M.

Qamar Habib (2018-CIV-73)

Table of Contents
Experiment No. 1: ..........................................................................................................................................................4
DETERMINATION OF pH OF WATER ..............................................................................................................................4
1. Objective: .........................................................................................................................................................4
2. Significance: ......................................................................................................................................................4
3. Relevant Theory:...............................................................................................................................................4
Introduction: .........................................................................................................................................................4
pH:.........................................................................................................................................................................5
pH variation: .........................................................................................................................................................5
4. Apparatus: ........................................................................................................................................................5
5. Procedure: ........................................................................................................................................................5
6. Observation and Calculations: ..........................................................................................................................6
7. Comments: .......................................................................................................................................................6
8. Reference: ........................................................................................................................................................6
Experiment No. 2: ..........................................................................................................................................................7
DETERMINATION OF THE TURBIDITY OF WATER ..........................................................................................................7
1. Objective: .........................................................................................................................................................7
2. Reagents: ..........................................................................................................................................................7
3. Scope & Significance: ........................................................................................................................................7
4. Relevant Theory:...............................................................................................................................................7
Introduction: .........................................................................................................................................................7
Turbidity Measurement: .......................................................................................................................................8
Reasons of Turbidity: ............................................................................................................................................8
Nephelometer: ......................................................................................................................................................8
Types of Nephelometers: ......................................................................................................................................8
Principle of Nephelometer:...................................................................................................................................9
5. Procedure: ........................................................................................................................................................9
6. Observations & Calculations:..........................................................................................................................10
7. Comments: .....................................................................................................................................................10
Experiment No. 3 .........................................................................................................................................................11
To determine the solids (content) in water sample ....................................................................................................11
1. Objective.........................................................................................................................................................11
2. Environmental Significance: ...........................................................................................................................11
3. Apparatus .......................................................................................................................................................11
4. Related Theory ...............................................................................................................................................11
Solids: ..................................................................................................................................................................11
Size classification of solids in water ....................................................................................................................12
Types of solids:....................................................................................................................................................12
Total Solids (TS) ...................................................................................................................................................12
Total Suspended Solids (TSS) ..............................................................................................................................12
Total Dissolved Solids (TDS) ................................................................................................................................12
Settleable Solids (SS) ...........................................................................................................................................12
5. Procedure .......................................................................................................................................................12
1. For TS ..............................................................................................................................................................12
2. For TDS ............................................................................................................................................................13
3. For TSS.............................................................................................................................................................13
4. For SS ..............................................................................................................................................................13
6. Observations & Calculations:..........................................................................................................................13

1|Page
 M. Qamar Habib (2018-CIV-73)

7. Results & Comments: .....................................................................................................................................14

8. Reference: ......................................................................................................................................................14
Experiment No. 4: ........................................................................................................................................................15
DETERMINATION OF HARDNESS OF DRINKING WATER ..............................................................................................15
1. Objective: .......................................................................................................................................................15
2. Apparatus: ......................................................................................................................................................15
3. Reagents: ........................................................................................................................................................15
4. Relevant Theory:.............................................................................................................................................15
Hardness: ............................................................................................................................................................15
Hardness Of Water: ............................................................................................................................................16
Types Of Hardness: .............................................................................................................................................16
Temporary Hardness...........................................................................................................................................16
Permanent Hardness ..........................................................................................................................................16
Effects Of Hardness: ............................................................................................................................................17
Methods To Remove Hardness ...........................................................................................................................17
Determination Of Hardness: ...............................................................................................................................17
Calculation Method ............................................................................................................................................17
EDTA Titrimetric Method ....................................................................................................................................17
5. Significance: ....................................................................................................................................................18
6. Procedure: ......................................................................................................................................................18
Total Harness ......................................................................................................................................................18
Calcium Hardness................................................................................................................................................19
Magnesium Hardness .........................................................................................................................................19
7. Observations & Calculations:..........................................................................................................................19
8. Comments: .....................................................................................................................................................20
9. References: .....................................................................................................................................................20
Experiment No. 5: ........................................................................................................................................................21
DETERMINATION OF CHLORIDES .................................................................................................................................21
1. Objective: .......................................................................................................................................................21
2. Significance: ....................................................................................................................................................21
3. Apparatus: ......................................................................................................................................................21
4. Reagents: ........................................................................................................................................................21
5. Relevant Theory:.............................................................................................................................................22
Chloride: ..............................................................................................................................................................22
Chlorides in water ...............................................................................................................................................22
Disadvantages of chloride concentration: ..........................................................................................................22
Usual methods for determination of chloride: ...................................................................................................22
Mohr’s method: - ................................................................................................................................................22
Limiting Value: ....................................................................................................................................................23
Natural sources: ..................................................................................................................................................23
Anthropogenic sources: ......................................................................................................................................23
6. Procedure: ......................................................................................................................................................23
7. Precautions: ....................................................................................................................................................23
8. Observations & Calculations:..........................................................................................................................24
9. Comments: .....................................................................................................................................................24
10. References: ................................................................................................................................................24
Experiment No. 6: ........................................................................................................................................................25
DETERMINATION OF DISSOLVED OXYGEN (DO) IN WASTEWATER .............................................................................25
1. Significance: ....................................................................................................................................................25

