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Subject Chemistry

Paper No and Title 4 Environmental Chemistry

Module No and Title 10 : Part 1 Analytical Techniques for Measuring Water Quality
Parameters
Module Tag CHE_P4_M10_E_Text

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Dissolved Oxygen
3.1 Determination of DO
4. Biochemical Oxygen Demand
4.1 Determination of BOD
4.2 Chemical Oxygen Demand
4.3 Total Organic Carbon
5. Summary

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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1. Learning Outcomes
After studying this module, you shall be able to

• Know various parameters for determining water quality standards

• Learn the importance of dissolved oxygen
• Identify the purity of water sample by various tests
• Evaluate the bio chemical and chemical oxygen demand

2. Introduction
An adequate qualitative and quantitative water supply is most essential for small as well as big
cities and towns. Along with water supply, then there should also be a means of disposal of waste
water. Disposal of waste water is of widespread national concern. Municipal waste and industrial
activities generate a large number and variety of waste products, which are generally discharged
into water streams. The situation is particularly critical in developing countries where there are no
stringent laws to check that the industries treat the waste generated prior to disposal. The analysis
of the most common industrial solvent water is extremely important as it contains a large number
of impurities or pollutants which are necessary to be checked before the water is used for any
specific purpose. The ways in which water is used are so varied that no single purity standard can
be applied. If water is to be used for cleaning or washing purposes, no special treatment is
required. If water is to be used for drinking purposes, then it is most essential to determine colour,
turbidity, dissolved solids, hardness, alkalinity, acidity, free chlorine etc. In order to control water
pollution, quantitative measurement of extent of water pollution is extremely necessary. A
specific treatment cannot be undertaken without knowing the substances and their quantities in
water. The measurement of water quality is, however, very tedious process and a large number of
quantitative analytical techniques are used for these purposes.
We shall now discuss some analytical procedures for water pollutant analysis. In this module we
shall study three important parameters (dissolved oxygen, Biological Oxygen Demand, Chemical
Oxygen Demand) as an index for water pollution.

3. Dissolved Oxygen
Oxygen is very essential component for the existence of all forms of life. It is present in water in
as dissolved oxygen (DO). It enters water as dissolved oxygen by the process of diffusion from
the surrounding air, or by aeration (rapid movement), and also as a byproduct of the process
photosynthesis in plants. In the dissolved form, i.e as dissolved oxygen, it is very significant for
aquatic life and is considered as one of the most important indicators of the quality of water in
this context. The dissolved oxygen (DO) can be easily measured. In this quantitative analysis, the
amount of gaseous oxygen (O2) dissolved in an aqueous solution is measured. For good quality
water to support the aquatic life, the reference value is 5.0 mg/L of dissolved oxygen. There will
be risk of aquatic life if dissolved oxygen level is below 5.0 mg/L. The lower the value of the

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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dissolved oxygen, the greater is the stress on the aquatic life. The value of dissolved oxygen
below 1-2 mg/L for a few hours can be very devastating as it can result in large fish kills.

The amount of DO is less in polluted water. Hence lesser value of DO is an indication of more
pollution in water. Let us understand how the value of dissolved oxygen decreases in polluted
water. Wastewater from sewage treatment plants most often contains organic materials dissolved
in them. These organic materials are attacked by microorganisms for their decomposition. This
process consumes the dissolved oxygen present in water. This, in turn, results in the decrease of
the already present amount of dissolved oxygen of that water body.

If more amount of oxygen is consumed than is produced, the levels of dissolved oxygen decline.
This results in stress for aquatic life and some sensitive animals may either move away, weaken,
or even die.

Variation in DO Levels:

DO levels are not same always. They fluctuate seasonally and also over a 24-hour period. The
DO levels vary also with altitude and water temperature.

In general,
• The oxygen level of cold water is higher than the hot water.
• At higher altitudes, less DO is present in water.

Dissolved oxygen levels in all water bodies, i.e, natural as well as waste water depend on
physical, chemical and biological activities of the water body. The analysis of DO is very
important in water pollution control as well as waste water control.

