CMT 565

RESUBMIT REPORT
EXPERIMENT 2
CHEMICAL OXYGEN DEMAND, CLOSED
REFLUX, TITRIMETRIC METHOD (COD)
NAME INAS SYUHAIDAH BINTI CHAIRIL ANWAR
STUDENT ID 2017420012
GROUP AS245 4M3C
NAME OF PARTNERS 1. NURUL AFIQAH BINTI MAT AZMAN
2. MUHAMMAD SHUKERI BIN RAZMAN
3. NURFAZA BINTI ZAIMON
NAME OF LECTURER PUAN NORJANAH YURY
DATE OF EXPERIMENT 20 MARCH 2019
DATE OF SUBMISSION 3 MAY 2019
 EXPERIMENT 1 :

CHEMICAL OXYGEN DEMAND, CLOSED REFLUX, TITRIMETRIC

METHOD (COD)

1. OBJECTIVE

To determine and measure of oxygen requirement of the sample waste water through
chemical oxygen demand (COD) process

2. INTRODUCTION

Chemical oxygen demand (COD) is determines the amount of oxygen required

for chemical oxidation of organic matter using a strong chemical oxidant such as
potassium dichromate under reflux conditions. Performing COD testing the right way is
important in determining wastewater treatment effectiveness and can help diagnose any
problems in treatment. A COD test can be used to easily quantify the amount
of organics in water. COD is used to monitor the treatment process in day-to-day
operations. The COD test takes only a few hours to complete. The most common
application of COD is in quantifying the amount of oxidizable pollutants found in surface
water or wastewater. COD is useful in terms of water quality by providing a metric to
determine the effect an effluent will have on the receiving body. COD is measured the
organic matter by using a chemical oxidant. A strong enough oxidant is used to react with
virtually all organic material in the sample. For this experiment, potassium permanganate
filled this role. In this experiment, method that used to determine the COD is closed
reflux. This method is conducted with ampules and culture tubes with pre-measured
reagents. Measurement of sample volume and reagent volume are critical. This method is
economical in the used of metallic salt reagents and generate smaller quantity of
hazardous wastes. Volatile organic compounds (VOC) gets completely oxidized in a
closed system than the open because of longer contact time with oxidants. Next,
 titrimetric method was used. The excess dichromate is reacted with a reducing agent,
ferrous ammonium sulfate. As the ferrous ammonium sulfate (FAS) is added slowly, the
excess dichromate is converted into its trivalent form.

3. LITERATURE REVIEW

The COD test is used as one of the components of a suite of determinants that
water utilities and regulators use to charge dischargers for their part of effluents that enter
a waste water treatment works. COD is also recognised in the Urban Waste Water
Directive (91/276/EEC), in which the potassium dichromate is used as a limiting
substance, with a limiting value of 125 mg/l. The higher the chemical oxygen demand,
the higher the amount of pollution in the water sample. However, COD is considered one
of the important quality control parameter of an effluent in wastewater treatment facility
[Guoqing Wu, Weihong Bi, Jiaming Lv, and Guangwei Fu].With water pollution
becoming a serious issue, water quality assessment and pollutant control have become
global imperatives (Wang, J., Li, K., Zhang, H., Wang, Q., Wang, Y., Yang, C., Guo, Q.,
Jia, J.) COD is measured the organic matter by using a chemical oxidant. The complete
oxidation of organic compounds under such strong oxidizing conditions produces carbon
dioxide (CO2 ) and water (H2O). The COD is defined as the number of oxygen
equivalents consumed in the oxidation of organic compounds by strong oxidizing agents,
such as dichromates and permanganates, and is indicative of the amount of organic
pollutants present in the tested sample [Lee, K.H].

The formula of COD (mg/L)

𝐵𝑙𝑎𝑛𝑘 𝑇𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛−𝑆𝑎𝑚𝑝𝑙𝑒 𝑇𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛 ×𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝐹𝐴𝑆 ×8000

= 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑆𝑎𝑚𝑝𝑙𝑒 (𝑚𝐿)

8000 is milli equivalent weight of oxygen (8) ×1000 mL/L.

