ENVIRONMENTAL ENGINEERING

LABORATORY MANUAL

ENVIRONMENTAL AND WATER RESOURCES ENGINEERING DIVISION

DEPARTMENT OF CIVIL ENGINEERING INDIAN INSTITUTE OF
TECHNOLOGY MADRAS CHENNAI -600 036

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 LIST OF ENVIRONMENTAL ENGINEERING EXPERIMENTS

Experiment Title of the Experiment Page no

No
E1 Determination of the turbidity, electrical conductivity and pH of 3-5
the given sample
E2 Determination of solids 6-8
E3 Determination of acidity, alkalinity and types of hardness 9-16
E4 Analysis of ions: copper, chloride and sulfate 17-20
E5 Estimation of optimum coagulant dosage 21-22
E6 Determination of chemical oxygen demand (COD) 23-24
E7 Determination of dissolved oxygen (D.O) and biochemical
Oxygen demand (BOD) 25-28
E8 Determination of break point chlorination 29-30

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 Experiment No.E1

TURBIDITY, ELECTRICAL CONDUCTIVITY AND pH

Aim: To determine turbidity, electrical conductivity and pH of the given samples.

(i) Turbidity: Turbidity is a measure of suspended matter that affects the light scattering/light
absorption properties of water. Jackson (light absorption principle) and Nephelometric
(intensity light scattering principle) meters are mostly used to measure turbidity of water
samples. The units of turbidity are Jackson turbidity unit (JTU) and Nephelometric turbidity
unit (NTU).

Principle: Turbidity is measured photo-metrically by determining the percentage of light of a

given intensity is scattered or absorbed.

Apparatus: Turbidity meter; sample tubes

Reagents: Reference standard turbidity solutions (0.2, 10 and 1000 NTU)

Procedure:
1. Switch on turbidity meter and wait for few minutes till the instrument warms up.
2. Shake the standard solution present in the cell/bottle before keeping it in sample
chamber/holder and measure the turbidity of the reference standard solutions.
3. Any deviation in reading of the reference solution, calibrate the instrument using
calibration switch.
4. Shake the sample before keeping it in sample chamber/holder and note down the
turbidity of the sample.

(ii) Electrical Conductivity: The electrical conductivity (EC) is a measure of the capacity of
a substance or solution to carry an electrical current. The conductivity is represented by
reciprocal value of electrical resistance in ohms relative to cubic centimeter of water at 25oC.
The measured EC value is used as an alternate method to estimate the total dissolved solids
(TDS) concentration of the sample. EC is represented by the symbol ‘k’ and its units are
millisiemens per meter (mS/m) or micromhos per centimeter [µmho/cm].

Principle: Conductivity is determined using the distance between the electrodes and their
surface area. According to Ohm’s law, the current through a conductor between two points is
directly proportional to the potential difference across the two points.

Apparatus: Conductivity meter, small beakers

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Reagent:

Distilled water or deionized water: The water is to have an electrical conductivity of less than
0.01 mS/m (< 0.1 µmho/cm). Boil the water shortly before use to minimize CO2 content (equal
to atmospheric equilibrium).

0.01M Standard potassium chloride solution (KCl): Take 745.6 mg of anhydrous KCl
(dried 1 hour at 180°C) in 1000 ml standard flask and make up to mark with distilled water.
This solution has an electrical conductivity of 141.2 mS/m (1412 µmho/cm) at 25o C.
Procedure:
1. Rinse conductivity cell with 0.01M KCl solution. Calibrate the conductivity
meter using the KCl reference solution to obtain cell constant.
2. Measure the electrical conductivity of the 0.01M KCl solution at room
temperature.
3. Rinse cell with sample. Measure the electrical conductivity of the sample.
4. Rinse the cell with deionized water between samples.
5. Thoroughly rinse the cell in distilled water after measurement, keep it in
distilled water when not in use.

Calculations

Compute the cell constant, KC according to the formula:

The conductance (G in µmho) of standard potassium chloride (KCl) solution is measured and
from the corresponding conductivity, a cell constant ‘C’ is calculated by the expression:
C = (k)/G. For 0.01 M KCl solution the ‘k’ value is 1412 µmho/cm.

EC= Gs x C (µmho/cm)
Where Gs= measured conductance of the given sample.
The TDS of an unknown sample is calculated using the following relationship:
TDS (mg/l) = C x EC (mmho/cm), where C is empirical constant (it varies between 0.55 to
0.9, depending upon the soluble solids present in water).

(iii) pH: pH is a measure of the hydrogen ion concentration of a solution. . Solutions with a
high concentration of hydrogen ions have a low pH and solutions with a low concentration of
hydrogen ions have a high pH. The pH scale is used to express the concentration of hydrogen
ions in a liquid. The pH scale ranges from 1 to 14 i.e. most acid to most alkaline. The hydrogen
ion concentration is an important parameter in determining the quality of water and
wastewater. The pH of the water/wastewater sample is measured by pH meter. A pH meter
consists of a measuring probe connected to electronic meter that measures and displays the pH
reading.

Principle: The electro chemical potential between a known liquid inside glass electrode and
unknown liquid outside. The meaning of pH is potential of hydrogen (H).

Apparatus: pH meter

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Procedure:

1. Rinse the probe with distilled water. Calibrate the pH meter using reference solution.
2. Rinse the probe with sample and dip the pH measuring probe in sample and read the
value of pH on the screen of the pH meter.
3. Rinse the probe with distilled/deionized water between samples.
4. Thoroughly rinse the probe in distilled water after measurement, keep it in
distilled water when not in use.

