LAB MANUAL

ENVIRONMENTAL ENGINEERING

SUBMITTED BY:

ABID HUSSAIN
2018-Civ-311

SUBMITTED TO:

ENGR.INTEZAR HUSSAIN

University of Engineering and Technology Lahore

(Narowal Campus)
 TBALE OF CONTENTS

1. To determine the pH of the given sample of water using electrodes.............................1

2. To determine Turbidity in different samplesof water....................................................4
3. Determination of Hardness of Water.............................................................................7
4. To determine the amount of total dissolved solids in water.........................................11
5. To Determine Amount of dissolved oxygen (DO) in water.........................................14
6. To determine the amount of BOD in Domestic Waste Water.....................................17
7. To determine chemical oxygen demand (COD) in water............................................21
8. To determine the amount of nitrogen in given water sample.......................................23
9. Determination of Chlorides in drinking water.............................................................26
10. To determine the Electrical Conductivity in different water samples………………..27
11. To Determine the Amount of Calcium and Magnesium in Given Water
Sample……………………………………………………………………………….30.
12. To Determine the Amount of Calcium and Magnesium in a Given Water
Sample………………………………...........................................................………..32
 EXPERIMENT NO. 1
TO DETERMINE THE PH OF THE GIVEN SAMPLE OF WATER
USING ELECTRODES

SCOPE:

It is a critical parameter in

 Agricultural Research
 Chemical production
 Environmental monitoring
 Life sciences research
 Food Industry
 Beverage Industry
 water and waste water treatment for industrial and municipal applications. etc

SIGNIFICANCE:

1 In the field of water supplies, it is a factor that must be considered in chemical

coagulation, disinfection, water softening and corrosion control.
2 In wastewater treatment employing biological processes, pH must be controlled
within a range favorable to the particular organisms involved.
3 In chemical processes used to coagulate wastewaters, dewater sludge’s, or oxidize
substances, such as cyanide ion, require that the pH be controlled within rather narrow
limits.
4 pH is the important parameter in studying the properties of concrete. Low and high
pH both creates problem in concrete in terms of corrosion and spalling. For this
ASTM has recommended 0.6% alkalinity of cement or mineral admixtures (if
alkaline) for use in concrete.
5 For construction use, recommended value of pH should be 7.2-7.8.
6 The decrease in pH of the concrete mix before casting and molding affects the early
hydration and strength but improves the later age concrete properties.
7 Decreasing the pH level signifies the increase of acidity in the concrete. Thus,
corrosion of reinforcement bar in the concrete when pH value is less than 7 will
increase the action of corrosion. 

THEORY:

pH is a term used universally to express the intensity of the acid or alkaline condition of a
solution. PH refers to the hydrogen ion activity.It is expressed as the negative logarithm ofthe
reciprocal of the hydrogen ion activity in moles per litre. It is the way of expressing the
hydrogen ion activity. The pH scale is usually represented as ranging from 0 to 14, with pH 7
at 250 C as neutral.It can be measuredby PH paper or electrometrically by measuring of
hydrogen ion by potentiometricmeasurement using a standard hydrogen electrode and a
reference electrode.Some of the processesin water quality engineering that require pH

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monitoring and control are the following: disinfection,coagulation, softening, biological
treatment etc. Natural waters usually have pH values close to neutral.
Below figure shows pH values of commonly used household products.

PRINCIPLE:

pH is measured by pH meter using a glass electrode which generates a potential varying

linearly with the pH of the solution in which it is immersed. Calomel of Ag/AgCl/KCl
reference electrode is usually used for determination.

APPARATUS:

1. pH meter
2. Standard Hydrogen Electrode
3. Reference electrode
4. Sample Electrode
5. 50ml sample
6. Beaker

Figure no 1: PH calculation by PH meter

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PROCEDURE:

1. Remove the pH electrode from storage bottle. Rinse with distilled water to remove
any impurities.
2. Press ON to switch meter on
3. Press MODE key to select pH measurement mode.
4. Take 50ml of sample in a beaker.
5. Dip the probe into the sample for which the pH measurement is required. Also dip the
conductivity cell also as it contains temperature sensor. Stir gently to create
homogeneous sample.
6. Allow time for the reading to stabilize. Note the reading on the display after ready
indicator is appears.
7. Follow the same procedure for different samples.
8. Rinsing the electrode before immersing in the next solution.

OBSERVATIONS AND RESULTS:

Table #1: ph calculation

Sr# Sample name Temp PH

1 Drinking water

2 Rain water

PRECAUTIONS:

1) Periodically check for damage to electrodes.

2) Electrode tip should be kept moist during storage. Follow manufacturer’s instructions.

CONCLUSION/COMMENTS:

For construction purposes, the recommended pH of water has range of 7.2-7.8. Form the
above results, it is clear that none of the sample is suitable for use in construction. Using
water with pH not in the given range will have adverse effect on quality of concrete as it will
affect early hydration and strength of the concrete mix. It will also have negative effect on the
reinforcements provided in concrete. Overall, all of the 2 samples are not recommended of
use for any kind of construction purposes.

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 EXPERIMENT NO.2
TO DETERMINE TURBIDITY IN DIFFERENT SAMPLES OF
WATER
 
SCOPE:

Turbidity in water is due to suspended particles like clay, silt and finely divided organic
matter and microscopic organisms.Suspension of such particles in water which interfere with
the passage of light is called turbidity.
Turbidity is a measure of the loss of transparency of water due to thepresence of suspended
particles. The more total suspended solids in the water, more non-transparent it seems and the
higher the turbidity. Turbidity is a good measureof the quality of water. Turbid water is
undesirable from aesthetic point of view in drinking water supplies andmay also affect
products in industries. It also causes a number of problems in water treatment plants. The
permissible limits of turbidity for drinking water is 5 to 10 ppm. The WHO establishes that
the turbidity of drinking water shouldn't be more than 5 NTU and should ideally be below 1
NTU.
Turbidity is measured in NTU: Nephelometric Turbidity Units. The instrument used for
measuring it is called nephelometer or turbidimeter, which measures the intensity of lights
scattered at 90 degrees as a beam of light passes through a water sample.