2|Page
 M. Qamar Habib (2018-CIV-73)

2. Apparatus: ......................................................................................................................................................25
3. Reagents: ........................................................................................................................................................25
4. Relevant Theory:.............................................................................................................................................26
Factors affecting dissolved oxygen concentration:.............................................................................................26
Importance of DO: ..............................................................................................................................................26
5. Procedure: ......................................................................................................................................................26
6. Observation and calculations: ........................................................................................................................27
7. Comments: .....................................................................................................................................................27
Experiment No. 7: ........................................................................................................................................................28
DETERMINATION OF BIOCHEMICAL OXYGEN DEMAND (BOD) FOR WASTEWATER ...................................................28
1. Objectives: ......................................................................................................................................................28
2. Significance: ....................................................................................................................................................28
3. Related Theory: ..............................................................................................................................................29
Definition: ...........................................................................................................................................................29
Introduction: .......................................................................................................................................................29
Principle: .............................................................................................................................................................29
4. Apparatus: ......................................................................................................................................................29
5. Reagents: ........................................................................................................................................................29
6. Procedure: ......................................................................................................................................................30
7. Observations and calculations:.......................................................................................................................31
8. Comments: .....................................................................................................................................................32
9. Reference: ......................................................................................................................................................32
Experiment No. 8: ........................................................................................................................................................33
DETERMINATION OF CHEMICAL OXYGEN DEMAND (COD) .........................................................................................33
1. Objective: .......................................................................................................................................................33
2. Scope and significance:...................................................................................................................................33
3. Apparatus: ......................................................................................................................................................33
4. Reagents: ........................................................................................................................................................33
5. Related Theory: ..............................................................................................................................................34
Introduction: .......................................................................................................................................................34
Definition: ...........................................................................................................................................................34
Use of Potassium Dichromate:............................................................................................................................34
Benefits of Potassium Dichromate: ....................................................................................................................35
Advantages of estimating COD: ..........................................................................................................................35
6. Procedure: ......................................................................................................................................................35
7. Observations and calculations:.......................................................................................................................36
8. Comments: .....................................................................................................................................................37
9. Reference: ......................................................................................................................................................37

3|Page
 M. Qamar Habib (2018-CIV-73)

Experiment No. 1:
DETERMINATION OF pH OF WATER

1. Objective:
To determine the pH of different Water Samples.

2. Significance:
 In the coagulation process, chemicals used have higher efficiencies within a
certain pH value range. Hence determination and adjustment of pH is very
important for effective and economic coagulation.
 In corrosion control, the pH of water should be maintained at appropriate level
as water of low pH is highly corrosive and damages the pipelines and valves
etc.
 In disinfection of water by excessive line treatment.
 In water softening process by lime soda.
 In sewage and industrial waste treatment employing biological treatment:
 The portability of water also depends on pH value
3. Relevant Theory:
Introduction:
The concept of pH of matters was given by a Danish Chemist, Peter Sorenson. pH
is a measure of concentration of hydrogen ions H+ in samples. It is used to find the
acidity or alkalinity of sample.
pH scale is used to locate the pH of sample to find its nature. Where pH of 7
indicates neutral matter while pH below 7 (1-7) shows acidity and pH above 7 (7-
14) shows alkalinity.

4|Page
 M. Qamar Habib (2018-CIV-73)

pH:
pH is a scale of acidity from 0 to 14. It tells how acidic or alkaline a substance
is. More acidic solutions have lower pH. More alkaline solutions have higher pH.
pH = -log[H+]
This means pH is the negative base 10 logarithm ("log" on a calculator) of the
hydrogen ion concentration of a solution.

pH variation:
The pH scale is logarithmic, which means that each step on the pH scale represents
a tenfold change in
acidity.
For example, a water
body having pH of 5 is
10 times more acidic that
a water body having pH
of 6.00

4. Apparatus:
• pH meter
• Beakers
• Chemicals
• Burette
• Pipette
5. Procedure:
 Calibrate the instrument by giving it values of
standard electrode and range of values.
 Take the sample in the beaker.
 Dip the pH electrode in the beaker.
 Note the reading from digital meter when it
becomes stable.

5|Page
 M. Qamar Habib (2018-CIV-73)

6. Observation and Calculations:

Sample pH Comments
- - -
NaOH 12.2 Basic
H2SO4 2.2 Acidic
Tap-water 7.1 Almost Neutral

7. Comments:
 pH value of 6.5 to 8.5 is acceptable.
 Higher values of pH reduce the germicidal potential of chlorine.
 pH below 6.5 starts corrosion in pipes.
 Water of pH which ranges from 6.5 to 8.5 is suitable for cementation
purposes.
 For construction purposes, pH of water should be strictly in between 7.2 to
7.8 as cement reacts with alkali. This can affect the durability of concrete.
8. Reference:
AWWA, WEF, APHA, 1998, Standard Methods for the Examination of Water and
Wastewater (2540D. Total Suspended Solids Dried at 103-105oC; 2540 E. Fixed
and Volatile Solids Ignited at 550oC)
Sawyer, C.N., McCarty, P.L., and Parkin, G.F. 2000. Chemistry for Environmental
Engineering 4th Edition. Tata McGraw-Hill Publishing Company Limited

