EVT 577

WASTEWATER TECHNOLOGYY

LABORATORY REPORT

EXPERIMENT 3: CHEMICAL OXYGEN DEMANDS (COD)

NAME INTAN NAJUWA BINTI MOHD FADIL

STUDENT ID 2017747011
CLASS AS2293C
LECTURER’S DR ALI JAWAD
NAME
DATE OF TUESDAY, 22/3/2019
EXPERIMENT
DATE OF TUESDAY, 26/3/2019
SUBMISSION
CHEMICAL OXYGEN DEMANDS (COD)

OBJECTIVE

1. To determine the Chemical Oxygen Demand (COD) in wastewater sample.

INTRODUCTION

Chemical oxygen demand (COD) is utilized as a degree of oxygen requirement of a water

sample when it is oxidised by strong chemical oxidant such as potassium dichromate,
potassium iodate, and potassium permanganate, beneath acidic conditions. However,
potassium dichromate is favored over other oxidants due to its predominant oxidising ability,
pertinence for various samples and ease of manipulation. Oxidation of most organic
compounds is 95-100% of the theoretical value.

Chemical oxygen demand is related to biochemical oxygen demand (BOD), another

standard test to test the strengths that require oxygen from wastewater. However,
biochemical oxygen demand measures only the amount of oxygen utilized by microbial
oxidation and is best suited to waters that are wealthy in organic matter. It is vital to know
that COD and BOD do not necessarily measure the same types of oxygen consumption. For
example, COD does not measure the oxygen-consuming potential related with certain
dissolved organic compounds such as acetate. However, acetate can be metabolized by
microorganisms and thus recognised in BOD test. On the other hand, the oxygen-consuming
potential of cellulose is not measured during the short-term BOD test, but it is measured
during the COD test.

METHODOLOGY

METHOD I: Dichromate (Open Reflux)

First, 50 mL of wastewater sample placed in refluxing flask. The blank is prepared by using
50 mL of deionised water, which was the precise measurement and 50 mL a volumetric
pipette is used. After that, 5 to 7 glasses boiling beads added and followed by 1 g of
mercuric sulphate (HgSO4), 5 mL of concentrated sulphuric acid-silver sulphate solution and
mixed until HgSO4 was in solution. The function of the mercuric sulphate is to bind or
complex chlorides.
Next, 25 mL of 0.25 N potassium dichromate (K 2Cr2O7) added and mixed with the solution.
Then, an additional 70 mL of concentrated sulphuric acid-silver sulphate solution added
while mixing (cooled in a beaker of ice water).

After through mixing, the flask is attached to the reflux condenser, heat applied, and the flask
refluxed for 2 hours. A reagent blank containing 50 mL of deionised water treated with the
same reagent as the sample should be refluxed with each set of samples. FAS solution
standardized while waiting 2 hours of digestion.

The FAS solution titrant has been standardized by diluting 10 mL of the standard K 2Cr2O7
solution to 10 mL with distilled water. Then, 30 mL of concentrated sulphuric acids slowly
added and cooled to room temperature. After that, the solution titrated with FAS titrant, using
2 to 3 drops of Ferroin indicator.

After doing 2 hours reflux, the apparatus cooled to room temperature. The interior of the
condensed and flask are washed down with approximately 25 mL portions of distilled water.
Then, 5 drops of Ferroin indicator and a magnetic stirring bar added. Lastly, the flasks
(samples and blank) are placed on a magnetic stirred and rapidly titrated with 0.1 N ferrous
ammonium sulphate to the first red-brown endpoint.

METHOD II: Reactor Digestion (Close Reflux)

First, the COD reactor is turned on and preheat to 150°C. Next, the caps of a COD digestion
reagent vials are removed. While holding the vial at a 45° angle, a 2.0 mL of the sample
pipetted into the vial. The vials were capped tight and the outside of the vial rinsed with
deionised water and wiped clean with tissue paper. Then, the vial inverted several times to
mix the contents, and placed in the preheat COD reactor.

A blank prepared by repeating step above, substituting 2.0 mL deionised water for the
sample. The accuracy of the reagents with each set of samples is checked, and the vials
were heated for 2 hours.

