Title: Determination of COD in a Wastewater Sample & Determination of the Water Quality of a

Wastewater Sample by Biological Oxygen Demand.

Name:
Date: Mar 31, 2017 Lab Partner:
Objectives:
The objective is to determine the COD Chemical Oxygen Demand in a water sample by
titration with ferrous ammonium sulphate.
To determine the quality of quality of a water sample by Winkler method.
Introduction:
Biological Oxygen Demand is a measure of the amount of oxygen that is dissolved in a water
sample that is needed to break down organic matter present in said sample. BOD is sometimes
also referred to as Biochemical Oxygen Demand.
Dissolved oxygen is the key factor for the survival of many aquatic creatures as it is the source of
oxygen for these animals. This is why air pumps or bubblers must be present in fish tanks at
homes or in aquariums as it increases the amount of dissolved oxygen. Dissolved oxygen
concentrations can be lowered in a water source by fish and other aquatic life or by organic
matter.
Generally, organic matter consists or decomposing plants or animal tissues. When
microorganisms break down organic matter the concentration of dissolved oxygen will lower.
For example, in 2008 an eruption of a different type of algae beached 50 tons of fish, which
were starving for oxygen and rotted along the coast of Oman. (Caole Vila, 2017). However, the
main cause of this event was attributed to climate change for the proliferation of algae, a food
source must be present .i.e. organic matter.
Measuring the amount of DO Dissolved Oxygen present in a body/sample of water is
therefore a good indicator of the quality of that water. The Winkler method and the use of a
dissolve oxygen meter are ways of measuring the DO, but for this experiment; the Winkler
method will be used. The Winkler method consists of fixing the amount of DO in water sample.
This is done as DO levels can be depleted naturally by temperate and pressure changes. So as to
not obtain incorrect results, the oxygen is fixed. Fixing is done by adding manganese sulphate and
an alkaline solution with iodine to the water sample. This causes the DO to precipitate out of
solution as Magnesium Oxide.

Mn2+ + 12 O2 + 2 2 () + 2

The magnesium oxide and water solution is then kept airtight. The iodine present in the alkaline
solution further goes on to react with the magnesium oxide once the solution is made acidic i.e. after
addition of an acid.

2 + 2 + + Mn2+ + 2 + 22
The solution can then be titrated against sodium thiosulphate, which reacts with the iodine in the
solution. The amount of iodine in the solution can be related to amount of oxygen present. This
can be represent as:
2 + 22 32 24 32 + 2
However, the overall equation is:

24 32 + 2+ + 12 O2 24 62 + 2
COD Chemical Oxygen Demand is another useful way of gauging the quality of water, similar to
BOD. It is a laboratory assay, which indirectly measures the amount of organic matter contained in a
water sample.
It can be defined as the amount of oxygen consumed for the oxidation of total organic matter. COD is
measured in milligrams of O2 per litre of water.
In comparison to BOD a measure of the amount of oxygen that microorganisms will consume in a
water sample while decomposing organic matter COD does not discriminated against organic and
inorganic matter and is a measure of the total quantity of oxygen required to oxidise all organic
material into CO2 in a water sample. BOD results can be related to COD results in a ratio value. Other
differences from these tests are that for BOD to take place, an incubation period of 5 days must take
place. Whereas with COD, it is rapid taking around 2 hours to complete.
The basic principle in a COD test is that all organic matter can be oxidised to CO2 in a water sample
with a strong oxidising agent under high temperature and acidic conditions. After this step, the
concentration of organic substance in the sample is calculated from titration. The concentration can
also be determined by spectrophotometric analysis, but for this experiment titration will be used.
After boiling the water sample under reflux with a known excess of potassium dichromate under
acidic conditions, the sample will be titrated against ferrous ammonium sulphate. With the use of an
indicator, the amount of ferrous ammonium sulphate required to see a colour change can be related to
the amount of potassium dichromate that remains in the solution. A blank sample must be done
alongside the water sample, as there are some expected negligible amounts of chemically oxidised
material. This blank is also titrated against ferrous ammonium sulphate.