6|Page
 M. Qamar Habib (2018-CIV-73)

Experiment No. 2:
DETERMINATION OF THE TURBIDITY OF
WATER
1. Objective:
The objective of this experiment is to determine turbidity of given samples of water.
2. Reagents:
 Turbid free water
 Stock Turbidity Suspension Solution 1
 Stock turbidity Suspension Solution 2
3. Scope & Significance:
a) Turbid water is not essential acceptable to the consumer. So, it is required to
know the turbidity.
b) Turbidity indicates the pollution, which may be responsible for water borne
diseases.
c) It determines the type of water treatment to be adopted.
d) Turbidity interferes with the process of disinfection, specially chlorination ad
application of ozone. Turbidity adheres to the pathogenic organisms without
proper contact with disinfectant.
e) Turbidity interferes with the water purification process, particularly ion
filtration by frequently clogging the filters and consequently the filters and
consequently reducing the filter run.
4. Relevant Theory:
Introduction:
The first practical attempt to quantify turbidity was done by “Whipple and Jackson”.
They developed a standard suspension fluid using 1,000 parts per million (ppm) of
diatomaceous earth in distilled water. Dilution of this reference suspension resulted
in a series of standard suspensions, which were then used to derive a ppm-silica scale
for calibrating turbidimeters. Turbidity is measured by instrument Nephelometer. It
was invented by “Theodore William Richards”. He was an American chemist and
first scientist to receive Nobel prize in Chemistry.
Turbidity of water is due to suspended solids such as clay, plankton, silt, finely
divided organic matter, microscopic organisms, and similar materials. These solids

7|Page
 M. Qamar Habib (2018-CIV-73)

will deflect (or scatter) light as it passes through the sample. The more light that is
deflected the higher the turbidity of the sample.
Turbidity Measurement:
The measuring device used in today’s laboratories is called a nephelometric meter.
This type of meter does not measure all of the deflected light, only that which is
deflected at a right angle (90°) from the sample and light source. Turbidity is read
as nephelometric turbidity units (NTU).
Reasons of Turbidity:
Turbidity depends on three things,
Planktons (Algae and microorganisms)
Organic Material
Silt and sediments
Turbidity is measured or observed by deep penetration of light.
More turbidity means more cloudiness and vice versa.
Nephelometer:
It is an instrument used to measure the size and concentration of particles suspended
in a liquid or gas, especially by means of the light they scatter. It measures light
scattering (light reflected off the particles in a sample), not the attenuation of light
(absorbance) caused by turbidity. It is measured in units of NTU (SI units).

Types of Nephelometers:
There are two types of Nephelometers,
a) Manual Nephelometer
b) Digital Nephelometer

8|Page
 M. Qamar Habib (2018-CIV-73)

Principle of Nephelometer:
Turbidity of sample is measured from the amount of light scattered by the sample
taking a reference with standard turbidity suspension. The higher the intensity of
scattered light, the higher is the turbidity.

5. Procedure:
1) Calibrate the instrument
2) Select the scale.
3) Add the standard solution in turbidimeter cell and placed it in turbidimeter.
4) if the turbidity of the laboratory grade water is 0.05 NTU or higher, pass the
water through a membrane filter having precision-sized holes of 0.2 m m.
5) Rinse collecting flask twice with filtered water.
6) Discard the next 200 mL of filtered water, then start collecting filtered water
to prepare standards.
7) Commercially prepared water can be substituted when its turbidity is lower
than what is available in the laboratory.
8) Weigh 1.00 gram of hydrazine sulfate, (NH2)2·H2SO4.
9) Dissolve the 1.00 gram of hydrazine sulfate in a 100 mL volumetric flask.
10) Use turbid free water to fill to the 100mL line on the volumetric flask
11) Prepare stock solution monthly.
12) Caution: hydrazine sulfate is a known carcinogen: avoid inhalation, ingestion
and contact with skin.
13) Weigh 10.00 grams hexamethylenetetramine, C6H12N4.
14) Dissolve the 10.00 grams of hexamethylenetetramine in a 100mL volumetric
flask.
15) Use turbid free water to fill to the 100-mL mark on the volumetric flask.
16) Prepare stock solution monthly.
17) Turbidity test should be determined on the day the sample is taken.
18) If this is not possible, refrigerate the sample at 4° C for up to 24 hours.
19) Remember to vigorously shake all samples before examination.
20) Calibrate the instrument.
21) Thoroughly shake sample. Wait until air bubbles disappear before pouring
sample into turbidity tube.
22) When necessary, immerse turbidity tube in an ultrasonic bath for 1 to 2
seconds to dislodge bubbles.

9|Page
 M. Qamar Habib (2018-CIV-73)

23) Letting the sample stand for a period to allow air bubbles to dissipate will also
allow solids to settle thus changing the characteristics of the sample being
evaluated.
24) Wipe outside of tube to remove fingerprints, dust dirt, and water droplets.
Place tube in turbidimeter.
25) Read turbidity from instrument direct reading scale or convert from
calibration curve.
6. Observations & Calculations:

Sample No. Source Turbidity (NTU)

1 Syphon 56.5
2 Head Balloki 348
3 River Chenab 977
4 Tap-water 4.34

7. Comments:
• Sediments from erosion and dead organic matter are the major sources of
turbidity.
• Turbidity of drinking water should be less than 5 NTU and our tap water value
comes out to be 0.55.
• Distilled Water has 0 NTU.
• Higher values of turbidity protect microorganisms from disinfection and
stimulate the growth of bacteria.