3.1 Determination of DO:

Three methods are widely used for the determination of DO. These are Winkler or Iodometric
Method (titrimetric method), polarographic method and the Electrometric Method, using a
membrane electrode.
3.1.1 Titrimetric Method: It depends how dissolved oxygen get oxidized. There are four
different titrimetric methods based on the water sample, which is to be tested
1 Winkler Method
2 Azide modification
3 Alum flocculation modification
4 Permanganate modification

All the above methods have the same basic principle. The choice of method depends on the
sample to be tested.
1 Azide Modification: This method involves the remove of nitrile interference because
nitrile causes interference in biologically treated effluent.
2 Alum flocculation modification: If the sample contains relatively large amounts of
suspended solids then this method should be used.

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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3 Permanganate modification: If the sample contains ferrous ions then this method is
most suitable. Addition of 1 cm3 of azide solution can be adopted to suppress the interference due
to ferric ions.

4. Winkler Method
This method is used in determining the concentration of oxygen in the given water sample. This
method is firstly proposed by Winkler (1888) and later modified by Strickland and Parsons
(1968). In this method titrimetric principle is used. Oxygen in the water sample oxidizes iodide
ion (I-) to iodine (I2) quantitatively. The iodine produced is titrated with a standard solution of
thiosulfate (S2O3-2). And starch is used to visualize the change at end point. The concentration of
oxygen is then calculated from the titer. While sampling, Mn(II) under basic conditions is added
in order to fix the dissolved oxygen result in the formation of manganic hydroxide (MnO(OH)2),
a brown precipitate, manganic hydroxide (MnO(OH)2). In this method sample is first acidified to
pH 1.0-2.5 which results in dissolution of hydroxides precipitates and liberate Mn(III) ions that
results in oxidation of iodide ions to iodine. The liberated iodine is then titrated with thiosulfate
and oxidizes it to tetrathionate.

Nitrite Interference and Azide modification

Nitrite in water samples causes oxidation of iodide as shown below and N2O2 then oxidised
during titration:

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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It results in erroneous high value and end point could not be detected.
It may be eliminated by addition of NaN3 to alkaline I-solution. On acidification NO2 is
decomposed.

3.1.2. Polarographic Method

The method is based on the fact that oxygen is readily reduced at the dropping mercury electrode.
An aqueous solution saturated with air exhibits two polarographic waves, which are attributed to
oxygen. The first wave is obtained as a result of reduction of oxygen to peroxide, and the second
as a result of further reduction of peroxide into water.

Thus oxygen is polarographically active and is reduced (first to H2O2 and then to H2O) in water at
0.05 V and -0.94 V. The polarograms given by oxygen serve as a means of determining DO in
water. Thus in polarographic analysis, usually nitrogen is passed through the solution for several
minutes, just before the determination. In addition to dropping mercury electrode, O2 can be
reduced at several other electrodes in aqueous solution if a small negative voltage is applied. The
determination of the magnitude of the current flowing through the solution can be done by the
rate of diffusion of O2 to the electrode.
Because of the fact that the mercury electrodes get poisoned by impurities of test solution over
time, this method is not so widely used in the DO analysis of domestic or industrial waste water.

3.1.3 Membrane Electrode Method

In this method, two metal electrodes of Ag and Pb are dipped in a saturated solution of KHCO3,
which is separated from the water sample by using a polyethylene membrane (0.06 mm thick).
Thus, a galvanic cell can be plugged to a pH meter to give a direct reading of DO in mg/L (The 0-
14 pH scale in pH meter becomes 0-14 mg/L DO). The current is measured for
(i) for the sample
(ii) for a standard (sample after saturation with air)
(iii) for the blank (sample after treatment with Na2CO3 to expel O2)

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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At Ag electrode (negative electrode)

At Pb electrode (positive electrode)

4. Biochemical Oxygen Demand

It is the standard measure of concentration of the oxygen required by the microorganisms to cause
bio degradation of a part of the organic and inorganic pollution load. Microorganisms consume
the organic matter like starch and sugars as food. The inorganic constituents like sulfides, sulfites
and ferrous ions are attacked by oxygen in presence of enzymes released by microorganisms.
Eventually, the pollution load is converted into simple, non-hazardous compounds and in this
process, the dissolved oxygen is utilized. The BOD value is directly proportional the amount of
oxygen required to break down the organics. The BOD test is most frequently used to measure
waste loading at treatment plants and also in evaluating the effectiveness of the treatment process
of waste water.