Observations and calculations:

Sample Turbidity Electrical conductivity pH

(NTU) (μS)

Results

Turbidity = ……………………………..NTU
Electrical conductivity = …………………………….μS/cm

pH =………………………………

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 Experiment No.E2
SOLIDS

Aim: To find the total, suspended, dissolved, volatile, fixed, settleable solids present in
the given sample.
Solids: Solids refers to the residue remaining after a water/waste water sample has been
evaporated and dried at a specified temperature (103-105ºC). High concentration of total solids
will make drinking water unpalatable and might have an adverse effect on human beings. The
main source of solids in water includes industrial discharge, sewage treatment plant, fertilizers,
road runoff, soil erosion etc.
Total solids (TS) consist of total suspended solids and dissolved solids. Total dissolved solids
(TDS) are mainly due to the inorganic matter present in solution in water. The main
constituents are calcium, magnesium, sodium and potassium. Hardness, scaly deposits,
sediments are some the effects caused by TDS. Total suspended solids (TSS) are the materials
that are retained in the filter paper when the TDS is filtered.
The term fixed solids (FS) are applied to the residue remaining after evaporation, drying at
103ºC followed by ignition at 600ºC. The loss of weight in oxidation and volatilization on
ignition is called volatile solids (VS). Determination of fixed and volatile solids does not
distinguish precisely between inorganic and organic matter because loss on ignition is not
confined to organic matter. It includes losses on volatilization of some mineral salts. The ratio
of the VS to FS is often used to characterize the waste water with respect to amount of organic
matter present.
The term settleable solid refers to the materials in suspension settled due to gravitational force
under quiescent condition. Settleable solids in surface and saline waters as well as domestic
and industrial wastes may be determined and expressed in ml/L. It can be either determined by
volumetric and gravimetric method. It is usually conducted in Imhoff cone which is graduated
glass cone of 1L capacity with a narrow apex.

Principle: Gravimetric and filtration

Apparatus: Evaporating dishes/porcelain dish or crucible, drying oven, desiccator, weighing

balance, Whatman filter paper, muffle furnace, filtration apparatus, Imhoff cone

Procedure:

(i) Total solids:

1. Dry evaporating dish at 104 ±1°C for 1 hour, cool and store in a desiccator.
2. Weigh the dish immediately before use. Note down the weight as B.
3. Stir sample with a magnetic stirrer. While stirring, pipette a measured volume into the pre-
weighed evaporating dish using a wide bore pipette.
4. Evaporate the sample to dryness in an oven at 104 ±1°C.If necessary add successive
portions to the same dish after evaporation.
5. To prevent splattering, the oven temperature may be lowered initially by 2°C below

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 boiling point and raised to 104°C after evaporation for 1 h. Cool in a desiccator and
note down the weight as A.

(ii) Total dissolved solids:

1. Measure the empty weight of porcelain dish and note down the reading as B.
2. Take known quantity of sample and pass it through the filter paper and collect the
filtrate.
3. Dry the filtrate sample in oven at 103ºC and cooled in a desiccator and note down the
final weight as A.

(iii) Total suspended solids:

1. Measure the empty weight of filter paper and note down reading as D.
2. Dry the filter paper with filtered sample in oven at 103ºC. Then cool it in a desiccator
and note down the final weight as C.

(iv)Total Volatile and fixed solids:

1. Keep the sample which is oven dried (sample used total solids, whose weight=A) in muffle
furnace at a temperature of 600ºC for 1 hour.
2. Cool the sample and note down the final weight as B. This will give the amount of volatile
solids.
3. The difference between total solids and total volatile solids gives total fixed solids.

(v) Settleable solids:

1. Fill the imhoff cone with sample and mix thoroughly.

2. Allow the solids to settle for 1 hour and note down the volume of solids settled at the apex
(in mL/L).

Observations and calculations:

Total solids, mg/L = {(A-B)/V}*1000

Where A= weight of dish + residue, mg after evaporation and drying of sample at

103oC
B = weight of dish, mg
V = volume of sample (mL)

Total dissolved solids, mg/L = {(A-B)/V}*1000

A= Final weight of the dish, mg

B = weight of dish, mg
V = volume of sample (mL)

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Total suspended solids, mg/L = {(C-D)/V}*1000

C= final weight of the filter paper containing the residue (mg)

D= initial weight of the filter paper (mg)
V= volume of sample (mL)

Total volatile solids, mg/L = {(A-B)/V}*1000

Where A= weight of dish + residue, mg after evaporation and drying of sample at

103oC
B = Final weight of the dish, mg after evaporation of sample at 600ºc
V = volume of sample (mL)

Total fixed solids, mg/L = Total solids – Total volatile solids

Sample No TS TDS TSS TFS TVS SS

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Results

1). Total solids (TS) present in the given sample was found to be =…………..

2). Total dissolved solids (TDS) present in the given sample was found to be =…….

3). Total suspended solids (TSS) present in the given sample was found to be =……..

4).Total fixed solids (TFS) present in the given sample was found to be =…………..

5).Total volatile solids (TVS) present in the given sample was found to be =…………..

6).Total settable solids (SS) present in the given sample was found to be =…………..

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 Experiment No.E3

ALKALINITY, ACIDITY AND HARDNESS

(i) Alkalinity: The alkalinity of water is a measure of its capacity to neutralize acids i.e. to
absorb hydrogen ions, without significant pH change. The alkalinity in water is primarily due
to the presence of salts of weak acids and strong bases. It is caused by presence of hydroxides
(OH-), carbonates (CO32-) and bicarbonates (HCO3-).
Aim: To determine the alkalinity in the given water and waste water samples.