10 | P a g e
 M. Qamar Habib (2018-CIV-73)

Experiment No. 3
To determine the solids (content) in water
sample
1. Objective
To determine the total dissolved solids, settleable solids, total suspended solids and
total solids in the water sample.
2. Environmental Significance:
i. The consumption of hard water means containing high solid amounts result
in kidney problems, the range of hard water which causes problem is more
than 180mg/L.
ii. The total permissible limit of solids in water is 500mg/L, although higher
amounts up to 1000mg/L are sometimes permitted but are likely to produce
certain psychological effects on human.
iii. Suspended materials are aesthetically displeasing and provide adsorption
sites for chemical and biological agents.
iv. Suspended organic solids may be degraded biologically, resulting in
objectionable by products.
v. Biologically active suspended solids may include disease causing organisms
as well as organisms such as toxin producing strains of algae.
vi. Quite often, two or more dissolved substances, especially organic substances
and members of halogen group will combine to form a compound whose
characteristics are more objectionable than those of either of the organic
materials.

3. Apparatus
a) China Dish
b) Water Bath
c) 0.45µm filter paper
d) Oven
e) Mhoff Cone
4. Related Theory
Solids:
Any time of minerals, cations, or anions. salts and metal dissolved in water are
called solids.

11 | P a g e
 M. Qamar Habib (2018-CIV-73)

Size classification of solids in water

Dissolved solids: 10-5 -10-3μm
Colloidal solids: 10-3-1μm
Suspended solids: 1-100μm
Types of solids:
i. Total solids (TS)
ii. Total dissolved solids (TDS)
iii. Total Suspended solids (TSS)
iv. Settleable solids (SS)
Total Solids (TS)
It is the material residue left in a dish after evaporation of a sample and its
subsequent drying in an oven at a defined temperature. Total solids include total
suspended solids and total dissolved solids.
Total Suspended Solids (TSS)
It is the solid material in water or wastewater sample, which is retained by a filter
of 2µm nominal size under specified conditions.
Total Dissolved Solids (TDS)
It is portion of solids present in water or wastewater through a filter of 0.45µm
nominal pore size under specified conditions. The principal ions contributing to
TDS are carbonate, bicarbonate, chloride, sulfate, nitrate, sodium, potassium,
calcium and magnesium. TDS in water may originate from natural source or
sewage effluent discharges.
Settleable Solids (SS)
It refers to material settling out of suspension within a defined period.
5. Procedure
1. For TS
 Take 100ml of sample
 Take a China dish and note its empty weight
 Pour the sample in china dish
 Place it in water bath, as a result solid residues will be left in china dish.
 Take the weight of this china dish
 TS in mg/L = A − B x 100 x 0.01 x 1000 /Volume of sample

12 | P a g e
 M. Qamar Habib (2018-CIV-73)

2. For TDS
 Take 100ml of sample of water.
 Pass it through 0.45µm filter paper.
 Take the filtrate and pour it in china dish
 Dry it in water bath and then take the weight the china dish.
 TDS in mg/L = A−B x 1000 x 1000 /Volume of sample
3. For TSS
 Take 100ml of sample of water.
 Take a filter paper and note its weight
 Pass it through filter paper
 Take the filter paper and dry it in oven and then note the weight
(A−B) x 1000 x 1000
 TDS in mg/L =
Volume of sample

4. For SS
 Take 1litre of sample in Imhoff Cone
 Settle it for 45 minutes
 After 45 minutes, gently stir this sample from edges 1-2 times
 Wait for 15 minutes and note the settleable solids.
6. Observations & Calculations:
For Total Solids:
W1= 47.0705g
W2=53.1851g
TS= ((53.1851-53.2353) *10002)/100
= 502mg/l
For TDS:
TDS= ((w2 – w1) *1000)2/100
= ((47.0705-47.0320) *10002)/100
= 385mg/l
For TSS
TSS= ((F2– F1) *1000)2/100
= ((0.0972-0.0961) *10002)/100
= 11mg/l
For Total settle-able solids:
Total settle able solids = 2.7mg/l

13 | P a g e
 M. Qamar Habib (2018-CIV-73)

7. Results & Comments:

Total solids (TS) = 502mg/l

Total dissolved solids (TDS)= 385mg/l

Total Suspended solids (TSS)= 11mg.l

Settleable solids (SS)= 2.7mg/l

From the experiment, the water we used has the total dissolved solids 502 mg/Liter.
The water used for drinking purpose must have the total solids less than
100mg/Liter due to aesthetics that is color and taste. For human consumption the
limit is 500mg/Liter and for agricultural purposes the value must be less than
1000mg/Liter depending upon the type of crop. So, the water tested in the lab can
be used for agricultural purposes but cannot be used for any type of human
consumptions.
8. Reference:
 AWWA, WEF, APHA, 1998, Standard Methods for the Examination of
Water and Wastewater (Methods: 2340 C. EDTA Titrimetric Method)
 Sawyer, C.N., McCarty, P.L., and Parkin, G.F. 2000. Chemistry for
Environmental Engineering 4th Edition. Tata McGraw-Hill Publishing
Company Limited.

