SCHOOL OF THE BUILT ENVIRONMENT
BASICS OF WATER QUALITY (BWAQ)
DISSOLVED OXYGEN
Lecture 5.0
DO – GENERAL CONSIDERATIONS, SIGNIFICANCE AND
INTRODUCTION
All living organisms are dependent upon oxygen in one form or
another to maintain the metabolic processes that produce
energy for growth and reproduction.
Aerobic processes are the subject of greatest interest because of
their need for free oxygen.
Humans are vitally concerned with the oxygen content
of the air that they breathe, since they know from
experience that an appreciable reduction in oxygen content
will lead to discomfort and possibly death.
For this reason, the number of occupants within enclosures
must be carefully restricted to the ventilating capacity. 2
SIGNIFICANCE
Environmental engineers and scientists are, of course,
interested in atmospheric conditions in relation to humans,
but, in addition, they are vitally concerned with the
“atmospheric conditions” that exist in liquids, water being
the liquid in greatest abundance and importance.
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DEFINITION AND SIGNIFICANCE OF DISSOLVED
OXYGEN
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DIVERSITY AND EQUITABILITY OF AQUATIC ORGANISMS
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SCHEMATIC OF A LAKE ECOLOGY
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SOLUBILITY OF OXYGEN IN WATER
All the gases of the atmosphere are soluble in water to some degree.
Both nitrogen and oxygen are classified as poorly soluble, and since
they do not react with water chemically, their solubility is directly
proportional to their partial pressures.
The solubility of both nitrogen and oxygen varies greatly with the
temperature over the range of interest for natural waters.
Figure 1 shows solubility curves for the two gases in distilled or low-
solids-content water in equilibrium with air at 760mm Hg (or 1 atm)
pressure.
The solubility is less in saline waters.
At saturation, the dissolved gases contain about 38 percent oxygen
on a molar basis, or nearly twice as much oxygen as in the normal
atmosphere. 7
SOLUBILITY CONT…
The solubility of atmospheric oxygen in fresh waters ranges from
14.6mg/l at 0oC to about 7mg/l at 25oC under 1 atm of pressure.
Since it is a poorly soluble gas, its solubility varies directly with the
atmospheric pressure at any given temperature.
This is an important consideration at high altitudes.
Most of the critical conditions related to dissolved-oxygen
deficiency in natural waters occurs during the summer
months when temperatures are high and solubility of oxygen
is at a minimum.
For this reason it is customary to think of dissolved-oxygen
levels of about 8mg/l as being the maximum available 8
under critical conditions.
SOLUBILITY CONT…
The low solubility of oxygen is the major factor that limits the
purification capacity of natural waters and necessitates
treatment of wastes to remove pollution matter before discharge to
receiving streams.
In aerobic biological treatment processes, the limited solubility of
oxygen is of great importance because it governs the rate at which
oxygen will be absorbed by the medium and therefore the cost of
aeration.
The solubility of oxygen is less in salt-containing water
than it is in clean water.
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FIGURE 1 : SOLUBILITY OF OXYGEN AND NITROGEN IN DISTILLED WATER
SATURATED WITH AIR AT 1 ATMOSPHERE
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For this reason, the solubility for a given temperature
decreases as one progresses from fresh water to estuary
water to the ocean.
The extent of this effect is indicated in Table 2, which contains a
listing of oxygen solubility as a function of temperature and
chloride content.
Chloride concentration is used as a measure of the seawater-fresh
water mix in a sample. The chloride content of seawater is about
19000 mg/l.
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In polluted waters the saturation value is also less
than that of clean water.
The ratio of the value in polluted water to that in
clean water is referred to as the β value.
The rate of absorption of oxygen in polluted waters is
normally less than in clean water and the ratio is
referred to as the α value.
They may range as low as 0.8 for β and 0.4 for α in
some wastewaters.
Both α and β values are important design factors in
selection of aeration equipment.
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ENVIRONMENTAL SIGNIFICANCE
In liquid wastes, dissolved oxygen is the factor that determines
whether the biological changes are brought about by aerobic or
by anaerobic organisms.
The former use free oxygen for oxidation of organic and inorganic matter
and produce innocuous (inoffensive) end products, whereas the latter
bring about such oxidations through the reduction of certain inorganic
salts such as sulfate, and the end products are often very obnoxious
(loathsome).
Since both types of organisms are ubiquitous (ever-present) in
nature, it is highly important that conditions favorable to the aerobic
organisms (aerobic conditions) be maintained; otherwise the anaerobic
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organisms will take over, and development of nuisance conditions will
result.
ENVIRONMENTAL SIGNIFICANCE
Thus, dissolved-oxygen measurements are vital for maintaining
aerobic conditions in natural waters that receive pollutional
matter and in aerobic treatment processes intended to purify
domestic and industrial wastewaters.
In most instances involving the control of stream pollution, it is
desirable to maintain conditions favorable for the growth and
and reproduction of a normal population of fish and other aquatic
organisms.
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ENVIRONMENTAL SIGNIFICANCE
This condition requires the maintenance of dissolved oxygen levels that
will support the desired aquatic life in a healthy condition at all times.
Determination of dissolved oxygen serve as the basis of the BOD
test; thus, they are the foundation of the most important determinations
used to evaluate the pollutional strength of domestic and
industrial wastes.