Principle: Alkalinity can be obtained by neutralizing OH-,CO32-and HCO3-with standard

H2SO4. Titration to pH 8.3 or decolourisation of phenolphthalein indicator will show complete
neutralization of OH- and ½ CO32 -, while to pH 4.4 or sharp change from yellow to pink of
methyl orange indicator will indicate total alkalinity.

Ca(OH)2 + H2SO4→ CaSO4 + 2H2O

2CaCO3 + H2SO4→Ca(HCO3)2 + CaSO4

Ca(HCO3)2 + H2SO4→ CaSO4 + CO2

Apparatus: Burettes, volumetric flasks, conical flasks, measuring cylinder and beakers.

Reagents:

0.05N Standard sodium carbonate solution: Dry 3 to 5 g of sodium carbonate, Na2CO3, at

250°C for 4 hour and cool in a dessicator. Accurately weigh 2.5 g and dissolve in distilled water
and make to 1L.

0.1N Standard H2SO4 solution: Take 250 mL of distilled water and carefully add 2.8 mL of
conc. sulphuric acid to 1L distilled water. Standardise against 40.00 mL 0.05 N Na2CO3 with
about 60 mL distilled water, in a beaker by titrating potentiometric ally to pH 5. Lift out
electrodes, rinse into the same beaker and boil gently for 3 to 5 min under a watch glass cover.
Cool to room temperature, rinse cover glass into beaker and finish titration to pH 4.3. Calculate
normality of sulphuric acid:

Normality, N = (A×B)/(53.00 × C)

where:

A = g Na2CO3 weighed into the 1L-flask for the Na2CO3 standard

B = mL Na2CO3 solution taken for standardization
C = mL acid used in standardization

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0.02N Standard sulphuric acid solution:Dilute approximate 0.1 N solution to
1L.Calculate volume to be diluted as:
Volume (ml) = N/20
Where: N = exact normality of the approximate 0.1 N solution.

Phenolphthalein indicator solution (alcoholic, pH 8.3) - Dissolve 5 g phenolphthalein in

500 mL of 95% ethyl alcohol. Add 500 mL distilled water

Mixed indicator (Methyl Orange Indicator) - Dissolve 20 g of methyl red, 100 mg of

bromocrysol green in 100 mL 95% ethyl or isopropyl alcohol.

Procedure

Phenolphthalein alkalinity:

1. Take 25 to 50 mL sample in a conical flask.

2. Add 2 to 3 drops of phenolphthalein indicator. If it turns pink (pH > 8.3), titrate with
0.02 N H2SO4 till the pink colour disappear. Record volume (mL) of titrant used.

Observations and Calculations

Titration 1 (For Phenolphthalein alkalinity)
Burette solution: H2SO4
Pipette solution: Sample
Indicator: phenolphthalein
End Point: Disappearance of pink colour

Volume of
Sample Burette reading Volume of H2SO4
(ml) (ml)
Sl. No
Initial(ml) Final(ml)

Total alkalinity:

1. Add a drop of mixed indicator to the solution in which the phenolphthalein alkalinity
is determined.
2. Titrate it against 0.02 N sulphuric acid. Appearance of pink colour indicates the end
point.

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Observations and Calculations

Titration 2 (For total alkalinity)

Burette solution: H2SO4
Pipette solution: Sample
Indicator: mixed indicator (methyl orange)
End Point: Appearance of pink colour (yellow to pink)

Volume of Burette reading

S.No sample(ml) Volume of H2SO4
(ml)
Initial(ml) Final(ml)

Phenolphthalein alkalinity (as CaCO3 equivalent) = (V1*N of H2SO4* 50,000)/Vol. of

sample.
Total alkalinity (as CaCO3 equivalent) = (V2*N of H2SO4* 50,000)/Vol. of sample.

Result

Total alkalinity present in the water sample =

Phenolphthalein alkalinity present in the sample =
Methyl orange alkalinity present in the sample =

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 (ii) Acidity: Acidity is the measure of the amount of base required to neutralize a given
sample to the specific pH. Strong mineral acids, weak acids such as carbonic, acetic and
hydrolyzing salt such as ferric and aluminium sulphates may contribute acidity. It is
important because acid contributes to corrosiveness and influences certain chemical and
biological processes. Dissolved CO2 is usually the major acidity component of unpolluted
surface water. In the sample, containing only carbon dioxide-bicarbonate carbonate, titration
to pH 8.3 at 25°C corresponds to stoichiometric neutralization of carbonic acid to carbonate.
Since the colour change of phenolphthalein indicator is close to pH 8.3, this value is accepted
as a standard end point for the titration of total acidity. For more complex mixture or
buffered solution fixed end point of pH 3.7 and pH 8.3 are used. Thus, for standard
determination of acidity of wastewater and natural water, methyl orange acidity (pH 3.7)
and phenolphthalein acidity (pH 8.3) are used.

Aim: To determine the acidity in the given water and waste water samples.

Principle: Hydrogen ions present in a sample as a result of dissociation or hydrolysis of solutes

are neutralized by titration with standard alkali. The acidity thus depends upon the end point
pH or indicator used.

Apparatus: Burette, Pipette, conical flasks, measuring cylinder, volumetric flasks and beakers

Reagents

0.02N NaOH Solution: Dissolve 0.8 g of NaOH in distilled water and dilute to 1000 ml.

