4.2 Oxygen Demand and Kinetics 2

Other Measure of Oxygen Demand
Chemical Oxygen Demand (COD)

• In this test to determine the oxygen requirement of the wastewater,
strong oxidizing agent ‘potassium dichromate’ is used.
• Acidic environment is provided to accelerate the reactions by addition
of sulphuric acid.
• COD test measures virtually all oxidizable organic compounds
whether biodegradable or not, except some aromatic compounds
which resists dichromate oxidation.
• The COD is proportional to BOD only for readily soluble organic
matter in dissolved form e.g. sugars. For readily biodegradable waste,
such as dairy COD = BODu/0.92
• The correlation between BOD and COD for sewage is presented in the
below.
Correlation between BOD and COD for sewage at 20oC incubation and k=0.23per day CODb ,
b means biodegradable
• The COD is faster determination but does not give idea about the nature
of organic matter whether biodegradable or non biodegradable organic
matter.
• Hence, determination of BOD is necessary for the wastewater to know
biodegradable organic matter fraction.
• The BOD is not very useful test for routine plant control due to long
incubation period required, (5 days) to obtain results. Thus, it is
important to develop correlation between BOD and COD , so that COD
can be used as a parameter for routine analysis and control of the
treatment plant. Once COD values are known, the BOD can be
estimated using correlation.
Theoretical Oxygen Demand (ThOD)
• Theoretical oxygen demand for the wastewater is calculated as
oxygen required for oxidizing the organic matter to end products.
• For example, for glucose, the theoretical oxygen demand can be
worked out as below:
Self-Purification of Natural Streams
• The self purification of natural water systems is a complex process
that often involves physical, chemical, and biological processes
working simultaneously.
• The amount of Dissolved Oxygen (DO) in water is one of the most
commonly used indicators of a river health.
• As DO drops below 4 or 5 mg/L the forms of life that can survive begin
to be reduced.
• A minimum of about 2.0 mg/L of dissolved oxygen is required to
maintain higher life forms
Factors Affecting Self Purification
1. Dilution
When sufficient dilution water is available in the receiving water body,
where the wastewater is discharged, the DO level in the receiving stream
may not reach to zero or critical DO due to availability of sufficient DO
initially in the river water before receiving discharge of wastewater.
2. Current
• When strong water current is available, the discharged wastewater will
be thoroughly mixed with stream water preventing deposition of solids.
• In small current, the solid matter from the wastewater will get
deposited at the bed following decomposition and reduction in DO.
3. Temperature:
• The quantity of DO available in stream water is more in cold temperature than
in hot temperature.
• Also, as the activity of microorganisms is more at the higher temperature.
4. Sunlight: Algae produces oxygen in presence of sunlight due to
photosynthesis. Therefore, sunlight helps in purification of stream by adding
oxygen through photosynthesis.
5. Rate of Oxidation:
• Due to oxidation of organic matter discharged in the river DO depletion occurs.
• This rate is faster at higher temperature and low at lower temperature.
• The rate of oxidation of organic matter also depends on the chemical
composition of organic matter
Oxygen Sag Analysis
• The oxygen sag or oxygen deficit in the stream at any point of time
during self- purification process is the difference between the
saturation DO content and actual DO content at that time.
• Oxygen deficit, D = Saturation DO – Actual DO
• The saturation DO value for fresh water depends upon the
temperature and total dissolved salts present in it; and its value varies
from 14.62 mg/L at 0oC to 7.63 mg/L at 30oC, and lower DO at higher
temperatures
• The saturation of DO at 20 oC is 9.17mg/l
• The DO in the stream may not be at saturation level and there may be
initial oxygen deficit ‘Do’.
• At this stage, when the effluent with initial BOD load Lo, is discharged
in to stream, the DO content of the stream starts depleting and the
oxygen deficit (D) increases.
• The variation of oxygen deficit (D) with the distance along the stream,
and hence with the time of flow from the point of pollution is
depicted by the ‘Oxygen Sag Curve’ (Figure below).
The major point in sag analysis is point of minimum DO, i.e., maximum deficit. The maximum or
critical deficit (Dc) occurs at the inflexion points of the oxygen sag curve.
Deoxygenation and Reoxygenation Curves
• When wastewater is discharged into the stream, the DO level in the stream
goes on depleting. This depletion of DO content is known as
deoxygenation.
• The rate of deoxygenation depends upon;
i. The amount of organic matter remaining (Lt) to be oxidized at any time t, as well
as
ii. temperature (T) at which reaction occurs.
• The variation of depletion of DO content of the stream with time is

depicted by the deoxygenation curve in the absence of aeration.
• The ordinates below the deoxygenation curve (Figure above) indicate the
oxygen remaining in the natural stream after satisfying the bio-chemical
oxygen demand of oxidizable matter.
• When the DO content of the stream is gradually consumed due to
BOD load, atmosphere supplies oxygen continuously to the water,
through the process of re-aeration or re-oxygenation,
• i.e., along with deoxygenation, re-aeration is continuous process.
• The rate of re-oxygenation depends upon:
i) Depth of water in the stream: more for shallow depth.
ii) Velocity of flow in the stream: less for stagnant water.
iii) Oxygen deficit below saturation DO: Since solubility rate depends on
difference between saturation concentration and existing concentration of DO.
iv) Temperature of water: solubility of oxygen is lower at higher temperature
and also saturation concentration is less at higher temperature.
Mathematical analysis of Oxygen Sag Curve: Streeter – Phelps equation
• The analysis of oxygen sag curve can be easily done by superimposing the
rates of de-oxygenation and re-oxygenation as suggested by the Streeter –
Phelps analysis
• The rate of change in the DO deficit is the sum of the two reactions as
explained below
• Equation 4 and 5 is the Streeter-Phelps oxygen sag equation. The graphical
representation of this equation is shown in Figure below
NB:
• Deoxygenation and reoxygenation occurs simultaneously.
• After critical point, the rate of re-aeration is greater than the
deoxygenation and after some distance the DO will reach to original
level and stream will not have any effect due to addition of
wastewater.
Determination of Critical DO deficit (Dc) and distance Xc
• Determine Oxygen deficit at varying distance,x=20,40,80,100
Oxygen surge curve
10.00
9.00
8.00
7.00
6.00
DO (Mg/l)
5.00
4.00
3.00
2.00
1.00
0.00
0 10 20 30 40 50 60 70 80 90 100
Distance (km)
• Assignment 1 : To be submitted in one weeks time.

4.2 Oxygen Demand and Kinetics 2

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Other Measure of Oxygen Demand

Chemical Oxygen Demand (COD)

• The variation of depletion of DO content of the stream with time is

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