Particles with Specific Gravity < 1.2 are suspended in water.

Particles with Specific Gravity > 1.2 settle down in water.

ENVIRONMENTAL SIGNIFICANCE:

1. Turbid water is undesirable from aesthetic point of view. Consumers will hesitate to
drink the turbid waters.
2. Turbid waters pose problems in water treatment plants. Efficiency of the filters is
reduced.
3. Disinfections is also affected since pathogenic organisms will take shelter between
particles and will not get destroyed.
4. Excessive suspended sediment can impair water quality for aquatic and human life,
impede navigation and increase flooding risks.
5. The European standards for turbidity state that it must be no more than 4 NTU. The
World Health Organization establishes that the turbidity of drinking water should
not be more than 5 NTU and should ideally be below 1 NTU.
6. If the mixing water contains suspended particles in an amount up to 0.02 percent by
weight of total water used in concrete, it will not affect the concrete properties.
 
PRINCIPLE:

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When light is passed through a sample with turbidity, rays of light are scattered by the
particles. The scattering of the light is directly proportional to the turbidity. The turbidity of
a sample is thus measured from the amount of light scattered by the sample taking a reference
with standard turbidity suspension. Turbidity can be measured either by its effects on the
transmission of light which is termed as turbidimetry or its effects on the scattering of light
which termed as Nephelometry. Turbidimetry can be used for sample with moderate turbidity
and Nephelometer for sample with low turbidity. Higher the intensity of scattered lighthig her
the turbidity.

APPARATUS:

Nepheloturbiditymeter.

PROCEDURE:

1) Switch on the Nephelometer.

2) Take 50ml of well shaken sample in quartz cell.
3) Place it in turbidity meter.
4) Record the turbidity reading directly in NTU.

OBSERVATIONS AND CALCULATIONS:

Table #2 :
Sample Number Source Turbidity

1 S1

2 S2

3 S3

4 S4

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 EXPERIMENT NO 3
DETERMINATION OF HARDNESS OF WATER

SCOPE:
This test is done to determine the total hardness (Ca & Mg) present (as CaCO3) in the water
sample by EDTA method.
Following are the reasons for which determination of hardness of water is necessary
 Presence of some divalent ions like sulphide, chlorides etc. can decrease the
concrete strength due to cracking.
 Increasing the hardness of mixing water can reduce the air content of air-entrained
concrete.
 Presence of Ca2+& Mg2+ in hard water renders soaps activity for washing.
 Hardness of water is important aspect for existence of aquatic life.Calcium has an
important role in the biological processes of fish.
After determining the quantity of ions which are causing hardness of water then
precautionary measures can be taken.
Standard:ASTM D1126-17

ENVIRONMENTAL SIGNIFICANCE AND RELATED THEORY:

Hardness of Water:

Water hardness is the traditional measure of the capacity of water to precipitate soap. Hard
water requiring a considerable amount of soap to produce leather. It is mostly due to the
presence of divalent cations(mostly because of Ca and Mg). these divalent cations combine
with CO3, HCO3, Cl- and sulphides.
Hardness is commonly expressed as CaCO3 in mg/L. The degree of hardness of drinking
water has been classified in terms of the equivalent CaCO3 concentration as follows:

Classification of hard Water

Table #3:
Description Concentration (mg/L CaCO3)
Soft 0 – 60
Medium 60 – 120
Hard 120 – 180
Very Hard > 180

Temporary Hardness
Temporary hardness is due to the presence of carbonates. Mostly it is because of presence of
CO3 and HCO3.

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Following are the methods which can be performed to remove hardness due to carbonates and
bicarbonates:
 Water is boiled, the calcium and magnesium carbonates are precipitated out of the
water and collect as residue, the water can then be recollected and is free of these
minerals.
 By using slaked lime; Ca(OH)2. This process is also known as Clark’s method.
Permanent Hardness
Permanent hardness is due to the presence of non-carbonates. Mostly it is because of
presence of Cl- and sulphides.
Following are the methods which can be performed to remove hardness due to chlorides and
sulphides:
 By using washing soda, (Na2CO3.10 H2O)
 By using ion exchanger like (Na-zeolite)
Estimation of Hardness
Following are the methods which can be carried out in order to estimate the hardness of
water.
 O.Hehner's method
 Soap titration method
 EDTA method
Total Hardness
Total hardness is due to the presence of bicarbonates, chlorides and sulphates of calcium and
magnesium ions.
The total hardness of water is estimated by titrating the water sample against EDTA using
Eriochrome Black-T (EBT) indicator in the presence of ammonia buffer (mixture of
ammonium chloride and ammonium hydroxide, pH 10).
Calcium Hardness
Calcium hardness is due to the presence of bicarbonates and carbonate ions.
The calcium hardness of water is estimated by titrating the water sample against EDTA using
Eriochrome Blue Black-R (EBBR) indicator in the presence of ammonia buffer (mixture of
ammonium chloride and ammonium hydroxide, pH 10).
Magnesium Hardness
The magnesium hardness is calculated from the total and calcium hardness.
Temporary Hardness = Total Hardness - Permanent Hardness
Note: Here an assumption is made that total hardness in water is due to the presence of
Calcium and Magnesium ions only.
Advantages of EDTA Method
This method is preferable to the other methods, because of
 Greater accuracy
 Convenience
 More rapid procedure
Permissible limits of Hardness for Drinking and Construction
For normal drinking purpose, WHO does not limit any value of hardness. But according to
Pakistan standard values maximum total hardness in water should be less than 500mg/L.