Methyl orange indicator: Dissolve 50 g of methyl orange powder in distilled water and
dilute to 100 ml.
Phenolphthalein indicator: Dissolve 1 g of phenolphthalein in 100 mL of 95% ethyl alcohol
or isopropyl alcohol, and add 100 mL of distilled to it. Add 0.02 N NaOH solution drop wise
until faint pink colour appears.

Procedure

1. Pipette out 25 mL of sample into conical flask. Add 2 drops of methyl orange indicator
to the sample solution.
2. Titrate the sample solution against 0.02 N sodium hydroxide solution. The end point is
noted when the colour changes from orange red to yellow.
3. Add two drops of phenolphthalein indicator and continue the titration till a faint pink
colour appears. Note down the volume of the titrant consumed.

Observations and calculations

Burette solution: NaOH

Pipette solution: Sample
Indicator: Methyl orange, Phenolphthalein
End Point: Yellow, Pink

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 Burette reading Volume of
Volume of
S.No
sample(ml)
Initial (ml) Final (ml) NaOH (ml)

Methyl orange acidity due to mineral acids (as CaCO3 equivalent) =

(V1*N of NaOH *50,000)/Vol. of sample

Phenolphthalein acidity =
Total acidity (as CaCO3 equivalent) = (V2*N of NaOH *50,000)/Vol. of
sample

Result

Methyl orange acidity =

Phenolphthalein acidity =
Total acidity =
(iii) Hardness: It is the property of water that requires considerable amount of soap to produce
a foam or lather and produces scales in the hot water units. Hardness in water is caused by
multivalent metallic cations.

Aim: To determine the total hardness, calcium hardness and magnesium hardness of the given
water sample.

Principle: In alkaline solution ethylene diamine tetra acetate (EDTA) react with Ca and Mg to
form a soluble chelated complex. Ca and Mg ions develop wine red color with Eriochrome
black T under alkaline condition. When EDTA is added as titrant, Ca and Mg divalent ions get
complex resulting in sharp change from wine red to blue which indicates end point of the
reaction.

Ca2+ + Mg 2+ + EDTA PH 10 Ca EDTA + Mg EDTA

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Apparatus: Burette, Pipette, conical flasks, measuring cylinder, volumetric flasks and
beakers.

Reagents

Buffer solution: Dissolve 16.9 g NH4Cl in 143 mL conc. NH4OH. Add 1.25 g magnesium
salt of ethylene diamine tetra acetate (EDTA) and dilute to 250 mL with distilled water. Store
it in air tight plastic bottle for up to one month.

Complexing agent: Magnesium salt of 1, 2 cyclohexane diamine tetra acetic acid. Add 250
mg per 100 mL sample only if interfering ions are present and sharp end point is not obtained.

Indicator: Eriochrome Black T sodium salt. Dissolve 0.5 g dye in 100 mL triethanolamine or
2 ethylene glycol monomethyl ether. The salt can also be used in dry powder form by grinding
0.5 g dye with 100 g NaCl.

0.01M Standard EDTA solution: Weigh 3.723 g di-sodium salt of EDTA dihydrate, dissolve
in distilled water and dilute to 1000 mL. Store in polyethylene bottle.

Standard Calcium Solution: Weigh 1.000 g anhydrous CaCO3 in a 500 mL flask. Add 1mL
HCl slowly through a funnel till all CaCO3 is dissolved. Add 200 mL distilled water and boil
for a few minutes to expel CO2. Cool and add a few drops of methyl red indicator and adjust
to the intermediate orange color by adding 3N NH4OH as required. Transfer quantitatively and
dilute to 1000 mL with distilled water, 1 mL = 1mg CaCO3.

Procedure

Total hardness:

1. Take 25 ml of sample in a conical flask. Add 2 ml of ammonia buffer and a pinch of

eriochrome black T to it. The sample will turn to wine red in color.
2. Titrate the sample with 0.01 M EDTA till the wine red color turns to blue. Note down
the volume of EDTA used (V1).

3. Repeat the procedure with blank sample and note down the volume of EDTA used
(V2).

Calcium hardness:

1. Take 25 ml sample in a conical sample. Add 1 ml of 1 M NaOH to the sample to

raise pH to 12. Add a pinch of muroxide indicator to it. The sample will turn to pink
in color.
2. Titrate the sample with 0.01 N, EDTA till the pink color turn to purple color. Note
down the volume of EDTA used (V3).
3. Repeat the experiment for blank sample and note down the volume of EDTA used
(V4).

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 Permanent hardness:

1. Take 25 ml of sample in a conical flask. Add 2 ml of ammonia buffer and 2-3 drops
of EBT to it. The will turn to wine red in color.
2. Titrate the sample with 0.01 M EDTA till the wine red color turns to blue. Note down
the volume of EDTA used (V5).
3. Repeat the procedure with blank sample and note down the volume of EDTA used
(V6).

Observations and calculations

Initial burette Final burette Difference

reading reading

Total hardness Sample (V1)

Blank (V2)
Calcium
hardness Sample (V3)

Blank (V4)

Permanent Sample (V5)

hardness
Blank (V6)

Total harness (in mg/L as CaCO3 equivalent) = {(V1-V2) x1000} / vol of

sample (mL)

Calcium harness (in mg/l as CaCO3) = {(V3-V4) x1000} / vol of sample (mL)

Permanent hardness (in mg/l as CaCO3) = {(V5-V6) x1000} / vol of sample (mL)

Magnesium hardness = total hardness -calcium hardness

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Results

Total harness (in mg/L as CaCO3) = ………………………..