Method & Materials:

As per lab manual
Experimental Results:

Dissolved Oxygen Titration

Sample Amount of 0.025 M Na2S2O3 (ml)

Day 1 Day 7
Pond Water 3.63 3.6 2.5 2.4
Day 1 Day 21
Slang River 1.6 0.55
Effluent N/A N/A

Standardisation of Ferrous Ammonium Sulphate

Group Ferrous Ammonium Sulphate (ml)

1 10.25
2 10.15

COD Titration

Sample Ferrous Ammonium Sulphate (ml)

River Water 24.1
Pond Water 24 21.65
Blank 24.7 24.9 24.8
Analysis of pH, Conductivity, and Suspended Solids

Measurement River Pond Effluent

pH 8.2 7.78 7.75 7.61
Weight of Solids (mg) Slight Dif. in weight 25 38 59.4
Conductivity (s) 637 522 515 600
Suspended solid mg/L N/A 157.5 297

Calculations:
Dissolved Oxygen Titrations
River water Day 1
Pond water Day 1
Average Titre 3.615 ml 1 1 2 2
=
0.025 (0.0016 ) = 0.05
1 1 2 2 4 1
= 4 105 = 0.05
0.025 (0.003615 ) = 0.05 4 1
4 1 4 105 (1) = 0.05 (4)
9.0375 105 = 0.05
4 1 4 105 = 0.2
9.0375 105 (1) = 0.05 (4) 5
= 4 10 0.2
9.0375 105 = 0.2
5 = 2104
= 9.0375 10 0.2
= 4.5186 104
Conversion to mg/L
Conversion to mg/L
2 104 32 = 0.0064
4
4.5186 10 32 = 0.0145 6.4 of dissolved O2 was present.
14.5 of dissolved O2 was present.

Pond water Day 7 River water Day 21

Average Titre 2.45 ml

1 1 2 2
= 1 1 2 2
0.025 (0.00245 ) = 0.05 =
4 1 0.025 (0.00055 ) = 0.05
0.025 (0.00245 ) = 0.05 4 1
4 1 1.375 105 = 0.05
6.125 105 = 0.05 4 1
4 1 1.375 105 (1) = 0.05 (4)
6.125 105 (1) = 0.05 (4)
1.375 105 = 0.2
6.125 105 = 0.2 5
5 = 1.375 10 0.2
= 6.125 10 0.2
= 6.875 105
= 3.0625 104
Conversion to mg/L
Conversion to mg/L
6.875 105 32 = 0.0022 /
3.0625 104 32 = 0.0098 /
2.2 of dissolved O2 was present
9.8 of dissolved O2 was present.
 Normality of FAS COD Titration

( 2 2 7 7)(0.25) Average Titre Value Blank: 24.8 ml

=

(10 )(0.25) River 24.1 ml
=
10.2
= 0.2451 (24.8 24.1 )(0.2451) 8000
=
50
(0.7 )(0.2451) 8000
=
BOD7 test Pond water 50
1372.56
=
Dissolved oxygen day 1 - 14.5 50
Dissolved oxygen day 7 9.8 = 27.45/ of O2
7 = 14.5 9.8
7 = 4.7 Average pond titre value 22.852 ml

BOD21 test River water (24.8 22.851 )(0.2451) 8000

=
50
Dissolved oxygen day 1 - 6.4 (1.949 )(0.2451) 8000
=
Dissolved oxygen day 21 2.2 50
21 = 6.4 2.2 3821.6
=
21 = 4.2 50
= 76.43 / of O2

Discussion:
Analysis of pH, Conductivity, and Suspended Solids

This procedure was carried out by taking 200 ml of each water sample. The samples were then
tested for pH and conductivity by using a pH/conductivity meter. After readings were taken, the
samples were filtered under vacuum through a pre-weighed filter paper. The difference in the
weight of the filter paper is represented as Weight of Solids (mg) in table X.
From this testing it was possible to conclude that the pond water sample was more basic than the
effluent and the river water sample was more basic than the pond.
Considering that there was a trend in the results that the higher the amount suspended solids in a
sample, the higher the conductivity.
The effluent had 49.97% more suspended solids and was 56.79% higher in conductivity than the
average of the pond samples. However, the only data for weight of solids for the river sample was
only quoted as Slight difference in weight; - meaning there was a slight difference between the
pre-weighed filter paper and used filter paper no answer for suspended solids (mg) per litre can
be obtained.
The pond water samples were expected to have less suspended solids than the effluent. Pond
water generally has little to no flow allowing a lot of sediment present to settle. Whereas
effluent is a where a stream of water meets a river. The effluent sample contained (59.4 mg)
46.97% more solids than the pond sample, which had an average of 31.5 mg.
The river water sample was the most basic out of the three samples, being 5.3% more basic than
the average of the pond samples (pH 7.765) and 7.19% more basic than the effluent sample (pH
7.61).
Dissolved Oxygen Titration