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CHEMICALS:
 Buffer Solutions (NH4OH)
 EBT indicators
 NaOH
 Standard EDTA (0.01M)
 Sample

APPARATUS:

Apparatus required to perform the experiment is as follows:

 Conical Flask
 Burette
 Pipette
 Spatula
PROCEDURE:

Total Hardness
 Take 50ml of sample in a titration flask.
 Add 1ml of ammonia (NH4OH). By adding NH4OH, it
changes pH between 7 to 10.
 Add pinch of EBT indicator. Solution color changes to
violet. Sample color can interfere with EBT color so, it Burette Stand with Burette
can be pink.
 Titrate it against 0.01M EDTA solution till color changes to blue.
 Suppose volume of EDTA used is ‘A’ then:

Total Hardness as CaCO 3 (Lmg ) = AVolume

× M × ( M.W of Calcium Carbonate ) ×1000
of Sample

After Addition of EBT (Right), After Titration (Left)

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Calcium Hardness
 Take 50ml of sample in a titration flask.
 Instead of using NH4OH use NaOH. It will change pH between 12 to 14.
 Add pinch of EBBR indicator instead of EBT. Sample color changes to pink.
 Titrate it against 0.01M EDTA solution till color changes to blue.
 Suppose volume of EDTA used is ‘A’ then:

Calcium Hardness as CaCO 3 ( )

mg A × M × ( A.W of Calcium ) ×1000
L
=
Volume of Sample

After Addition of EBBR (Right), After Titration (Left)

Magnesium Hardness
The magnesium hardness is calculated from the total and calcium hardness.
Temporary Hardness = Total Hardness - Permanent Hardness

PRECAUTIONS:

Make sure to use proper protective equipment while performing the experiment. Handel the
fragile equipment with care and avoid contact with any chemicals. Wash the flasks
thoroughly before and after using them in the experiment.

OBSERVATION AND CALCULATION:

Following are the observation and calculation done in the experiments

Table #4: hardness calculations
Observation and Calculation (Total Hardness)
Burette Reading Volume of EDTA added Total Hardness
Initial (mL) Final (mL) (A) (mg/L)
Sample 1
Sample 2
sample 3

Observation and Calculation (Calcium Hardness)

Burette Reading Volume of EDTA added Calcium
Initial (mL) Final (mL) (A) Hardness

9
 (mg/L)
Sample 1 0 34.5 34.5 276
Sample 2 0 16 16 128
Tap Water 0 6 6 48

Observation and Calculation (Magnesium Hardness)

Total Hardness Calcium Hardness Magnesium Hardness
(mg/L) (mg/L) (mg/L)
Sample 1 1000 276 724
Sample 2 460 128 332
Tap Water 270 48 222

EXPERIMENT NO. 4
TO DETERMINE THE AMOUNT OF TOTAL DISSOLVED SOLIDS IN
WATER

SCOPE:

The determination of total solids is important due to application in

 Determination of sediment formation
 Control of biological treatment process
 Irrigation engineering
 Corrosion control

ENVIRONMENTAL SIGNIFICANCE:

 Total solids also affect water clarity. Higher solids decrease the passage of light
through water, thereby slowing more rapidly and hold more heat; this, in turn, might
adversely photosynthesis by aquatic plants. Water will heat up affect aquatic life that
has adapted to a lower temperature regime.
 Water with total solids generally is of inferior palatability and may induce an
unfavorable physiological reaction. It may be esthetically unsatisfactory for purposes
such as bathing.
 Total solids will be higher in highly mineralized waters, which result in unsuitability
for many industrialapplications.
 It indicates effectiveness of sedimentation process and it affects effectiveness of
disinfection process in killing microorganisms.
 If the solids in wastewater are mostly organic, the impact on a treatment plant is
greater than if the solids are mostly inorganic.
 It determines the flow of water in and out of the cells of aquatic organisms

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PRINCIPLE:

The sample is evaporated in a weighed dish on a steam bath and is dried to a constant mass in
an oven either at 103-105C or 179-181C.Total solids/residue is calculated from increase
in mass.

APPARATUS:

 Crucible
 Oven
 Desiccators
 AnalyticalBalance
 DishTongs
 MagneticStirrer
 WashBottle

PROCEDURE:

 To measure total solids, take a clean porcelain dish which has been washed and dried
in a hot air oven at 105C for onehour.
 Now weigh the empty evaporating dish in analytical balance. Let’s denote the weight
measured as (W1).
 Now we should have to decide what should be the volume of sample to be taken
foranalysis.
 Volume may be estimated either from values of specific conductance or general
thumb rule.
 In general, select a sample volume that will yield residue between 2.5 and 200 mg
afterdrying.
 Using pipette transfer 75mL of unfiltered sample in the porcelaindish.
 Switch on the oven and allowed to reach 105°C. Check and regulate oven and furnace
temperatures frequently to maintain the desired temperature range.
 Place it in the hot air oven and care should be taken to prevent splattering of sample
during evaporation orboiling.
 Dry the sample to get constant mass. Drying for long duration usually 1 to 2 hours is
done to eliminate necessity of checking for constantmass.
 Cool the container in a desiccator. Desiccators are designed to provide an
environment of standard dryness. This is maintained by the desiccant found inside.
Don't leave the lid off for prolonged periods or the desiccant will soon be exhausted.
 Keep desiccator cover greased with the appropriate type of lubricant in order to seal
the desiccator and prevent moisture from entering the desiccator as the test
glasswarecools.

11
  We should weigh the dish as soon as it has cooled to avoid absorption of moisture due
to its hygroscopicnature.
 Sample need to measure accurately, weighed carefully, dried and cool completely.
Note the weight as residue ( W1).