Calcium harness (in mg/L as CaCO3) = …………………………

Permanent hardness (in mg/L as CaCO3) = ….………………………

Magnesium hardness (in mg/L as CaCO3) = ………………………….

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 Experiment No.E4

IONS: CHLORIDE, SULFATE AND COPPER

(i) Chloride: Chloride is present in water and wastewater in varying concentration. Various
sources such as mineral contents, sea water droplets, human excreta discharging to natural
water bodies contribute chloride concentration to water.

Aim: To determine the chloride concentration present in given water sample.

Principle: Chloride ion concentration in the water can be determined by titration with silver
nitrate. As the silver nitrate solution is slowly added, a precipitate of silver chloride forms.
Ag+ (aq) + Cl– (aq) →AgCl (s)

The end point of the titration occurs when all the chloride ions are precipitated. Then additional
silver ions react with the chromate ions of the indicator, potassium chromate, to form a red-
brown precipitate of silver chromate.

2Ag+ (aq) + CrO42– (aq) → Ag2CrO4 (s)

Titration should be carried out under conditions of pH 6.5 – 9. At higher pH silver ions may
be removed by precipitation with hydroxide ions, and at low pH chromate ions may be removed
by an acid-base reaction to form hydrogen chromate ions or dichromate ions, affecting the
accuracy of the end point.

Apparatus: Burette, pipettes, conical flasks, beakers, measuring cylinders, weighing

balance, stirrer etc.

Reagents

Indicator 5% K2CrO4: 1.0 g of K2CrO4 dissolved in 20 mL of distilled water.

AgNO3 solution: weigh 9.0 g of AgNO3 and transferred to a 500 mL volumetric flask and
make up to the mark with distilled water. The resulting solution is approximately 0.1 M.

Procedure

1. Take 25 ml of sample in the conical flask. Adjust the sample pH between to be 7 to 8 by

adding sulphuric acid or sodium hydroxide solution.
2. Add 1 ml of potassium chromate to get light yellow color.
3. Titrate with standard silver nitrate (AgNO3) solution till the color changes from yellow to
brick red. Note down the volume of AgNO3 solution added (V1).

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4. Repeat the above procedure for the blank sample (distilled water) and note down the
volume of AgNO3 solution added (V2).

Observations and calculations:

Trial Volume of AgNO3 (mL)

Initial Final
FR-IR
Reading(IR) Reading(FR)

Blank

Chloride in mg/L = {(V1-V2) * N of AgNO3 *35.45* 1,000}/Vol. of sample

Result

Chloride concentration in the given sample =

(ii) Sulfate: The sulfate ion is one of the major anions occurring in natural water. The presence
of sulfate increases the formation of hard scales in boilers and heat exchanger. Reduction of
sulfate to hydrogen sulfate under anaerobic conditions causes odour and sewer corrosion
problems.

Aim: To determine the sulfate concentration present in given water sample.

Principle: The concentration of sulfate is determined by light absorption principle. Sulfate ion
(SO42-) is precipitated in an acetic acid medium with barium chloride (BaCl2) so as to form
barium sulfate (BaSO4) crystals of uniform size.

SO42- (aq) + Ba2+ (aq) → BaSO4 (s)

Light transmittance of the BaSO4 suspension is measured by turbidity meter and the
SO42- concentration is determined by comparison with the standard chart.
Apparatus: Turbidity meter, weighing balance, stirrer, conical flasks, beakers, measuring
cylinders

Reagents

BaCl2
Buffer solution

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 Procedure

1. Take 100 ml of sample in a conical flask and add 20 ml buffer solution and mix in a stirring
apparatus. During stirring add one spoon of BaCl2 crystal and stir it for 1-2 minutes at
constant speed.
2. Pour the solution in to spectrometer (420 nm) absorption cell and measure the absorbance
within 5 minutes.
3. Estimate SO42- concentration in the sample by comparing sample absorbance with standard
chart.
4. Repeat the above procedure for determining the absorbance of known SO42-concentration
in the range of 0 to 40 mg/L with an increment of 5 mg /L and prepare standard chart.

Observations and calculations:

Sulfate concentration Absorbance

(mg/L)

Result

Sulfate concentration in the given sample =

(iii) Copper: Copper rarely occurs naturally in water. Most copper contamination in drinking
water is due to corrosion of the copper pipes or fittings. At very high concentrations, copper
causes bitter metallic taste in water and result in blue-green stains on plumbing fixtures. At
low concentrations, copper is not harmful to human.

Aim: To determine the copper concentration present in given water sample

Principle: The concentration of copper is determined by light absorption principle.

Apparatus: UV-Visible Spectrophotometer, weighing balance, conical flasks, beakers,

measuring cylinders.

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Reagents
1N Acetic acid
5 % Potassium ferrocyanide [K4 Fe (CN)6]

Procedure

1. Take known quantity of sample and add 1 mL of 1 N acetic acid and 5 mL of 5 %

K4 Fe (CN)6 and mix thoroughly.
2. Dilute the sample using distilled water and make up to 25 ml. Transfer the solution in to
spectrometer absorption cell and measure the absorbance at 480 nm.
3. Find out the copper concentration from the standard graph corresponding to the sample
absorbance.