14 | P a g e
 M. Qamar Habib (2018-CIV-73)

Experiment No. 4:
DETERMINATION OF HARDNESS OF DRINKING
WATER
1. Objective:
To find out
 Total hardness
 Calcium Hardness
 Magnesium Hardness
2. Apparatus:
 Muffle furnace for operating at 5500C
 Desiccators provided with a desiccant containing a color indicator of
moisture concentration
 Drying oven, for operation at 103 to 105 0C
 Analytical balance capable of weighing 0.1 mg
 Magnetic stirrer
 Wide-mouth pipettes
 Glass fiber filter disks without organic binder
 Filtration apparatus
 Suction flasks sufficient capacity for sample size selected
 Aluminum weighing dishes
3. Reagents:
 EDTA (Ethylene diamine tetra acetic acid) titrant (0.01 M)
 Eriochrome black T indicator (EBT)
 Ammonia buffer solution
 Eriochrome blue black R indicator (EBBR)
 Sodium Hydroxide
4. Relevant Theory:
Hardness:
Hardness is caused by polyvalent metallic cations, though the divalent cations, such
as calcium and magnesium cations are usually the predominant cause of hardness.
In addition, hardness is also caused by Fe2+ and Mn2+ ions. For example, when hard
water is heated, Ca2+ ions react with bicarbonate (HCO3-) ions to form insoluble
calcium carbonate (CaCO3) (Eq. 1). This precipitate, known as scale, coats the

15 | P a g e
 M. Qamar Habib (2018-CIV-73)

vessels in which the water is heated, producing the mineral deposits on your cooking
dishes. Equation 2 presents magnesium hardness.

Total hardness is defined as the sum of the calcium and magnesium concentrations,
both expressed as calcium carbonate in mg/L. When hardness (numerically) is
greater than the sum of carbonate and bicarbonate alkalinity, amount of hardness
equivalent to the total alkalinity is called “Carbonate hardness”.
Carbonate hardness (mg/L) = Alkalinity
When alkalinity > Total hardness:
Carbonate hardness (mg/L) = Total hardness
The amount of hardness more than this is called “non-carbonate hardness (NCH)”.
These are associated with sulfate chloride, and nitrate ions. It is calculated using Eq
(2c):
NCH (mg/L) = Total Hardness-Carbonate hardness (2c)
Hardness Of Water:
Hardness is the total concentration of mainly calcium and magnesium ions expressed
as calcium carbonate. Other hardness producing metallic ions should be included if
present in significant amounts.
It is expressed as milligrams of calcium carbonate per liter (mg/ as CaCO3).
Types Of Hardness:
Temporary hardness
Permanent hardness
Temporary Hardness
Temporary hardness is caused by the presence of dissolved bicarbonate (calcium
bicarbonate & magnesium bicarbonate). It can be reduced either by boiling the
water, or by the addition of lime (calcium hydroxide) through the softening process
of softening.
Permanent Hardness
Permanent hardness is caused by sulfate and chloride compounds.
Total Hardness = Calcium Hardness + Magnesium Hardness

16 | P a g e
 M. Qamar Habib (2018-CIV-73)

Hardness mg/L as CaCO3 Type of water

0 – 75 Soft water
75 – 150 Moderately hard water
150 – 300 Hard water
above 300 Very hard water

Effects Of Hardness:
Hardness is the reason of scales in in the boilers.
Water becomes bitter if hardness is high.
Hard water is the main reason of cardiovascular disease.
Methods To Remove Hardness
 Physical methods
 Chemical methods
 Membrane methods
Determination Of Hardness:
Hardness is expressed as mg/L CaCO3. The first method is calculation-based method
and the second method is titration method using EDTA.
Calculation Method
For this method, concentration of cations should be known and then all
concentrations are expressed in terms of CaCO3 using Eq. 3:
Hardness (in mg/L as CaCO3) = [M2+ (in mg/L) × 50]/ (E.Wt. of M2+) (3)
Where: M2+ = mass of divalent ions (mg/L) and E.Wt. = Equivalent weight of
divalent ions (g/mole)

Example: If in a sample, 15 mg/L Ca2+are present (, hardness is given by

Hardness (in mg/L as CaCO3) = [mass of Ca2+ (in mg/L) × 50]/ (E.Wt. of Ca2+) Here,
E.Wt. of Ca2+ = (40g/mole)/2=20 g/mole
So, Hardness due to calcium ions = [15 mg/L × 50]/ (20) = 37.5 mg/L CaCO3

EDTA Titrimetric Method

This method uses ethylenediaminetetraacetic acid (EDTA), chelating agents, which
forms complex ions with Ca2+and Mg2+ and other divalent ions causing hardness
(Eq. 4a):
M2++ EDTA➔ [M. EDTA] complex (4a)

17 | P a g e
 M. Qamar Habib (2018-CIV-73)