In order to perform the BOD test, following steps are done:

• Incubating a sealed wastewater sample for the standard 5-day period
• Determination of the change in the concentration of dissolved oxygen.

Majority of wastewaters contain additional oxygen demanding materials than the amount of DO
available in air-saturated water. Hence, dilution of the sample is essential before its incubation in
order to bring the oxygen demand and supply into appropriate balance. Further, it needs to be
noted that the bacterial growth requires nutrients such as phosphorous, nitrogen, and trace metals.
Therefore, these these nutrients are added to the diluted water. The diluted water is also buffered
to maintain the pH value in the range of bacterial growth. In order to avoid long periods, and as a
standard norm, a 5-day period has been accepted as the standard incubation period. The result is
hence called the 5 day BOD. BOD is expressed in milligrams oxygen per litre of water or in ppm.

The value of BOD of pure drinking water, on the monthly average, must have 5 day BOD in the
range of 0.75-1.5 mg/L. In the units of ppm, the value of BOD for drinking water must be less
than 1 ppm. BOD values of several hundreds ppm indicate strong sewage. BOD value of a raw
sewage runs from 200-400 ppm.

The environmental impacts of BOD are:

1. It can quantitatively estimate the strength of domestic wastes and industrial wastewaters.
2. Sewage having High value of BOD creates environmental and health problems.
3. High value of BOD interferes with the aquatic life.
4.1 Determination of BOD

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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Let us understand how the determination of BOD is done. It depends upon the value of dissolved
oxygen (DO) over a specified period of time. For convenience, the BOD test is made over a five
day period, also called as a “Five Day BOD”, or a BOD5. In its simplest form, a BOD5 test
quantitatively measures the amount (or concentration) of DO in the sample at the beginning of the
study and again 5 days later. The difference of DO value initially and after 5 days, is the BOD5.
This is achieved by putting a sample of waste into a stoppered bottle for 5 days and measuring the
amount of DO initially and after 5 days.

An unpolluted stream may have BOD in the range 1 to 8 mg/L. If the value of BOD5 is below
7mg/L than dilution of sample is not required. But as it reaches above 7 mg/L the sample should
be in diluted form. It is also important to dilute the sample if DO consumed by microorganisms is
greater than the available DO available in the saturated air. BOD5 sample. For a water to be fit for
drinking purpose, BOD5 values are acceptable only if the DO concentration after 5 days is at least
1-2 mg/L lower in concentration than the initial DO. The BOD test is invalid, if during the 5 days
DO drops to zero. In such case, it is necessary to dilute the sample to keep final DO above zero.

4.1.1 Example of Unseeded 5 day BOD test

A 10.0 mL sample of sewage mixed with enough water to fill a 300-mL bottle has an initial DO
of 9.0 mg/L. For performing a test there should be a decrease in DO of at least 2.0 mg/L in 5
days. Also the final DO should be atleast 2.0 mg/L. For what range of BOD5 would this dilution
produce the desired results?

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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4.1.2 Example of Seeded 5 Day BOD Test

So far it is assumed that the dilution water added to the waste sample has no BOD of its own,
which would be the case if pure water were added. In some cases it is necessary to seed the
dilution water with microorganisms to assure there is an adequate bacterial population to carry
out the biodegradation. In such cases, to find the BOD of the waste itself, it is necessary to
subtract the oxygen demand caused by the seed from the demand in the mixed sample of waste
and dilution water.
In this case, two BOD bottles must be prepared, one containing just the seeded dilution water and
the other containing the mixture of both the waste water and seeded dilution water. The change in
DO from blank as well as mixture is then noted. The BOD of the waste is calculated from
following equation

Solved Example of BOD determination

A test bottle containing just seeded dilution water has its DO level drop by 1.0 mg/L in a 5 day
test. A 300-mL BOD bottle filled with 15 mL of waste water and the rest seeded dilution water
experiences a drop of 7.2 mg/L in the same time period. Determine the 5-day BOD of the waste.