PRECAUTIONS:

The following precautions should be observed while performing the experiment:

 Water or Wastewater samples which contain high concentrations of calcium, chloride,
magnesium or sulphate can rapidly absorb moisture from theair.
 Such samples may need to be dried for a longer period of time, cooled under proper
desiccation and weighed rapidly in order to achieve a reasonable constant weight.
 We should be aware prolonged drying may result in loss of constituents, particularly
nitrates and chlorides.
 Non-representative particulates such as leaves, sticks, fish and lumps of fecal matter
should be excluded from the sample if it is determined that their inclusion is not
desired in the finalresult.
 Floating oil and grease, if present, should be included in the sample and dispersed by
a blender device beforesub-sampling.
 Volume of sample should be adjusted to have residue left after drying as 100 to
200mg. It is mainly to prevent large amount of residue in entrapping water
duringevaporation.

 Highly mineralized water containing significant concentration of calcium,

magnesium, chloride, and/or sulphate may be hygroscopic. Hence prolonged drying,
desiccation and rapid weighing.
 We should be aware prolonged drying may result in loss of constituents, particularly
nitrates andchlorides.

OBSERVATION AND CALCULATIONS:

12
 EXPERIMENT NO 5
DETERMINE THE AMOUNT OF DISSOLVED OXYGEN (DO) IN
WATER

SCOPE:

The results from these experiments are used in water treatment plant and water disposal plant

 It is used to check the industrial sewage waste to be dispose of in main sewer or not.
 The concentration of DO is important for the health of aquatic animals and plants.
 It is used to estimate the amount and type of biomass a freshwater system can support.
 It also estimates the amount of decomposition occurring in lakes or streams.

RELATED THEORY
Dissolved Oxygen:
The dissolved oxygen (DO) is oxygen that is dissolved in water. The oxygen dissolves by
diffusion from the surrounding air; aeration of water that has tumbled over falls and rapids;
and as a waste product of photosynthesis

Importance of DO:
 Fish and aquatic animals cannot split oxygen from water (H2O) or other oxygen-containing
compounds.
 Only green plants and some bacteria can do that through photosynthesis and similar
processes.

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  A total of three-fourths of the earth’s oxygen supply is produced by phytoplankton in the
oceans.

Methods of Determination of Do in Water:

(1) Winkler Method

(2) Azide modification of Winkler Method

(3) Rideal Stewart method

(4) DO-meters
We perform Azide modification of Winkler Method.
PROCEDURE:
 Take BOD bottle (300 ml volume)
 Fill the bottle with water sample.
 Add 1 ml MnSO4 solution to it and mix uniformly with the help of pipette.
 Add 1ml alkali azide iodide solution. On addition, if white ppts. are formed, then there is no
DO in water. Formation of Reddish brown ppts. Indicates the presence of DO.
 If Reddish brown ppts are formed, stopper the bottle and shake it upside down for 20 times
and allow the ppts. To settle down for about 2 inches.
 Add 1 ml Concentrated H2SO4 and again shake for about 8 times.

 Take 200 ml of this water sample in a titration flask and titrate it with 0.025 N Na2S2O3 till
the appearance of light-yellow color.
 Then add 1ml starch solution. The color of solution becomes blue on this addition.
 Again, titrate it with 0.025N Na2S2O3 till the disappearance of blue color.
 Note the volume of titrant used.
ml of titrant used = DO in mg/liter
The above formula is applicable if we use 200ml of water sample solution and 0.025N Na2S2O3.
General formula is given by:
mean volume of titrant used∗N∗8000
DO (mg/l) =
F∗volume of sample∈ml
Volume of BOD bottle −volume of reagents used
Where, F =
Volume of BOD Bottle

RESULTS:
Table #5:
Color of
Sr. No. Sample DO (mg/L)
precipitates
1 Distilled Water White 0
Yellowish
2 Tap Water 5.5
Brown
Yellowish
3 Aerial Water 6.8
Brown

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COMMENTS:

Distilled Water is clear water and it contains no DO. On the other hand, rest of 2 samples show some
quantity of DO in them.

EXPERIMENT NO. 6
TO DETERMINE THE AMOUNT OF BOD IN DOMESTIC WASTE
WATER
SCOPE:

BOD test measure approximate amount of oxygen that will be absorbed by a wastewater. But
BOD test is limited in some application such as industrial wastewater which often contains
heavy metal ions, cyanides and other substances toxic to microorganisms. When
microorganisms become poisoned by toxic substance and they are unable to oxidize, in such
case the BOD test becomes an ineffective measure of organic pollution.
THEORY:
Biochemical Oxygen Demand (BOD):
Biological oxygen demand (BOD) is the amount of oxygen devoured by microorganisms as
they oxidize the soluble organic matter in wastewater. Devoured means that organic matter
can serve as food for the bacteria and energy is derived from its oxidation.
OR
Biochemical oxygen demand is a measure of the quantity of oxygen used by
microorganisms(e.g., aerobic bacteria)intheoxidationoforganicmatter.

BOD Level(inppm) WaterQuality

15
 1–2 Very good not much organic taste
4–5 Moderately clean
6–9 Somewhat polluted
10+ Very polluted

 Natural sources of organic matter include plant decay and leaf fall. However, plant
growth and decay may be unnaturally accelerated when nutrients and sunlight are
overly abundant due to human influence.
 Urban runoff carries per wastes from streets and sidewalks, nutrients from lawn
fertilizers; leaves, grass clippings, and paper from residential areas, which increase
oxygen demand.
PRINCIPLE:

The method consists of filling with sample, to overflowing, an airtight bottle of the
specified size and incubating it at the specified temperature for 5 days. Dissolved oxygen
is measured initially and after incubation, and the BOD is computed from the
differencebetweeninitialandfinalDO.BecausetheinitialDOisdeterminedshortly after the
dilution is made, all oxygen uptake occurring after this measurement is included in the
BOD measurement

APPARATUS:

a. Incubation bottles: Use glass bottles having 60mL orgreater capacity (300mL
bottle shaving ground-glasss topper and a flared mouth are preferred).
b. Air incubator or water bath, thermo-statistically controlled at 20 ± 1°C.
ExcludealllighttopreventpossibilityofphotosyntheticproductionofDO.
PROCEDURE:

1. First of all, it is important to know the no. of samples to be used for test. For this
purpose, the source of sample is to be recorded which will indicate the
approximate value of BOD5 for the sample.
(i) Domestic sewage BOD5=100-500mg/L
(ii) Effluent from treatment plant=20-80mg/L
(iii) River water =2-4mg/L
2. Take9BODbottlesnotetheirnumbersandarrangethemin3groups.
3. Fill each bottle half with dilution media ensuring that no air gets mixed.
4. Add 2ml sample in each of the three bottles marked as first group; 5 ml in each bottle
pf 2nd group and 10ml in each bottle of the 3rdgroup
5. Fill the bottle completely with dilution media and place the stopper such that no air
16
 bubbles are trapped.
6. Now take one bottle from each set and estimate its DO. This will be DO initial or
DO days.
7. For comparison prepare two more bottles with blank dilutions media (without
sewage sample) and find the DO from one bottle.
8. Place the rest of the six bottles with sewage samples and one bottle for blank in the
incubator at200C.
9. After 5 days find out DO in all bottles.
10. That value of oxygen depletion should be considered correct which gives an
oxygen depletion of at least 2 mg/L. and which have at least 0.5 mg/L DO after 5
days of incubation.
11. Calculate BOD5 at 200oC of the sample using following relationship:
BOD (mg/L) = DO depletion (mg/L)*300 / Volume of sample in bottle (ml)

PRECAUTIONS:

The BOD bottle during the 5-day incubation must have a water tight seal. It will prevent
the possible contamination. It will also prevent change in volume of solution in the bottle.

EXPERIMENT NO. 7
TO DETERMINE CHEMICAL OXYGEN DEMAND (COD) IN WATER

SCOPE:

To determine the amount of Chemical Oxygen Demand (BOD) in domestic waste Water.

ENVIRONMENTAL SIGNIFICANCE:

 The chemical oxygen demand (COD) test is commonly used to indirectly

measure the amount of organic compounds in water.
 COD is helpful in determining water quality because it determine the amount
of organic pollutants found in surface water (e.g. Lakes and rivers) or wastewater.
 If COD value is great than 150 mg/L, water should be treated before released into
rivers.
 COD is a good indicator of oxidable chemical waste in the water and thus most water
pollution controls focus on COD as it also reports the reduced substances like
sulfides, sulfites, ferrous iron along with organic carbon.
 As per (IS 10500:1991), COD for drinking water should be nil.

APPARATUS:

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  Reflex condenser, COD flask, Titration flask, Burette
SK2 Cr2O7,AgCl or HgCl2, H2SO4, Ferroin solution, FAS (0.025N)

THEORY:

Chemical oxygen demand (COD) is used to estimate the organic strength of wastes.
However, in this test, the organics are oxidized chemically& not using microorganisms. COD
is a measurement of the amount of material that can be oxidized in the presence of a strong
chemical oxidizing agent.
As a result of this the COD test needs much less time (say 2or 3 hours) to be conducted
unlike the five days for the standard BOD test. Also since all organics are oxidized
chemically, COD values will be higher than BOD values especially if biologically resistant
organic matter is present in the waste. Since the COD test can be performed in 2-4 hours
instead of 5 days for BOD, it is often used as a rough approximation of the water's BOD.
Similarly, like BOD test, the COD test is reported as mg/L of oxygen.

Relation b/w BOD & COD:

COD or Chemical Oxygen Demand is the total measurement of all chemicals (organics & in-
organics) in the water / waste water. BOD is a measure of, the amount of oxygen that require
for the bacteria to degrade the organic components present in water / waste water.
The ratio of BOD/COD is about; COD is higher than that of BOD; maximum of up to 4 times
in medium scale industries; but it varies based on the industrial process and nature of the raw
materials used.

PROCEDURE:
 Take COD flask and add 50 ml of sample in it.
 Add 6 to 8 glass beads to increase surface area then add a pinch of silver mercury salt
in it.
 Take two beakers. In one beaker, add 75 ml of concentrated sulphuric acid and in the
2nd beaker, add 25 ml of K2Cr2O7.
 Now add 10-15 ml of sulphuric acid from beaker to COD flask.
 After that add 25 ml of K2Cr2O7 in flask slowly.
 Now add remaining sulphuric acid in flask.
 Now transfer the flask for reflux for 2 hours.
 If green colour appear, repeat the whole procedure again by changing the
concentration of sample i.e. 45ml distilled water + 5ml sample.
 If organic matter is less than oxygen then orange colour will be appeared.
 If orange colour appears, then cool down flask and add 200 ml distilled water in it.
Sample is ready for titration.

18
  Take 100 ml in titration flask and add I ml of ferion as an indicator.
 Titrate it against 0.25N ferrous ammonium sulphate till reddish brown colour appears.
 Volume of FAS will give how much oxygen is left for oxidation.
 For total oxygen perform blank solution, In blank, instead of sample take 50 ml
distilled water while remaining procedure is same. Note the volume of FAS used for
blank and label it as B.

Oxygen consumed = B-A

( B− A)× N × Eq . Wt × 1000
COD (mg/l) = VOLUME OF SAMPLE
¿
¿

COMMENTS:

As per the given standards, this water sample is highly undesirable for drinking and it also
needs to be treated before throwing it in rivers as waste material.

EXPERIMENT NO 8
TO DETERMINE THE AMOUNT OF NITROGEN IN GIVEN WATER
SAMPLE.
SCOPE:

This experiment can be used to calculate the amount of nitrogen in given amount of water.