The successful use of EDTA for determining hardness depends on presence of an

indicator which can
show presence of excess EDTA in solution or when all the ions present in solution
have been complexed. Eriochrome Black T (EBT) (blue color solution) serves as an
excellent indicator to show when all hardness ions have been consumed. When small
amount of EBT is added to hard water with pH>10, it combines with Ca2+ and Mg2+
ions to form weak complex ions (wine-red color solution) (Eq. 4b):
M2++ Eriochrome Black T➔[M.Ericochrome Black T]complex (4b)
During the titration with EDTA, all free hardness ions are complexed as per Eq. 4a
and subsequently,
EDTA disrupts the wine red complex as it can form a stable complex with the
hardness ions. At this stage, solution color changes from red wine color to blue color,
indicating the end of the titration.
5. Significance:
1. Soap consumption by hard water represents an economic loss to the water
uses.
2. The precipitate by hardness and soap adheres to the surface of the tubs, skins
and dishwashs may stain dishes clothing and other items.
3. Residue of hardness of soap may remain in the pores of the clothes so the skin
may feel rough and uncomfortable.
4. Boiler scale, the result of carbonate hardness precipitate may cause
considerable economic loss through hardness of water heaters and hot water
pipes.
5. Food cooked in hard water become tasteless.
6. Procedure:
Total Harness
1. Take 25mL of sample and add 25 mL of distilled water in an Erlenmeyer
flask.
2. Add 1 mL of NH3 buffer solution.
3. Add pinge of EBT if solid and 1mL of EBT if liquid or in solution form.
4. The solution turns magenta in color.
5. Add the standard EDTA titrant slowly until the color changes to blue.
6. Note down the volume of EDTA added and label as “A” mL.
7. Repeat same procedure for blank (50 mL of distilled water).
8. Note down the volume of EDTA added and label as “B” mL.

18 | P a g e
 M. Qamar Habib (2018-CIV-73)

9. A-B = C mL
(𝐴𝐴−𝐵𝐵(𝑚𝑚𝑚𝑚)∗𝑁𝑁(0.02)∗𝐸𝐸𝐸𝐸.𝑊𝑊𝑊𝑊(50)∗1000)
10.Total hardness (mg/L as CaCO3) =
(𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 𝑜𝑜𝑜𝑜 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑖𝑖𝑖𝑖 𝑚𝑚𝑚𝑚)

Calcium Hardness
11.Take 25mL of sample and add 25 mL of distilled water in an Erlenmeyer
flask.
12.Add 2 mL of NaOH solution in it.
13.Add pinge of EBBR in it.
14.The solution turns magenta in color.
15.Add the standard EDTA titrant slowly until the color changes to blue.
16.Note down the volume of EDTA added and label as “A” mL.
17.Repeat same procedure for blank (50 mL of distilled water).
18.Note down the volume of EDTA added and label as “B” mL. (A-B = D mL)
(𝐀𝐀−𝐁𝐁(𝐦𝐦𝐦𝐦)∗𝐍𝐍(𝟎𝟎.𝟎𝟎𝟎𝟎)∗𝐄𝐄𝐄𝐄.𝐖𝐖𝐖𝐖(𝟓𝟓𝟓𝟓)∗𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)
19.Calcium hardness (mg/L as CaCO3) =
(𝐕𝐕𝐕𝐕𝐕𝐕𝐕𝐕𝐕𝐕𝐕𝐕 𝐨𝐨𝐨𝐨 𝐬𝐬𝐬𝐬𝐬𝐬𝐬𝐬𝐬𝐬𝐬𝐬 𝐢𝐢𝐢𝐢 𝐦𝐦𝐦𝐦)

Magnesium Hardness
(𝐂𝐂−𝐃𝐃(𝐦𝐦𝐦𝐦)∗𝐍𝐍(𝟎𝟎.𝟎𝟎𝟎𝟎)∗𝐄𝐄𝐄𝐄.𝐖𝐖𝐖𝐖(𝟓𝟓𝟓𝟓)∗𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏)
20.Magnesium hardness (mg/L as CaCO3) =
(𝐕𝐕𝐕𝐕𝐕𝐕𝐕𝐕𝐕𝐕𝐕𝐕 𝐨𝐨𝐨𝐨 𝐬𝐬𝐬𝐬𝐬𝐬𝐬𝐬𝐬𝐬𝐬𝐬 𝐢𝐢𝐢𝐢 𝐦𝐦𝐦𝐦)

7. Observations & Calculations:

Vol of EDTA for total hardness Total hardness

Sample
Take 1 Take 2 Take 3 Average Mg/l as CaCo3
1 24.5 23 25 24.17 960.8
2 44 45 39.5 42.83 1713.33
3 (tap water) 11.6 12.4 12.6 12.2 244

Sample Vol of EDTA for calcium hardness Calcium hardness

Take 1 Take 2 Take 3 Average Mg/l as Ca
1 20.5 20.5 23.5 21.5 860
2 44 55 52 50.3 1160
3 (tap water) 6.2 6.8 6.5 6.5 52

19 | P a g e
 M. Qamar Habib (2018-CIV-73)

Sample Total hardness Calcium hardness Magnesium hardness

Mg/l as CaCo3 Mg/l as Ca Mg/l as Mg
1 960.8 860 100.8
2 1713.33 1160 553.33
3 (tap water) 244 52 192

8. Comments:
 If hardness is more, then more will be the difficulty in producing foam.
 In water, permanent Hardness is due to sulphates, chlorides of divalent
carbonates.
 The values of Total Hardness for consumptive use should be less than 500mg/l
and its range for water treatment is 75mg/l-125mg/l.
 Temporary Hardness is due to carbonates and bicarbonates of divalent cations.
 Hardness of water is caused due to divalent cations.
9. References:
 ASTM D1126 – 17 Standard Test Method for Hardness of Water.
 ASTM D511 – 14 Standard Test Methods for Calcium and Magnesium in
Water.
 Hardness in Drinking Water, A background document for development of
WHO Guidelines for Drinking Water Quality.
 Quality of Mixing Water in Cement Concrete, A Review; Science Direct,
Materials today: proceedings.