Observations and calculations:

Copper concentration Absorbance

(mg/L)

Results

Copper concentration in the given sample =

20
 Experiment No.E5

OPTIMUM COAGULANT DOSAGE

Coagulation: Coagulation is the process of destabilizing colloidal particles so that particle

growth can occur as a result of particle collisions. In wastewater treatment settleable solids are
effectively removed by sedimentation process. But, the small size colloidal particles are not
possible to remove by gravitational settling due to Brownian motion. However, if the colloidal
particles are destabilized through agglomeration of particles into group/large particles, increase
in settling velocities, they can be effectively removed by sedimentation tank. The theory of
chemical coagulation is very complex. The exact mechanism of coagulation is not known,
however, following four mechanisms are thought to be occurring during coagulation process.
These include ionic layer compression, adsorption, charge neutralization and inter-particle
bridging. Typical coagulants used in wastewater treatment are synthetic organic polymers,
metal salts such as alum or ferric sulphate, prehydrolized metal salts (polyaluminum chloride
and polyiron chloride).

Aim: To find the optimum amount of coagulant required to treat given water sample.

Principle: Metal salts hydrolyse in presence of the natural alkalinity to form metal hydroxides.
The divalent cations can reduce the zeta-potential, while the metal hydroxides are good
absorbents and hence remove the suspended particles by enmeshing them.
Alum [Al2S(SO4)3. 18H2O] is the most widely used coagulant in water treatment. When alum
solution is added to water, the molecules dissociate to yield SO42- and Al3+. The +ve species
combine with negatively charged colloidal to neutralise part of the charge on the colloidal
particle. Thus, agglomeration takes place.

Coagulation is a quite complex phenomenon and the coagulant should be distributed uniformly
throughout the solution. A flash mix accomplishes this.

Apparatus: Jar test apparatus, turbid meter, beakers, pipette and pH meter.

Reagents

Alum, Ferric chloride

Procedure

1. Measure the initial turbidity of the given sample.

2. Find the pH of the sample and adjust it to 6 to 8.5.
3. Take six jars of 1L capacity and take 0.5 L of sample in each jar and add varying doses of
alum (1, 2, 4, 6, 8, 10 mg/l) of alum to each one of them.
3. Keep the sample in jar test apparatus and put it for rapid mixing at 100 rpm for 1 min and
then to slow mixing at 20 rpm for 20 min.

21
4. Stop the motor and allow the sample to settle for 30 min. Collect the supernatant from each
jar and find out the turbidity.
5. Plot a graph with alum dosage along x-axis and turbidity along y-axis.
6. The dosage of alum, which represents least turbidity, gives Optimum Coagulant Dosage
(O.C.D.).
7. Repeat steps 3–6 with higher dose of alum, if necessary.

Observations and calculations

Concentration (ppm) Turbidity (NTU)

Result

Optimum coagulant dosage = ……………………….. mg/L

22
 Experiment No.E6

CHEMICAL OXYGEN DEMAND

Chemical oxygen demand (COD): This test is used to measure the quantity of oxygen required
to oxidize the organic material in wastewater using dichromate in an acid solution. COD test is
widely used as a means of measuring the organic strength of domestic and industrial wastes. It
allows measurement of a waste in terms of the total quantity of oxygen required for oxidation
to CO2 and H2O. The major advantage of COD test is the short time required for evaluation.
Many organic matters which are difficult to oxidize biologically such as lignin can be oxidized
chemically.

Aim: To determine the Chemical oxygen demand (COD) of the given sample.

Principle: It is based on the principle that organic matter present in the sample gets oxidized
completely by potassium dichromate (K2Cr2O7) in the presence of sulphuric acid (H2SO4) and
catalyst silver sulphate (Ag2SO4) to produce CO2 and H2O. The excess of potassium
dichromate remaining after the reaction is treated with ferrous ammonium sulphate. The
dichromate consumed gives O2 required for oxidation of organic matter.

Apparatus: COD digestion vessel, COD digester, burette, pipette and beaker.

Reagents

Standard potassium dichromate solution: 0.0417M (0.25N): Dissolve 12.259 g K2Cr2O7,

primary standard grade, previously dried at 103ºC for 2 hours, in distilled water and dilute to
1L.

Sulphuric acid reagent:Add 5.5g Ag2SO4 technical or reagent grade, per kg of conc.H2SO4,
keep for a day or two to dissolve.

Ferroin indicator solution: Dissolve 1.485 g 1, 10-phenanthroline monohydrate and 695mg

FeSO4.7H2O in distilled water and dilute to 100 mL. Commercially prepared may also be
available.

Standard ferrous ammonium sulphate (FAS):0.25M: Dissolve 98 g Fe(NH4)2(SO4)2. 6H2O

in distilled water, add 20 mL conc. H2SO4, cool and dilute to 1L.

Procedure

1. Take 2.5 ml of the sample in digestion vessel and add 1.5 ml of 0.25 N K2Cr2O7 solution
and 3.5 ml of Ag2SO4 + H2SO4 solution.
1. Reflux the mixture on a hot plate/digester for 2 hrs at 150ºC and cool the mixture to room
temperature.
2. Titrate mixture against ferrous ammonium sulphate (FAS) solution using ferroin

23
 indicator till blue green color turns to reddish brown color. Note down the volume of
FAS used as ‘A’ ml.

4. Repeat the experiment for blank sample (distilled water) and note down the volume of
FAS used as ‘B’ ml.

Observations and calculations:

COD (mg/L) = [{(B-A) *M *8000} * dilution factor (if any)]/ Volume of Sample

where:

A = FAS used for sample, ml

B = FAS used for blank, ml
M = Normality of FAS

Sample no sample Burette reading Dilution factor Volume of FAS

consumed(ml)
Initial Final (if any)

Sample 1 Hot blank

Diluted sample

Sample 2 Hot blank

Diluted sample

Results

The COD of the given water sample was found to be………………..