In this experiment, titrimetric method was used to determine the COD value.
During experiment, excess dichromate concentration is determined by titrating it with
ferrous ammonium sulfate (FAS). The reaction is given by: 6Fe2+ + Cr2O72- + 14 H+ =>
6Fe3++ 2Cr3+ +7H2O
4. MATERIALS AND APPARATUS

 Standard potassium dichromate  Potassium hydrogen phthalate

solution standard
 Sulphuric reagent  Digestion vessel
 Standard ferrous ammonium  Retort stand
sulphate (FAS) titrant  Conical flask
 Ferroin indicator solution  Burette
 Mercuric sulphate  White tile

5. METHODS

Digestion vessel and caps was washed with 20% H2SO4 before used. Then, 2.5
mL sample, 1.5 Ml K2Cr2O7 solution and 3.5 mL sulfuric acid was added into digestion
vessel. The vessels was placed in block digester pereheated to 150◦C. The digestion
vessel was reflux for 2 hours behind a protective shield. The vessels was cooled to room
temperature for after 2 hours reflux and placed it in test tube rack. The cap is removed.
Small TFE-covered magnetic stirring bar was added ot the contents was transferred to a
larger container for titrating. Two drops of ferroin indicator was added and stirred rapidly
on magnetic stirrer while titrating with standardized 0.1M FAS. The colour change from
blue-green to reddish-brown. A blank containing the reagebts and distilled water was
refluxed and titrated.
 6. RESULTS

Tiration Volume of FAS (0.1M)

Sample Volume KHP Standard Section 7 Section 17 Blank Water

Sample 1 (mL) 0.90 1.40 1.20 1.60
Sample 2 (mL) 0.90 1.50 0.90 1.80
Sample 3 (mL) 1.00 1.50 1.20 1.60

CALCULATION

Molarity of FAS Solution

𝑉𝑜𝑙𝑢𝑚𝑒 0.01667𝑀 𝐾 𝐶𝑟 𝑂 7 𝑡𝑖𝑡𝑟𝑎𝑡𝑒𝑑,𝑚𝐿

= × 0.1
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐹𝐴𝑆 𝑢𝑠𝑒𝑑 𝑖𝑛 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛,𝑚𝐿

5
= 5.2 × 0.1

= 0.099615 M

COD,mg/L

𝐵𝑙𝑎𝑛𝑘 𝑇𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛−𝑆𝑎𝑚𝑝𝑙𝑒 𝑇𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛 ×𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝐹𝐴𝑆 ×8000

= 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑆𝑎𝑚𝑝𝑙𝑒 (𝑚𝐿)

KHP Standard

SAMPLE 1 SAMPLE 2 SAMPLE 3

(1.6−0.9)×0.09615×8000 (1.8−0.9)×0.09615×8000 (1.6−1.0)×0.09615×8000

= = =
2.5 2.5 2.5

= 215.38 mg/L =276.91 mg/L =184.61 mg/L

AVERAGE COD (mg/L) 225.63
Section 7

SAMPLE 1 SAMPLE 2 SAMPLE 3

(1.6−1.4)×0.09615×8000 (1.8−1.5)×0.09615×8000 (1.6−1.5)×0.09615×8000

= = =
2.5 2.5 2.5

= 61.54 mg/L = 92.30 mg/L =30.77 mg/L

AVERAGE COD (mg/L) 61.54

Section 17

SAMPLE 1 SAMPLE 2 SAMPLE 3

(1.6−1.2)×0.09615×8000 (1.8−0.9)×0.09615×8000 (1.6−1.2)×0.09615×8000

= = =
2.5 2.5 2.5

= 123.07 mg/L =276.91 mg/L = 123.07 mg/L

AVERAGE COD (mg/L) 174.35
7. DISCUSSIONS

Chemical Oxygen Demand are important in the control of the total content of
pollution and the management of water environment. The COD is measured using a
strong oxidant under acidic conditions. A known excess amount of the oxidant is added
to the sample. Once oxidation is complete, the concentration of organics in the sample is
calculated by measuring the amount of oxidant remaining in the solution. This is done by
titration, using an indicator solution. The organic matter was oxidized and the colour of
the solution was changed from light brown colour to light green which mean, the Cr2O72-
was reduced to Cr3+ .

The sample was titrated with standardized 0.10 M FAS. The molarity of FAS
solution was 0.09615 M. From that value, the COD (mg/l) of sample was calculated.

In this experiment, the Chemical Oxygen Demand (COD) of KHP standard, water
samples and blank was measured and calculated. The COD reading obtained for KHP
standard, water samples from section 7 and section 17 was 225.63 mg/L , 61.54 mg/L and
174.35 mg/L respectively. The water samples is with compared to two standards for
effluent discharge: Standard A and Standard B. Water sample from section 7 was
compared with Standard B based on table 1. This is because Standard B for discharge
downstream of any raw water intake. The Standard B shows that the value for COD was
200 mg/L. The water sample from section 7 was not beyond the expectation.Therefore, it
can conclude that the water sample was not polluted. The water sample was safely to
discharged. While, water sample from section 17 was higher than the standard B. It can
said the water was polluted and need further treatment. The water sample have many
organic compound that decompose and release dissolved oxygen. Moreover, around the
water samples there is factories that cause arise of bacteria. The higher the chemical
oxygen demand, the higher the amount of pollution in the test sample.
 Table 1: Environment Quality (Sewage) Regulation 2009 for new sewage treatment
system.