20 | P a g e
 M. Qamar Habib (2018-CIV-73)

Experiment No. 5:
DETERMINATION OF CHLORIDES

1. Objective:
The main objective of this experiment is to determine chloride concentration in given
samples.
2. Significance:
 Chloride in reasonable concentrations is not harmful to public health. At
concentrations above 250 mg/L, it gives a noticeable salty taste in drinking
water, which is objectionable.
 The presence of high quantity of chloride in river or stream waters may
indicate pollution of water due to sewage and/or industrial wastes.
 Increase in chloride level in water increases its corrosiveness.
 The chloride content of water used for irrigation is generally controlled along
with the total salinity of water. Evapotranspiration tends to increase the
chloride and salinity at the root zone of irrigated plants, making it difficult for
plants to make up water due to osmotic pressure differences between the water
outside the plants and within the plant cells.
3. Apparatus:
 Titration flask
 Burette
 Pipette
 Beaker
 Cylinder
 Mix indicator (Diphenyl carbazone & xylene cyanole)
4. Reagents:
 Conc. Nitric Acid
 Mercuric Nitrate
 Standard silver nitrate solution, AgNO3
 5% Potassium chromate solution

21 | P a g e
 M. Qamar Habib (2018-CIV-73)

5. Relevant Theory:
Chloride:
Chloride is a salt compound resulting from the combination of the gas chlorine and
a metal. Some common chlorides include sodium chloride, magnesium chloride and
calcium chloride. Chlorine alone as Cl2 is highly toxic, and it is often used as a
disinfectant. In combination with a metal such as sodium it becomes essential for
life.
Chlorides in water
All natural waters contain chloride and sulfate ions. Their concentrations vary
considerably according to the mineral content of the earth in any given area. In small
amounts, they are not significant. In large concentrations, they present problems. As
chlorides concentration increases, pH changes form basic to acidic. It results in
corrosion and affects the pH of concrete.
Disadvantages of chloride concentration:
High levels of chloride can corrode and weaken metallic piping. (especially
dangerous for pipes of water distribution system).
It gives a salty taste to drinking water, making it unpleasant for its drinking use.
Chlorine in water reacts with living tissues and organic matter causing cell death in
fish. High levels may cause fish to succumb in hours or even minutes.
High concentrations of chloride in water bodies cause long-lasting ill effects on
aquatic life.
Usual methods for determination of chloride:
 Mohr’s method
 Villard’s method
Mohr’s method: -
In Mohr’s method, the acidity of the water sample is removed by adding calcium
carbonate. Potassium chromate acts as an indicator for titration. Preferential
precipitation of white silver chloride over red silver chromate is the principle of this
method. The change of color from white to red indicates the end point. The reactions
are: -
NaCl+AgNO3 =AgCl +NaNO3

22 | P a g e
 M. Qamar Habib (2018-CIV-73)

Limiting Value:
The Limiting value of chloride in water is 250mg/l.
Natural sources:
Usually, chlorides are leached from various rocks into soil and water due to
weathering.
Anthropogenic sources:
Chlorides in water may be considerably increased by the treatment processes, used
for the purification of water, in which chlorine and chlorides are used. Chlorine level
in food in increased due to addition of salt in food during cooking process.

6. Procedure:
Take a titration flask and add 50 mL of sample in it
Add 0.5 mL of mix indicator
Then add 3 to 4 mL of concentrated nitric acid until pale yellow color appear
Titrate it against Hg(NO3)2 until violet color appear
Note the volume of mercuric acid
Then Take three readings and by taking average that volume is equal to A
Then using formula we can find Cl- in mg/L
Repeat the same procedure for sample 2 and tap water.
Equations:
A= Sample B= Distilled water/Blank
Volume of sample= 50ml
CL-1 mg/l = ((A-B) × N × 35.45 × 1000)/50
CL-1 mg/l = ((A-B) × 0.141 × 35.45 × 1000)/50

7. Precautions:
 A uniform sample size must be used, preferably 100 mL, so that ionic
concentrations needed to indicate the end point will be constant.
 The pH must be in the range of 7 to 8 as silver ions are precipitated as AgOH
at high pH levels and the7 chromate ions are converted to Cr2O 2- at low pH
values.
 A definite amount of indicator must be used to provide a certain concentration
of chromate ions, otherwise silver chromate may form too soon or not soon
enough.
 Caution should be made to notice indicator color change as it can varies
person-to-person. The usual range is 0.2 to 0.4 mL of titrant.