ENVIRONMENTAL SIGNIFICANCE:

All nitrogen present in the organic compounds may be considered as organic nitrogen. This
includes amino acids, amines, amides, nitro derivatives and no of other organic compounds.
In waters and waste water the form of nitrogen of greatest interest are organic –N and
ammonia-N, nitrates and nitrites. Organic nitrogen is defined functionally as organically
bound nitrogen in tri negative state. In wastewaters organic-N include such natural materials
like proteins, peptides, nucleic acids, urea and numerous synthetic organic materials.

19
PRINCIPLE:

In the presence of H2SO4, K2S04 and CuSO4, Ammonia nitrogen of many organic materials is
converted to ammonium sulfate. Free ammonia and ammonia nitrogen also are converted to
ammonium sulfate. During sample digestion a cupric ammonia complex is formed. After this
mercury ammonia complex in the digestion has been decomposed by sodium thiosulfate, the
ammonia is distilled from an alkaline layer and absorbed in boric acid.

Basic Steps involved:

1. Digestion

2. Distillation

3. Titration.

Titration theory:

The organic nitrogen is converted to ammonia nitrogen during the digestion. Boric acid isan
excellent buffer. It combines with ammonia in the distillate to form ammonia and borateions.

NH3 + H3 BO3 → NH4+ H2BO3

The ammonia then is measured by back titration with strong acid such as sulfuric
acid.Actually the acid measures the amount of boric ion present in the solution as follows.

H2BO3 + H
- +
→ H3BO3
Reagents:

1. Digestion reagent (dissolve 134g K2SO4 and 7.3g CuSO4 in about 800ml water carefully
add134ml Conc. H2SO4. Cool to room temperature, dilute to 1 lit with water. Mix well keeps
attempt 200C to prevent vaporization).

2. Phenolphthalein indicator

3. Sodium hydroxide

4. Mixed indicator solution

5. Indicating boric acid solution

6. Standard sulfuric acid titrant.

7. Hydroxide thiosulfate reagent.

20
APPARATUS:

a) Kjeldhal Flask

b) Pipette

c) Phenolphthalein Indicator

PROCEDURE:

(a) Digestion

1. Take 280ml of sample in a Kjeldhal flask.

2. Add few glass beads to it and add 50ml digestion reagent.

3.Mix heat and continue boiling until solution remains 25-50ml.

4. Cool it and add distilled water to it to make the volume 300ml.

5. Add 0.5 ml phenolphthalein indicator.

6. Add 50 ml thiosulfate hydroxide reagent solution.

7. If pink colour does not appears then add more 50 ml thiosulfate hydroxide reagent
solution.

(b) Distillation

1. Collect the distillate in a flask containing boric acid solution.

2. Collect 200ml distillate into 50ml boric acid solution.

(c) Titration

1. Titrate it against 0.02N H2SO4 solution until colour changes from purple to green.

2. Carry the blank titration, following all steps of procedure.

OBSERVATIONS & CALCULATIONS:

Total Nitrogen (mg/L) = ((A-B) ×200)/ml of sample

Where
A= volume of H2SO4 used for sample=
B= Volume of H2SO4 used for blank=
So,
Total nitrogen (mg/L) =

21
 EXPERIMENT NO. 9
DETERMINATION OF CHLORIDES IN DRINKING WATER

SCOPE:

To determine concentration of chlorides in drinking water sample

APPARATUS:

Titration flask, pipette, conical flask, 0.141N & 0.0141NMercurous nitrate (HgNO3)2, conc.
HNO3, Diphenyl Carbazone + Bromophenol indicator (for Cl conc. > 100mg/l), Diphenyl
Carbazone + Xylene Cyanol FF (for Cl conc. < 100mg/l).

THEORY:

Chloride in the form of chloride (Cl-) ion is one of the major inorganic anions in water and

22
wastewater. The chloride concentration is higher in wastewater than in raw water because
sodiumchloride is a common article of diet and passes unchanged through the digestive
system. Presence of Chlorine in water is responsible for hardness and taste of water. Some
waters containing 250 mg/L Cl- may have adetectable salty taste if sodium cation is present.
Excess of free chlorine in drinking water is undesirable, as it is not onlyunpleasant for
drinking but it also injurious for human metabolism. Hence, the amount offree chlorine in
municipal water is estimated prior to the domestic supply.
The EPA Secondary Drinking Water Regulations recommend a maximum concentration of
250 mg/lit for chloride ions (expressed as Cl-).

Methods of determination of Chlorides

1. Mohr’s method or Argentometric method
2. Mercuric Nitrate method
3. Potentiometeric method

PROCEDURE:

MERCURIC NITRATE METHOD

General Discussion
a. Principle: Chloride can be titrated with mercuric nitrate, Hg(N03)2 because of the
formation of soluble, slightly dissociated mercuric chloride. In the pH range 2.3 to 2.8,
diphenyl carbazone indicates the titration end point by formation of a purple complex with
the excess mercuric ions. Xylene cyanol FF serves as a pH indicator and end-point enhancer.
Increasing the strength of the titrant and modifying the indicator mixtures extend the range of
measurable chloride concentrations.

a. for Titration of chloride concentrations less than 100 mg/lit:

i. Take a 25-ml of chloride containing solution in titration flask.

ii. Add 1.0 ml indicator-acidifier reagent. It is a mixture of diphenyl carbazone and

Xylene cyanol.
iii. This will produce violet colour in the sample.

iv. Add conc. Nitric acid till violet colour disappears.

pH<2.30 then the color of the solution will be green

23
 pH=2.30 to 3.0 then the color of the solution will be bluish
green
pH>3.0 then the color of the solution will be blue
v. Titrate this sample with 0.0141N Hg(N03)2 titrant till a definite purple end point color
achieved.
vi. Take only reading and determine volume of the titrant Hg(N03)2 used

vii. Chloride ions concentration can be determined from following formula

−¿ x 10000
l (A ) x N x 35.4 x 10000
−¿ in mg/l=(A ) x N x EqW of C ¿¿ −¿ in mg/l= ¿
vol of sample in ml 25
Cl Cl
where:
A = mean volume of Hg(N03)2in ml used to titrate the sample
N = normality of Hg(N03)2i.e 0.0141N Hg(N03)2
b. for Titration of chloride concentrations greater than 100 mg/lit:
i. Take a 25-ml of chloride containing solution in titration flask

ii. Add 1 ml mixed indicator. It is a mixture of diphenylcarbazone and bromphenol. If

iii. Add few drops of 0.1N HN03 till color become violet.