Parameter Unit Standard A Standard B

Temperature ̊C 40 40
pH value - 6.0-9.0 5.5-9.0
BOD mg/L 20 50
COD mg/L 120 200
Suspended Solids mg/L 50 100
Oil and Grease mg/L 5.0 10.0
Ammoniacal Nitrogen (enclosed water body) mg/L 5.0 5.0
Ammoniacal Nitrogen (river) mg/L 10.0 20.0
Nitrate-nitrogen (enclosed water body) mg/L 10.0 10.0
Nitrate-nitrogen (river) mg/L 20.0 50.0
Phosphorus mg/L 5.0 10.0

The COD calculation also was compared with the other group. The average COD
reading (mg/L) obtained for standard, water sample from Section 7 and Section 17 are
shown below

Table 1 is COD result of water sample from Section 7 (Result was taken from
NurFarrah Atiqah’s group)

Sample 1 = (1.50-1.47) x 0.09434M x 8000 / 2.5ml

= 9.0566 mg/l
Sample 2 = (1.54-1.50) x 0.09434M x 8000 / 2.5ml
= 12.0755 mg/l
Sample 3 = (1.60-1.58) x 0.09434M x 8000 / 2.5ml
= 6.0378 mg/l

Therefore, its prove that the water sample from section 7 was not polluted while water
sample from section 17 was polluted.
 The COD calculation for water samples from section 7 and section 17 was
compared with Malaysian Water Quality Index for Chemical Oxygen Demand (COD).
The result for water sample section 17 was considered as level V which is more than 100
mg/l and need to treat because the amount of oxygen reduction is high. While, the water
sample from section 7 was considered as level IV which is less than 100 mg/L.

Parameter Classes
I II III IV V
COD value < 10 10-25 25-50 50-100 >100
Classes in Malaysian Water Quality Index for Chemical Oxygen Demand (COD)

There are some precautions steps should be taken in this experiment. Firstly, samples
must be mixed well and measured quickly to avoid settling errors. The wastewater samples
need to be shaken before pipette it for the dilution. The spectrophotometer must be warmed
up to 150◦C.

There are several ways to reduce the COD in the wastewater. Firstly, COD reducement
using precipitation process which is coagulation. TSS or no dissolved solids commonly called
sludge. The most important way to get rid of the sludge is to use coagulants and flocculants.
The principle is to bind the sludge to one another so that a larger clumps of sludge and then be
depoosited in a sedimentation tank. Some chemicals commonly used as a coagulant, among
others; PAC, FeCl3. Next, COD reduction process by the method of using bacteria or
microorganisms, devoted to COD derived from organic matter with a high content of
biodegradable. This process is done in two main ways, namely aeration and anaerobic.

The average BOD concentration of the water sample from section 7 is 2.38 mg/L.
Therefore, the amount of COD is higher than the BOD. This is because COD includes both
biodegradable and non-biodegradable substances whereas BOD contains only biodegradable.
8. CONCLUSION

Chemical oxygen demand (COD) of the sampel was measured. The COD value
(mg/L) obtained for KHP standard, water samples from section 7 and section 17 was
225.63 mg/L , 61.54 mg/L and 174.35 mg/L respectively. Water sample from section 17
was considered as level V while, the water sample from section 7 was considered as level
IV according to Malaysian Water Quality Index for Chemical Oxygen Demand (COD).

9. REFERENCES

 Chemical oxygen demand. (2019, March 03). Retrieved March 30, 2019, from
https://en.wikipedia.org/wiki/Chemical_oxygen_demand
 Hazmi, B. . Chemical Oxygen Demand (COD). Retrieved March 29, 2019, from
https://www.academia.edu/32962114/Chemical_Oxygen_Demand_COD_
 Masulli, D. (2017, May 10). Guide to Chemical Oxygen Demand (COD) Testing.
Retrieved April 2, 2019, from https://blog.hannainst.com/cod-testing
 Chemical Oxygen Demand I COD Analyzers & Sensors I Real Tech Water. (n.d.).
Retrieved April 2, 2019, from https://realtechwater.com/parameters/chemical-oxygen-
demand/
 The Nuts and Bolts of Chemical Oxygen Demand. (2003, May 06). Retrieved April 2,
2019, from https://www.wqpmag.com/nuts-and-bolts-chemical-oxygen-demand
 Yusuf, J. (2015, December 09). 5 Ways to Reduce COD in wastewater. Retrieved April
2, 2019, from https://medium.com/@MrJojo77/5-ways-to-reduce-cod-in-wastewater-
d217bb5d5574
APPENDIX

SOURCE : https://www.doe.gov.my/portalv1/wp-
content/uploads/2015/01/Environmental_Quality_Sewage_Regulations_2009_-_P.U.A_432-
2009.pdf