 g of potassium

bromide were dissolved in water and diluted to one litre.

2.5.10 Sodium hydroxide solution (0.1 N)

About 4 g of sodium hydroxide was dissolved in water and

diluted to one litre. The strength was determined by using a

standard solution of hydrochloric acid.

2.5.11 Acetic acid solution (0.15 N)

About 8.8 ml of glacial acetic acid was dissolved in 500 ml of

water. Exact normality was established by standardizing against

sodium hydroxide solution of known normality.

2.5.12 Phenol solution (0.1%)

About 0.10 g of phenol crystal was dissolved in water and

diluted to 100 ml of water.

2.5.13 Sodium sulphate solution (0.25 M)

About 35.5 g of anhydrous sodium sulphate was dissolved in

water and diluted to one litre of water.

2.5.14 p-Nitrophenol solution (1000 ppm)

About 1 g of p-nitrophenol was dissolved in water and diluted to

one litre using distilled water.

2.5.15 Dye solutions

Stock solution (1000 ppm) of dye solutions (DY-12, AR-114 and

DNB-106) were prepared in deionized water and diluted to get the

desired concentrations of the dyes.

The dye solutions were transferred into a 10 mm quartz cuvette

cell and their absorbances were measured against distilled water

blank as a reference using ELICO BL 222 double beam UV-Vis Bio-

spectrophotometer. The absorption spectra of DY-12, AR-114 and

DNB-106 showed an absorption maximum at 420 nm, 540 nm and

600 nm respectively (Fig. 2.4).

Fig. 2.4 : Absorption spectra of dye solutions

2.6 Verification of Beer’s law

To find out the concentration limits within which Beer’s law is

valid, the following procedure was adopted. In a series of polythene

reagent bottles, varying concentrations of dye in the range of

10-100 ppm were prepared and their absorbances were measured

against the water blank. The graphical representation of absorbance

against concentration is made to check the validity of Beer’s law.

2.7 Instruments used

1. ELICO BL 222 double beam UV-Vis Bio-spectrophotometer

with 10 mm quartz cuvette cells

2. Elico pH meter with combined glass electrode for pH


3. Rotatory mechanical shaker for equilibrium studies

4. Tempo air oven (max 200qC).

2.8 Batch experiments

Batch experiments were conducted in stoppered reagent glass

bottles of 150 ml capacity, which were provided with glass stoppers.

The stoppered reagent glass bottles were washed well with chromic

acid before use. 100 ml of the 100 ppm of dye solution under

investigation was taken in each stoppered reagent glass bottle. After

addition of carbon, the stoppered reagent glass bottles were

equilibrated for the predetermined period of time in a rotary

mechanical shaker. At the end of the equilibrium period, the

solutions were filtered and the optical density of the filtrates was


Batch experiments were conducted to optimize conditions for

maximum adsorption of dyes through the following parameters.

1. Effect of initial concentration of dye

2. Effect of contact time

3. Effect of pH

4. Carbon dose

5. Adsorption isotherms