4.
Materials and Methodology
4.1. Materials
All experiments were conducted with mustard oil (Fortune) as the vegetable oil source,
procured from a local supermarket. Tween 80 (polyoxymethylene (20) sorbitan monooleate;
SRL) and cetyltrimethylammonium bromide (CTAB; SRL) served as surfactants for emulsion
preparation, while deionised (DI) water was employed in all the solutions. Commercial
activated carbon acted as the adsorbent. For Chemical Oxygen Demand (COD) analysis,
phenol (SRL), ferrous ammonium sulphate (FAS; Hyma Laboratories), potassium dichromate
(Qualigens), sulphuric acid (98%; Loba Chemie), and ferroin indicator (Rankem) were utilised.
4.2. Instruments
All weight measurements were made using an analytical balance with a 0.01 mg accuracy. An
ultrasonicator bath (Elma Schmidbauer) and an orbital shaker are used for emulsification and
Batch adsorption. The H1839800 COD Reactor (Hanna Instruments) is used for COD
digestion.
4.3. Emulsification of Vegetable Oil
100 PPM Solutions of the required volume of Vegetable Oil emulsions are prepared by
measuring, adding 100 mg/L of vegetable oil and a surfactant at 4-10 wt% of oil in Deionised
water, and then ultrasonicating for 30 min and shaking through an orbital shaker for 1 hour.
4.4. Adsorption Studies and Post-Processing
Granular commercial activated carbon (GCAC) is sieved to a mesh size of 300 – 500 microns
using a multi-sieve system and a sieve shaker. Sieved GCAC of dosage 2.5 gm/L was added to
the prepared emulsions and kept in an orbital shaker at 180 rpm and 25 °C for 13 hours. The
solutions were removed post adsorption and filtered using a tea strainer to remove the GCAC.
All the solutions therefore were further utilised for COD measurement before and after
adsorption.
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Figure 1: Adsorption of 100PPM oil/water emulsion and filtration
4.5. Chemical Oxygen Demand(COD) Measurement
Chemical Oxygen Demand (COD) is measured using the standard closed reflux titrimetric
method 5220 C [6], following the procedure as follows:
4.5.1 Preparation of Reagents
1) Potassium Dichromate (0.1 N, 0.0167 M):
Weigh 491 mg of potassium dichromate (K₂Cr₂O₇) and dissolve it in 70 mL of distilled
water in a beaker. Add 16.7 mL of concentrated sulfuric acid (98%) carefully to the
same beaker and mix thoroughly. Add distilled water to make up the total volume to
100 mL.
2) Ferrous Ammonium Sulphate (0.01 N):
Weigh 392 mg of ferrous ammonium sulphate (FAS) crystals and dissolve them in 100
mL of distilled water.
4.5.2 Sample Preparation
Pipette 2.5 mL of the sample (whose COD is to be determined) into a clean Borosil vial
and add 1.5 mL of the prepared potassium dichromate solution using a micropipette.
Now, slowly add 3.5 mL of concentrated sulfuric acid (98%) along the vial wall using
a glass pipette inside a fume hood. Prepare at least 2–3 vials for each set: one before
adsorption, one after adsorption, and a blank (distilled water or distilled water with
surfactant). Seal the vials tightly and invert them several times to ensure careful and
thorough mixing and formation of a homogeneous solution.
4.5.3 Digestion:
Place the sealed vials in a COD digester preheated to 150°C for 2 hours to facilitate
complete oxidation of organic matter. The oxidation of the sample occurs according to
the below given equation:
Sample + K2Cr2O7+H2SO4→CO2+H2O+Cr2(SO4)3+K2SO4 - (1)
After digestion, allow the vials to cool to 60°C, then place them in a test tube stand to
cool to room temperature.
4.5.3 Titration and COD Determination:
Transfer each cooled solution into a conical flask and add 1–2 drops of ferroin indicator,
which turns the solution bluish green due to the presence of unreacted dichromate. Now,
titrate against the freshly prepared FAS solution until the colour changes distinctly from
blue-green to reddish-brown, indicating the endpoint. This colour change indicates the
oxidation of ferrous ions to ferric ions as per the equation below:
6Fe2+ + K2Cr2O7 +14H+→6Fe3++2Cr3++7H2O+2K+ - (2)
Record the burette readings for all samples (before adsorption, after adsorption, and
blank) and calculate the COD value using equation (1).
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𝑚𝑔 𝑛(𝐴 − 𝐵) ∗ 𝑁 ∗ 8000
𝐶𝑂𝐷 ( )= − (1)
𝐿 𝑉
Where, A = Volume of 0.01 N FAS Consumed for Blank (ml)
B = Volume of 0.01 N FAS Consumed for Sample (ml)
V = Volume of sample (mL)
8000 = Milli equivalent weight of oxygen x 1000 mL/L
Note that this method is applicable only for COD values in the range of 40–400 mg/L; for
higher concentrations, dilute the sample appropriately.
Figure 2: Standard titration methodology for COD determination of Oil samples
4.6. Gravimetric Analysis:
The weight of the adsorbent is measured both before and after adsorption (following filtration).
The difference between these two values represents the amount of oil adsorbed, calculated
using the following expression:
Weight of oil adsorbed (mg) = Weight of adsorbent after adsorption − Initial weight of adsorbent – (2)
4.7. Calculation of Adsorption Efficiency:
The adsorption efficiency of the adsorbent is evaluated based on its adsorption capacity and
percentage removal, calculated using the following equations. These parameters are reported
to facilitate comparison of adsorption performance under different conditions.
Initial Oil concentration (ppm)−Final oil concentration (ppm)
Percentage Removal of oil = – (3)
Initial Oil concentration (ppm)
Amount of oil adsorbed (mg)
Adsorption capacity (q) = – (4)
Amount of adsorbent used(gm)
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