4.2 Chemical Oxygen Demand

BOD does not give accurate results of pollution load because non-biodegradable wastes like
pesticides and detergents are resistant to microbial degradation and hence do not affect BOD.
Some other pollutants like cellulose get slowly oxidized. Thus, during the five days period
required for elucidation of BOD, these may be only partially oxidized. Sometimes the water
sample may contain toxic elements, which may poison the microbes even before they can act on
waste.

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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In order to overcome these problems another analytical parameter called chemical oxygen
demand (COD) is used. This is basically the measurement of oxygen-depletion capacity of
contaminated water sample. It is generally used as an indicator of water quality and is an
important part of water quality management programs. COD is also used to measure to BOD
(Biochemical Oxygen Demand) because both are strongly correlated, however COD is a much
faster, more accurate test. The process involves a two-hour digestion under acidic conditions and
high temperature. Potassium dichromate is used as an oxidant in this process. On the other hand
silver sulfate used as a catalyst and mercuric sulfate acts to complex out any interfering chloride.
The reduction process of Cr6+ to Cr3+ indirectly measures the oxygen demand. This can be done
by titration or spectrophotometry.
The water sample is heated with a known quantity of potassium dichromate for several hours and
the unreacted dichromate is then determined by titration with a standard Mohr’s salt solution.

4.2.1 Determination of COD

In the reflux flask add the following in sequence wastewater sample, standard potassium
dichromate and sulfuric acid reagent through sides of the flask. Cap and mix the contents and
reflux for about 1-2 hours. Repeat the procedure by substituting distilled water for sample.
Transfer the contents of the reflux flask in titration flask. Add distilled water to make the volume
to 50 cm3. At the end 1-2 drops of Ferroin indicator is added and titrated against standard ferrous
ammonium sulfate (Mohr’s salt) solution.
Calculation:

4.3 Total Organic Carbon (TOC)

This is the best method for the measurement of total organic matter in the water samples. TOC
involve heat, ultraviolet light, and a strong chemical oxidant for oxidation of organic compounds.
Oxygen demand is indirectly measured by estimating the amount of CO2 produced. This can take
several hours to complete.

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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Table 1: Difference in COD, BOD and TOC

Parameter COD BOD TOC

Oxidant Used K2Cr2O7, Mn2 (SO4)3 Oxidation by O2
microorganisms K 2 S 2O 8
Heat
Combination of the
above
Most Suitable Rapid and frequent monitoring Modeling treatment Measures amount of
Use of treatment plant efficiency plant process and the total organic carbon
and water quality effects of organic in samples
compounds on the
dissolved oxygen
content of receiving
waters
Test 1-1/2 to 3 hours 5 days Several minutes to
Completion hours
time
Advantages • Oxidant are unaffected by DO • Most closely models • Correlates with
• Short analysis time the natural BOD on waste with
environment when constant composition,
used with the proper but not as closely as
“seed” COD
• Short analysis
time
Disadvantages • Interference from • Toxic materials • Require
chloride ions kill microbes expensive
• Some organic • Microbes do not equipments
compounds are not oxidized oxidize all materials • Some organic
completely present in waste compounds are not
• Time consuming oxidized completely.
process • Measures total
organic carbon and
not oxygen demand

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters
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5. Summary

• Alkalinity, acidity, colour, turbidity, dissolved solids, hardness, free chlorine, BOD,
COD, DO, coliform count etc. are some of the parameters which are used to check the
quality of water.
• Biochemical oxygen demand (BOD) is a standard measure of the amount of oxygen that
would be needed by the microorganisms to cause bio degradation of a part of the organic
and inorganic pollution load.
• Pure drinking water, on the monthly average, should have 5 day BOD in the range of
0.75-1.5 mg/L. BOD value of a raw sewage runs from 200-400 ppm. BOD values of
several hundreds ppm indicate strong sewage.

CHEMISTRY PAPER No.4: Environmental Chemistry

MODULE No 10: Part 1 Analytical Techniques for
Measuring Water Quality Parameters