iv. Titrate this sample with high strength 0.141N Hg(N03)2 titrant till a definite purple
end point color achieved
v. Take three readings and determine mean volume.
−¿ x 10000
l (A ) x N x 35.4 x 10000
−¿ in mg/l=(A ) x N x MW of C ¿¿ −¿ in mg/l= ¿
vol of sample in ml 25
Cl Cl
where:
A = mean volume of Hg(N03)2in ml used to titrate the sample
N = normality of Hg(N03)2i.e 0.141N Hg(N03)2

SIGNIFICANCE:

 A high chloride contents may harm metallic pipes and structures as well asgrowing
plants.
 The measured chloride ions can be used to know salinity of different water sources.
 Chlorine is widely used for disinfections of potable and municipal water supplied to
remove bacteria, fungus andother pathogenic microorganism, and for deodorization.
 Construction chemicals are used to minimize effect of chlorides on construction
activity.
 Excess conc. Of Chlorides can cause cracks in the constructed structure.
 The passivity of steel is destroyed by aggressive ions(chlorides).

24
  Corrosion of steel may occur that produced iron oxides and hydroxides. Which have
volume much greater than original volume of Iron . This increase in volume cause
cracking in concrete. Thus, amount of chloride in water should be within the
acceptable limits.
 The maximum concentration level for prevention of corrosion by chloride varies with
agency and country. Many specifications limit chloride levels to 0.2% to 1% by
weight of cement. Others limit it, regardless of cement content, in relationship to
concrete volume.
 As per ACI Building Code 318, threshold chloride concentration values vary but are
typically in the range of 0.05 to 0.1% by weight of concrete – about 2 to 4 lbs/yd3 .
Chloride limits are expressed on the basis of the weight of portland cement. These
threshold chloride values can be approximated to about 0.4 to 0.8% by weight of
cement (assuming approximately 500 lb/yd3 of portland cement in concrete).

OBSERVATIONS AND CALCULLATIONS

Table #6:
Sr No Sample description Mean volume of Cl- in mg/lit
Hg(NO3)2 (ml)
1 Sample 1
2 Sample 2
3 Sample 3

CONCLUSIONS:

 Threshold value given by WHO guidelines is 250 (mg/l).

 Both sample 1 & 2 rejected because the chloride ion concentration for sample 1 &
2 is 519.1 &798.6 (mg/l) respectively which is greater than threshold value 250
(mg/l).
 Chloride ion concentrate on of sample # 3 is <250(mg/l). So,it is suitable.

EXPERIMENT NO. 10
DETERMINE THE ELECTRICAL CONDUCTIVITY IN DIFFERENT
WATER SAMPLES

INTRODUCTION:

The importance of conductivity is related to the measure of the chemical or solids usually
inorganic present in the water such as nitrate, phosphate, chloride, and sulphate ions being
anionic and magnesium, sodium, calcium etc. Being cationic. The compounds such as
phenol, sugar, alcohol, oil don’t conduct the electricity. This quality of water is highly
affected by the changes in the atmosphere.

25
RELATED THEORY:

The electrical conductivity of water is one of the most important parameter to determine the
quality of the sample of water. This variates with the difference in the elevation along with
the other factors. The one with the best quality is then kept as a standard for others or an
indicator to determine the quality of the structure.
The electrical conductivity is defined as:
“Ratio of the electric field intensity to the current density of the sample being an opposite to
the resistivity of the sample.”
S = J/e = 1/r

Sample Conductivity

Ultra-pure drinking water 5.5*10-6 S/m

Drinking water 0.005 – 0.05 S/m

Sea Water 5 S/m

This quality of the sample is determined by using a probe along with a meter. The probe is
provided with the voltage to the two electrodes in it which is later immersed into the sample
of water. This eventually causes a certain drop in the resistance of the sample resulting into a
source to be used for the calculations of the conductivity rate of the sample.
It converts the values into the units of micromhos/cm for the declaration of the results. The
meter with high precision and accuracy however adopted is highly cost effective being 350$
able to determine the samples accuracy its potentials and other credentials precisely.

STANDARDS:

The standard method that can be adopted for this method is #2510, APHA 1992.

APPARATUS:

 A jar for measuring

26
  Conducting material
 Magnetic stirrer
 A standard flask
 A beaker of 250 ml
 A funnel
 Tissue papers
 A solution of kCl.
 A sample of distilled water.

PROCEDURE:

The following procedure is however adopted.

1. The sample stored from the field in the laboratory is provided with the electricity for
the generation of the electric current.
2. The sample is now prepared of 0.1N solution of kCl.
3. The field sample is now placed in the electrode setting as shown in the above picture.
4. The knobs along with the other aspects are set as per the standards.
5. The solution is than added up with the prepared solution to undergo the conductivity.
6. The readings are than observed to determine the conductivity of the sample.
7. The set of readings are adopted being 3 to have an accuracy level. The analysis is to
be carried out within the 12 hours of the collection of the sample. It should be filtrated
against a filter paper of 0.45micro placed at a temperature of

PRECAUTIONS:

The following precautions are to be adopted.

 The sample obtained from the field is to be kept in proper atmosphere along with the
conditions as listed along with the standards mentioned.
 The instruments adopted are to be properly cleaned and obtained along the
considerable instructions provided.
 The setup provided is maintained at its best.
 The other parameters such as salinity or TDS can be determined later but the
conductivity is to be dealt with high precision and care.