After doing 2 hours of heating, the reactor turned off, and waited about 20 minutes for the
vials to cool at 120°C or less. After that, each vial was inverted several times and placed into
a rack and cooled to room temperature. Then, the colorimetric determination to measure the
COD was proceeded.
RESULTS AND DATA

METHOD I: DICHROMATE (OPEN REFLUX)

A. STANDARDIZE SOLUTION

Figure 1 Yellowish colour of standardize solution

 Figure 2 Light green colour of standardize solution

Figure 3 Red-brown colour of standardize solution

B. SAMPLE
 Figure 4 Orange colour of sample solution

Figure 5 Dark yellowish colour of sample solution

Figure 6 Light green colour of sample solution

Figure 7 Aqua blue colour of sample solution

 Endpoint of FAS titrant (mL)

Blank 57.0

Standard 21.1

Sample 51.5

Figure 8 Red-brown colour of sample (endpoint)

Table 1.1 Endpoint of FAS titrant

 Normality of FAS (N)= (mL K2Cr2O7) (0.25)
FAS required

N = (10 mL K2Cr2O7) (0.25)

21.1 mL FAS
= 0.1185 N of FAS

DATA INTERPRETATION
COD mg/L = (a-b) (N) x 8,000
Sample size (mL)

Where a = mL Fe(NH4)2 (SO4)2 used for blank

b = mL Fe(NH4)2 (SO4)2 used for sample
N = normally of FAS titrant [Fe(NH4)2 (SO4)2]
mL sample = the actual volume of sample used before dilution

CALCULATION
COD mg/L = (57.0 – 51.5)mL (0.1185 N) (8,000)
50 mL
= 104.28 mg/L

METHOD II: REACTOR DIGESTION (CLOSE REFLUX)

 435 COD HR/HRP

Blank 0 mg/L

Standard 85 mg/L

Sample 28 mg/L

DISCUSSION
This experiment was conducted to determine the amount of chemical oxygen demand in
wastewater sample using Dichromate Open Reflux method and the Reactor Digestion
method (Close Reflux). In this experiment, we measured the sum of oxygen required to
oxidize all organic matter into carbon dioxide and water by a strong chemical oxidant,
potassium dichromate (K2Cr2O7).

The COD procedure for open reflux was more complicated compared to close reflux
because it takes so much time, which is more than 3 hours to induce the result. Meanwhile,
the COD procedure for close reflux was extremely fast and easy as it only takes a few hours,
which is less than 3 hours to induce the result. The spectrophotometer has been used in the
calorimetric determination to measure the COD.

From the result, the COD value for Open Reflux is higher, which is 104.28 mg/L, while the
COD value for Close Reflux is 28 mg/L. The higher COD value of open reflux method
happened because this method has a higher oxidizing ability which can oxidize most of the
organic compound in the wastewater sample. According to the Water Quality Standard
Malaysia, the wastewater sample considered to be slightly polluted (classified as Class II)
which tend to release unpleasant smells. The COD value of the samples showed that the
wastewater is sensitive to aquatic species. The higher the chemical oxygen demand means
the amount of pollution in the test sample are also high.

In the Open Reflux method, the COD value will be influenced if HgSO 4 is not added. The
purpose of adding HgSO4 is to keep the solution acidic as well as act as an oxidizer. If
HgSO4 is not added, chloride will be oxidised by K 2Cr2O7. Therefore, it is vital to include
HgSO4 so that chloride is bound to Hg2+ and will not experience oxidation by K2Cr2O7.

There are a few safety measures in this experiment that we need to take care of. First, the
sample should be mixed well and measured quickly to avoid settling error. Next, the water
samples should be shaken thoroughly before pipette, so that we can get homogenised
samples.

CONCLUSION
In conclusion, the chemical oxygen demand (COD) in a wastewater sample was determined
using two methods which are Dichromate Reflux Method (Open Reflux) and Reactor
Digestion Method (Close Reflux), and the COD value obtained is 104.28 mg/L and 28 mg/L
respectively. The water sample for open reflux is considered as Class II while the water
sample for close reflux is considered as Class V in Water Quality Index.

REFERENCES
A. F. Gaudy, Jr., M. N. Bhatla, and E. T. Gaudy, (1964). Use of Chemical Oxygen Demand
Values of Bacterial Cells in Waste-Water Purification. Applied Microbiology,
12(3): 254–260.

Na Yao, Jinqi Wang, and Yikai Zhou, (2014). Rapid Determination of the Chemical Oxygen
Demand of Water Using a Thermal Biosensor. Sensors (Basel), 14(6).

Dave Masulli, (2017). Guide to Chemical Oxygen Demand (COD) Testing. Retrieved from:
https://blog.hannainst.com/cod-testing