The dissolved oxygen content of the effluent water sample was conclusive that there was 0%
dissolved oxygen in the sample. This was noted as no colour change was observed during the
titration; even when excess sodium thiosulphate was added.
The concentration of oxygen the pond water sample at day 1 was equal to 4.5186 x 10-4 M. After
a 7-day incubation period, the concentration was found to 3.0625 x 10-4 M. This represents a
32.22% drop in concentration.
The concentration of oxygen the river water sample at day 1 was equal to 2 x 10-4 M. After a 21-
day incubation period, the concentration was found to 6.875 x 10-5. This represents a 97.67%
drop in concentration
Due to the relationship of molarity and the molar mass; - multiplying the concentrations by the
molar mass of oxygen yields the amount of dissolved oxygen (grams) per litre.

BOD Testing

From the BOD testing two results were obtained; one for pond water and one for river. A result
for effluent could not be obtained, as the Wrinkle test could not be performed on the sample.
The BOD for the pond water sample was denoted by a 7 (.i.e. BOD7) as there was a 7 day
incubation period between both tests. Generally, these tests are conducted after a 5-day
incubation period.
However, the BOD after 7 days in the pond water was found to be 4.7 mg/L. According to the
European fresh water directive (78/659/EEC) fresh water should contain a BOD of 3mg/L for
salmonid water and 6mg/L for cyprinid waters.
The BOD of the pond water is only suitable for cyprinid water, but falls below the specifications
for salmonid waters by 36.17%.
The BOD for the river water sample was denoted by 21, as there was a 21-day incubation period.
The BOD21 for the river water 4.2 mg/L. This, like the pond water sample, only complies with
one of the two specifications of the European fresh water directive (78/659/EEC) in this case
being suitable for cyprinid containing waters. The river water sample fell below the specifications
for salmonid containing waters by 28.57%. In comparison to the pond water sample, there was a
difference 7.6% of BOD.
The BOD of a water drops as anaerobic microorganisms break down any organic matter present.
Organic matter consists of leaves, dead plants, grass etc. High levels of organic matter in a water
sample may lead to an increase in a population of microorganisms, thus a higher BOD of a water
sample.
The reason for an incubation period of these tests is to ensure that all organic matter present in the
sample has been degraded. The amount of dissolved oxygen present in the sample was tested for
as an initial test. This was then compared to the amount of dissolved oxygen after the incubation
period. The test was conducted as to ensure the water sources complied with the EU directive.
Standardisation of Ferrous Ammonium Sulphate

The FAS solution was titrated against a solution of potassium dichromate of known concentration
(0.0417 M). This was done twice by two separate groups. An indicator was used during both
titrations and an end-point was noted after reddish-brown colour change.
From these two titrations, an average titre value of 0.0102 L was noted.

COD Titration

The COD for the river water sample was found to be 27.45 mg/L while the COD for the pond
water was found to be 76.43 mg/L.

These values are significantly higher than the BOD values, this is due to more organic matter
present in each sample can be oxidised chemically, rather than biologically.

In this case, the O2 mg/L for the pond water was 93.85% higher in the COD test when compared
to the BOD test. The O2 mg/L for the pond water was 84.70% higher in the COD test when
compared to the BOD test.

Conclusion:
Caole Vila, A. (2017). The Ocean Can't Breathe: Mexico-Sized Algae Bloom in the Arabian Sea Should
Concern You. [online] Nature World News. Available at:
http://www.natureworldnews.com/articles/36817/20170328/the-ocean-cant-breathe-mexico-sized-
algae-bloom-in-the-arabian-sea-should-concern-you.htm [Accessed 5 Apr. 2017].