24
 Experiment No.E7
DISSOLVED OXYGEN (DO) AND
BIOCHEMICAL OXYGEN DEMAND (BOD)

(i) Dissolved Oxygen (DO): Dissolved oxygen is one of the most important constituents of
natural water system. It indicates the pollution status of river. The dissolved oxygen in water
depends upon its temperature and solubility. If DO is less, then it indicates the presence of
organic matter. At least 4 mg/L of DO is required for fish and other species for survival.
Aim: To determine the amount of dissolved oxygen present in the given sample

Principle: It is based on the principle that oxygen present in the sample oxidizes the divalent
manganous to its higher valence under alkaline conditions and that manganese in higher state
of valencies is capable of oxidizing I- to I2 under acidic conditions. Thus the amount of I2
released is equivalent to the dissolved oxygen present. The iodine is measured with standard
sodium thiosulphate solution.

If no oxygen is present, a pure white precipitate of Mn(OH)2 forms

Mn2++ 2OH-→Mn (OH)2 (s) ( white ppt)

If oxygen is present
Mn2+ + 2OH- + O2→ MnO2 (s) + H2O (red ppt)

Under low pH
MnO2 + 2I- + 4 H+→ Mn2+ + I2 + 2H2O

I2 is rather insoluble in water, but forms a complex with the excess iodide present. Thus
more soluble tri-iodate prevents escape of I2 from the solution.
I2 + I- ↔ I3-

Apparatus: 300 mL BOD bottles, burette, pipette, conical flask etc.,

Reagents
Manganous sulfate solution: Dissolve 480 g MnSO4 4H2O,or 400 g MnSO4 2H2O,or 364 g
MnSO4 H2O in distilled water, filter and dilute to 1 litre. This solution should not produce a
blue color with starch indicator when added to an acidified potassium iodide (KI) solution.
Alkaline-iodide-sodium azide solution: Dissolve 500g NaOH (or 700g KOH) and 135 g NaI
(or 150 g KI) in distilled water and dilute to I L. Add 10 g NaN3 dissolved in 40 mL distilled
water.

Starch indicator solution: Use either an aqueous solution or soluble starch powder mixture.
Prepare an aqueous solution by dissolving 2 g of laboratory grade soluble starch powder and
0.2 g of salicylic acid (as a preservative) in 100 mL of hot distilled water.
Sodium thiosulfate standard solution, 0.025 N: Dissolve 6.205 g Na2S2O3 5H2O in distilled

25
water. Add 1.5 mL 6 N NaOH or 0.4 g solid NaOH and dilute to 1 litre. Standardize with bi-
iodate solution.
Procedure

1. Collect the sample to be tested in a 300 mL BOD bottle taking special care to avoid
adding air to the liquid being collected. Fill bottle completely and add stopper.
2, Remove bottle stopper and add 2 mL of the manganous sulfate solution at the surface of the
liquid. Add 2 mL of the alkaline-iodide-sodium azide solution at the surface of the liquid.
Replace the stopper, avoid trapping air bubbles and shake well by inverting the bottle
several times.
3. Repeat shaking after floc has settled halfway. Allow floc to settle a second time.
4. Add 2 mL of concentrated sulfuric acid and close the bottle with stopper. Rinse the top of
the bottle to remove any acid and shake well until the precipitate is completely dissolved
(uniform yellow color).
5. Take 203 mL of sample from the BOD bottle into a conical flask and titrate with
0.0250 N sodium thiosulfate until the solution is a pale yellow (straw) color.
6. Add a small quantity (approximately 1 mL) of starch indicator continue the
titration with 0.0250 N sodium-thiosulfate until blue colour disappears (blue to
colorless). Record the mL of sodium-thiosulfate used.

Observations and Calculations

Calculate the concentration of DO in the sample using the following formula:

Burette reading mL of (Na2S2O3 5H2O)

Sample Final reading (FR) Initial reading (IR)

I II Avg I II Avg FR-IR

Result
DO of the given sample =

26
(ii) Biochemical Oxygen Demand (BOD): BOD is defined as the amount of oxygen required
by bacteria while stabilizing decomposable organic matter under controlled aerobic conditions.
This test is widely used to determine the pollution strength of domestic and industrial wastes
in terms of the oxygen demand. The BOD test relies on measurable depletion of dissolved
oxygen (DO) over a specified period of time, generally 5 day at 20o C incubation. The BOD is
considered complete after 20 days. 20 Days is too long to wait and 5 days is a reasonable period
as most of the BOD to be exerted is about 70 to 80 % of total BOD.

Aim: To determine the BOD of the given sample

Principle: The BOD is measured by determining the oxygen consumed (by the bacteria) from
a sample placed in an air-tight container and kept in a controlled environment for a
preselected period of time.

Apparatus: BOD bottles, burette, pipette, conical flask, BOD Incubator

Reagents

Phosphate buffer solution: Dissolve 8.5 g KH2PO4, 21.75 g K2HPO4, 33.4 g Na2HPO47H2O,
and 1.7 g NH4Cl in about 500 mL distilled water and dilute to 1 L. The pH should be 7.2 without
further adjustment. Alternatively, dissolve 42.5 g KH2 PO4 or 54.3 g K2HPO4 in about 700 mL
distilled water. Adjust pH to 7.2 with 30% NaOH and dilute to 1 L.
Magnesium sulfate solution: Dissolve 22.5 g MgSO47H2O in distilled water and diluteto 1 L.
Calcium chloride solution: Dissolve 27.5 g CaCl2in distilled water and dilute to 1 L.