OBSERVATIONS AND CALCULLATIONS

Table #7:

27
 EXPERIEMENT NO 11 &12
HOW TO DETERMINE THE AMOUNT OF CALCIUM AND
MAGNESIUM IN A GIVEN WATER SAMPLE

SCOPE:

1. Determine the amount of calcium and magnesium present in the given sample of water.
2. Total hardness of calcium and magnesium ions in the given sample.

Provided

28
 0.01M EDTA

Introduction for Calcium

The classic method of determining calcium and other suitable cations is titration with a
standardized solution of ethylenediaminetetraacetic acid (EDTA). EDTA has the
structure shown below. Instead of repeatedly drawing this structure or writing out the
chemical formula, the EDTA molecule is represented as “H4Y”.
Each acid hydrogen on EDTA can be removed, producing H3Y-‐1, H2Y-‐2, HY-‐3, and Y-‐4
ions. The disodium dihydrate of EDTA, Na 2H2Y2H2O is commonly used to prepare
standard EDTA solutions. This salt is readily available from many commercial sources,
and often in such a high purity that solutions need not be standardized for routine work.
Primary standard calcium carbonate can be used to standardize EDTA solutions.
Of the various EDTA species, only the Y4-‐ ion (the completely deprotonated anion of
EDTA) forms a 1:1 complex with metal ions. To increase the fraction of Y4-‐, the pH
needs to be increased to 10 in this experiment.
The endpoint of an EDTA titration is determined with a metallochromic indicator. These
indicators are complexing agents that change color when combined with metal ions. A
variety of indicators can be used for EDTA titrations.

This indicator (shown as H2In-‐ in the equations below) changes from blue to red when
combined with a metal ion, forming a complex ion:

M2+ H2In- + 2H2O <-> MIn- + 2H3O+

Blue Red
EDTA is a stronger complexing agent than the indicator, and displaces the indicator from
the metal ion allowing the indicator to return (through shades of violet) to a pure blue
color, indicating the end of the reaction.

MIn- + Y4- <-> MY2- + H2In-

Red blue
Calcium ion (Ca+2) does not form a stable red complex with the EBT indicator; therefore,
the direct titration of Ca2+ by EDTA may not cause a sharp color change of EBT indicator
at the end point. The magnesium complex with EBT is stable and the Kf of Mg2+ with
EDTA is lower than the Kf of Ca2+ with EDTA. Thus, a displacement titration of Ca2+ by
the mixture of Mg2+ and EDTA will help to determine the end point with the following
mechanism:

CaIn- + MgY2- <-> CaY2- + MgIn-

To accomplish this displacement titration, a small amount of Mg2+ will be mixed with the
EDTA solution. The EDTA-Mg mixture will titrate the unknown Ca2+ solution. At the end
point, Mg2+ will be released from the EBT indicator and complexed with EDTA, causing the
color change from red to blue

INTRODUCTION FOR MAGNESIUM:

29
Many metal ions react with electron pair donors to form coordination compounds or complex

ions. The formation of a particular class of coordination compounds, called chelates, are
especially well suited for quantitative methods. A chelate is formed when a metal ion
coordinates with two (or more) donor groups of a single ligand. Tertiary amine compounds
such as ethylenadiaminetetraacetic acid (EDTA) are widely used for the formation of
chelates.
Complexometric titrations with EDTA have been reported for the analysis of nearly all metal
ions.
Because EDTA has four acidic protons, the formation of metal-ion/EDTA complexes is
dependent upon the pH. For the titration of Mg2+, one must buffer the solution to a pH of 10
so that complex formation will be quantitative. The reaction of Mg2+ with EDTA may be
expressed as:
Mg2+ + H2Y2- = MgY-2 + 2H+
The structure of EDTA and the magnesium-EDTA complex (without the hydrogen atoms) is
shown below:

The endpoint of the titration is determined by the addition of Eriochrome Black T, which
forms a colored chelate with Mg2+ and undergoes a color change when the Mg2+ is released
to form a chelate with EDTA. While it is possible to achieve relatively good results by
titration with EDTA prepared directly from the solid, better results should be obtained when
the EDTA is standardized against a solution containing a known amount of metal ion. You
will be provided with a standard solution of Zn2+ which you will use to standardize your
EDTA solution.

THEORY

The solution is first titrated against EDTA solution using Erichrome black T as indicator.
This gives the total amount of calcium and magnesium present in the sample.
This solution is again titrated against EDTA solution using calcon as indicator. The second
titration is conducted in the presence of high concentration of sodium hydroxide which
precipitates out magnesium as magnesium hydroxide. Thus in the second titration only
calcium reacts with EDTA solution. This titration gives the amount of calcium in the
solution. The difference between the first and the second titration gives the magnesium
content present in water.

30
For finding out the total hardness of water the total molarities of calcium and magnesium ions
in the water.

PROCEDURE

1. Take EDTA solution in the burette.

2. Pipette out 20ml of the mixture solution in a conical flask. Dilute the solution to about
50ml with 20-30ml of distilled water.
3. Add 5ml Of NH4Cl and NH4OH buffer solution. Add 3 to 4 drops of erio chromic Black T
indicator and heat the solution to 60oC
4. Run EDTA solution from the burette into the titration flask gradually until the color of the
solution changes from wine red to pure blue.
5. Repeat the titration till at least three reading.

SECOND TITRATION

1. Pipette out 20 ml mix sol into a 250ml titration flask. Dilute the sol to about 50ml with 20-
30ml of distilled water.
2. Add 3-4ml of 50%sodium hydroxide sol when a white ppt’s of Mg(OH)2 appears. Shake
it. Add 2-3 drops of calcon indicator.
3. Run the EDTA sol from the burette dropwise and with continuous stirring of the contents
of the titration flask
4. Continue adding EDTA sol slowly until a blue color appears this is the end point.
5. Repeat the titration until at least three readings.

31