Oxygen is a significant factor in the corrosion of iron and steel,
particularly in water distribution systems and in steam boilers.
Removal of oxygen from boiler-feed waters by physical and chemical
means is common practice in the power industry.
The dissolved oxygen test serves as the means of control.
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COLLECTION OF SAMPLES AND DETERMINATION OF DISSOLVED OXYGEN
A certain amount of care must be exercised in the collection of
samples to be used for dissolved oxygen determinations.
In most cases of interest, the dissolved oxygen level will be
below saturation, and exposure to the air will lead to
erroneous results.
For this reason, a special sampling device is needed. E.g Van
Dorn Bottle, Bailers, Automatic (Autosamplers).
All such samplers are designed on the principle that contact
with air cannot be avoided during the time the sample
bottles are being filled.
However, if space is available to allow the bottles to overflow, a
sample of water that is representative of the mixture being 18
sampled can be obtained.
COLLECTION OF SAMPLES AND DETERMINATION OF DISSOLVED OXYGEN
Most samplers are designed to provide an overflow of
two or three times the bottle volume to ensure
collection of representative samples.
Also, as oxygen readily penetrates most rubber and
plastic tubing, great caution is required in their use for
sampling.
Most samples for dissolved oxygen are collected in the field,
where it is not convenient to perform the entire determination.
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COLLECTION OF SAMPLES AND DETERMINATION OF DISSOLVED
OXYGEN
Since oxygen values may change radically with time because
of biological activity, it is customary to “fix” the samples
immediately after collection.
The usual procedure is to treat the samples with conventional
reagents used in the dissolved oxygen test and then perform the
titration when the samples are brought to the laboratory.
This procedure will give low results for samples with a high iodine
demand, and in this case it is better to preserve the sample by
addition of 0.7ml concentrated sulphuric acid and 0.02g sodium
azide.
When this is done, it is necessary to add 3ml of alkali-iodide reagent
rather than the usual 2ml because of the extra acid the sample
contains.
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COLLECTION OF SAMPLES AND DETERMINATION OF
DISSOLVED OXYGEN
Better results are also obtained if the “fixed” samples are
stored in the dark and on ice until the analyses can be
completed.
The chemical treatment employed in “fixing” is radical
enough to arrest all biological action, and the final
titration may be delayed up to 6 hours.
There are two standard procedures for measuring dissolved
oxygen.
The older and still primary procedure is through oxidation-
reduction titration using iodometric procedures.
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WINKLER’S METHOD OF DETERMINING DO
1. Take 250ml of sample, measure its temperature and make sure it has no
air bubbles.
2. Add a spatula-ful of manganous sulphate monohydrate, this is a source of
Mn2+ ions.
3. Add an alkaline iodide azide pillow to increase the pH and to introduce
the iodide ions.
4. Cork the 250ml volumetric flask up in a manner that eliminates air
bubbles, shake it hard to homogenize the mixture. If oxygen is present, it
will change colour from colourless to light brown (actually yellowish). This
is caused by Mn2+ which is being oxidized to Mn4+.
5. Put it down and allow the yellowish-brown precipitate to settle half-way
through the base of the volumetric flask. Watch out for air bubbles, if
present the experiment fails.
6. Remove stopper and add 2ml or more (in excess) of concentrated sulphuric
acid. This suppresses the pH and forces the previous yellowish-brown
colour to change to dark brown. This is because iodine molecules are being
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formed, and the cloudy Mn4+ is being reduced to Mn2+.
WINKLER’S METHOD OF DETERMINING DO
7. Transfer half the mixture into a 250ml beaker and titrate it
with sodium thiosulphate. (Na2S2O3) which will turn the brown
iodine molecules (I2) into colourless iodide ions (I-).
8. Add the non-toxic starch solution (1 to 2 pinches) to sharpen
the end-point.
9. Allow the sodium thiosulphate to run from the burette into
the beaker until the colour of the mixture gets changed from
dark brown to colourless by addition of one drop.
10. Read off the volume of sodium thiosulphate and stop the
titration.
11. Volume used +molarity of S2O32- → moles of S2O32
→moles of I2 → moles of MnO2 → moles of O2 used.
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E4---9.1 Winkler Experiment for Dissolved Oxygen (Chemical equations too) [SL IB Chemistry].mp4
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Most volumetric methods of determining dissolved oxygen
depend upon reactions that release an amount of iodine
equivalent to the amount of oxygen originally present, with
subsequent measurement of the amount of iodine released by
means of a standard solution of a reducing agent.
Sodium thiosulphate is the reducing agent normally used,
and starch solution is used to determine the end point.
All reactions in the determination of oxygen involve oxidation and
reduction.
However, starch is used as the end-point indicator.
It forms a starch-iodine complex with iodine from dilute solutions
to produce a brilliant blue colour and returns to a colorless form
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when the iodine is all reduced to iodide ion.
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Sample Questions.
What precautions do you need to take during DO
measurement in raw wastewater sample?
Hint: This sample can have both oxidizing and
reducing agents.
Outline the procedure of Winkler’s method of
determining DO with possible reactions where
possible.
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Texts : Environmental Engineering 4th edition By
Ruth F. Weiner and Robin Matthews
Chemistry for Environmental Engineering and
Science by Clair & Sawyer
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