Ferricchloride solution: Dissolve 0.25 g FeCl36H2O in distilled water and dilute to 1 L.

Dilution water: Place desired volume of distilled water in a suitable bottle and add 1 mLeach
of phosphate buffer, MgSO4, CaCl2, and FeCl3 solutions/L of water. Seed dilution water, if
desired. pH of the dilution water should be between 6.5- 8.5 ( it is customary to buffer the
solution by means of a phosphate system at about pH 7) calcium and magnesium salts are
added to give buffering capacity and proper osmotic conditions also serve to provide with any
of these elements that are needed in growth and metabolism. Ferric chloride and magnesium
sulphate supply the requirements for iron sulphur and nitrogen. The phosphate buffer furnishes
any phosphorous that may be needed. The nitrogen should be eliminated in cases where
nitrogenous oxygen demand is being measured.
Procedure
1. Dilute the settled sewage provided to 30-40 times using aerated tap water.
2. Fill the BOD bottle in duplicate with diluted sewage by taking care that no air bubble
entraps.

3. Determine the DO of the BOD sample and blank.

4. Incubate both the sample and blank BOD bottles at 200 C. After 5 days take the bottles
having sewage and blank and measure DO calculate BOD5.

27
Observations and calculations
0th day reading

Sample Burette reading mL of (Na2S2O3 5H2O) DO in mg/L

Final reading (FR) Initial reading (IR) FR-IR

Blank

BOD sample

5 day reading
Burette reading mL of (Na2S2O3 5H2O) DO in mg/L
Sample
Final reading (FR) Initial reading (IR) FR-IR

Blank

BOD sample

5 day BOD,= BOD5 (mg/l) = {[D1-D2]-[B1-B2]}/ P

D1= DO of the sample immediately after preparation, mg/L,

D2= DO of the sample after 5 day incubation at 20°C, mg/L,
B1= DO of blank immediately after preparation, mg/L,
B2= DO of blank after 5 day incubation at 20°C, mg/L,
P= dilution factor

Ultimate BOD, Lt=L0(1-e-kt)

Lt= BOD at any time t

L0= ultimate BOD
t= time in days
k= BOD rate constant (0.23/day)

Result

BOD of the given sample =

28
 Experiment No.E8

BREAK POINT CHLORINATION

Chlorination: Water used for drinking and cooking should be free of pathogenic
(diseasecausing) microorganisms that cause such illnesses as typhoid fever, dysentery, cholera,
and gastroenteritis. Purification of drinking water containing pathogenic microorganisms
requires specific treatment called disinfection. Several disinfection methods eliminate disease-
causing microorganisms in water, chlorination is the most commonly used.

Aim: To determine the chlorine demand for given sample and break point chlorination.

Principle: Chlorine combines with water to form hypochlorous and hypochloric acid.
Hypochlorous acid dissociates to give the OCl- and HOCl depend upon pH of the solution.
Hypochlorides also give the OCl- ions, HOCl rupture the cell membrane of microbes (disease
producing organisms). These also react with the impurities like ammonia, oxidizable organic
matter like ferrous ions, nitrites, etc. to form chloramines and stable ions of the latter
respectively.

The “Breakpoint Chlorination” Curve: Reaction of HOCl with Pure H2O + NH3

Regions 1 and 2: Formation of combined Cl2 dominates over oxidation of N; concentration of

residual Cl2 increases with increasing Cl2:N ratio
Region 3: Oxidation of N dominates over formation of combined Cl2; when Cl2:N ratio
increases, more combined Cl2 is oxidized than is formed
Region 4: All N oxidized; increase in Cl2:N ratio leads to increase in free Cl2 residual

Apparatus: Beakers, conical flasks, burette

29
Reagents: Standard chlorine solution, acetic acid, potassium iodide, 0.025N standard
sodium thiosulphate solution, starch indicator.

Procedure:

1. Take 1 liter of samples in six jars and add varying amount (1, 2, 3, 4, 5, 6, 8 mg/l)
chlorine solution to each jar.
2. Stir the sample with a glass rod/mechanical mixer for complete mixing. Allow 20
minutes contact time for chemical reaction.
3. Take 25 ml of sample in a conical flask and add 5 ml of acetic acid and 1 gram of
potassium iodide and allow the reaction to complete.
4. Titrate the sample with 0.025 N standard sodium thio-sulphate solution until the
yellow color of the librated iodine is almost faded out.
5. Add 1 ml of starch indicator, the solution turns blue. Continue the titration till the blue
color disappears. Note down the volume of sodium thio-sulphate consumed (A).
6. Repeat the procedure for blank sample (B).
7. Determine the available residual chlorine in the sample using following equation: {(A-
B)*N*35.45*1000}/volume of sample in ml.
8. Plot graph between concentration of chlorine added and residual chlorine to find out the
break point chlorination.

Observations and Calculations

Chlorine dosage (mg/l) Residual chlorine(mg/l)

Result

Break point chlorination: …………………..

30
References

Standard Methods for the Examination of Water and Waste Water, 1995. 20th Edition,
APHA.

Peavy, H.S., Rowe, D.R., Tchobanoglous, G. Environmental Engineering, 1985.McGraw

Hill International Editions, New York.

Sawyer, C.L., McCarthy, P.L. and Parkin, G. F.,1994. Chemistry for Environmental
Engineering.McGraw Hill International Editions, New York.
MetCalf and Eddy.,1991. Wastewater Engineering, Treatment, Disposal and Reuse.3rd
Edition, Tata McGraw Hill, New Delhi.

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