23 | P a g e
 M. Qamar Habib (2018-CIV-73)

8. Observations & Calculations:

Initial reading Final reading Difference A (ml)
Sample 1
0 4.5 4.5 2.967
4.5 5.9 1.4
5.9 8.9 3
Sample 2
0 4.5 4.5 4.33
4.5 9 4.5
9 13 4
Sample 3 (tab water)
0 0.4 0.4 0.367
0.4 0.7 0.3
0.7 1.1 0.4

Sample No. A (ml) Cl- mg/l

1 2.967 593.72
2 4.33 866.46
3 (tap water) 0.367 73.44

9. Comments:
a) According to WHO, the permissible limits of chlorides in drinking water is
200 mg/l hence, Sample 1 is not suitable for drinking purposes.
b) If the sample has value of more than 1000 mg/l then we will reject the sample.
c) When it exceeds 250 mg/l then it imparts a peculiar taste to water rendering it
unacceptable for drinking purpose.
d) Threshold chloride concentration values vary but are typically in the range of
0.05 – 0.1% by weight of concrete.
e) Sample 1 is suitable for all sorts of construction purposes as per different
standards.

10. References:
• ASTM D512-12, Standard Test Methods for Chloride Ion in Water.
• ASTM D4458-15, Standard Test Methods for Chloride Ions in Brackish
Water, Seawater and Brines.
• ASTM C1218-17 Standard Test Method for Water-Soluble Chloride in
Mortar and Concrete.

24 | P a g e
 M. Qamar Habib (2018-CIV-73)

Experiment No. 6:
DETERMINATION OF DISSOLVED OXYGEN (DO)
IN WASTEWATER
1. Significance:
 High concentration of DO causes the death of aquatic lives. The high
concentration at which DO affects the environment is 115 – 120% of air
saturation for period. The concentration becomes high due to excessive
photosynthesis of aquatic plants.
 The normal range of DO is 5 mg/L if the concentration exceeds this range like
if the range is between 1-2mg/L the environment is badly affected. This is
because of excessive growth of algae in environment due to algae growth
other plants die which become food for bacteria as they decompose and as a
result of which bacteria increases in number and use the DO which result in
less amount of DO in water.
2. Apparatus:
 BOD bottle (Incubator Bottle 300ml)
 Titration flask
 Pipette
 Burette
 Beakers
 Cylinder
3. Reagents:
 Manganese sulfate solution: Dissolve 480 g MnSO4.4H2O, 400 g
MnSO4.2H2O or 364 g MnSO4.H2O in distilled water, filter, and dilute to 1L.
The MnSO4 solution should not give a color with starch when added to an
acidified potassium iodide (KI) solution.
 Alkali-iodide-azide reagent
 Sulfuric acid: One mL is equivalent to ~ 3mL alkali-iodide-azide reagent.
 Starch solution: Dissolve 2 g laboratory-grade soluble starch and 0.2 g
salicylic acid as preservative in 100 mL hot distilled water.
 Standard sodium thiosulfate titrant: Dissolve 6.205 g Na2S2O3 .5H2O in
distiller water and add
 1.5 mL 6N NaOH or 0.4 g solid NaOH and dilute to 1000 mL. Standardize
with bi-iodate solution.

25 | P a g e
 M. Qamar Habib (2018-CIV-73)

 Standard potassium bi-iodate solution (0.0021M): Dissolve 812.4 mg

KH(IO3) in distilled water and dilute to 1000 mL.
 Standardization: Dissolve e ~ 2 g KI, free from iodate in an Erlenmeyer flask
with 100 to 150 mL distilled water; add 1 mL 6N H2SO4 or a few drops of
conc. H2SO4 and 20.00 mL standard bi-iodate solution. Dilute to 200 mL and
titrate liberated iodine with thiosulfate titrant, adding starch toward end of
titration, when a pale straw color is reached. When the solution is of equal,
mL 0.025M Na2S2O3 should be required. If not, adjust the Na2S2O3 solution
to 0.025M.
4. Relevant Theory:
“Dissolved oxygen (DO) is a measure of how much oxygen is dissolved in water or
the amount of oxygen available to living aquatic organisms”
Factors affecting dissolved oxygen concentration:
 Photosynthesis
 Respiration
 Decomposition
It affects the DO concentration by using the carbon dioxide and releasing the
oxygen as byproduct. While in case of respiration and it uses oxygen and releases
carbon dioxide which results in decrease in oxygen concentration. In case of
decomposition, it affects the DO concentration because bacteria and fungi use
oxygen for decomposing organic matter.
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.
 A total of three-fourths of the earth’s oxygen supply is produced by
phytoplankton in the oceans.
5. Procedure:
 Take BOD bottle.
 Fill it with sample solution till it overload. Place the cap.
 Discard the excess volume
 Remove the cap and add 1ml of MnSO4and add 1ml of alkali azide

26 | P a g e
 M. Qamar Habib (2018-CIV-73)

 Place the cap and discard the excess volume and we assume that brownish
precipitate occurs.
 Leave the bottle for 5-10 minutes. Brown Precipitate settle down
 Remove the cap and add 1ml of concentrated H2SO4
 Place the cap and discard the excess volume
 Reddish brown color appears in overall solution
 Sample is ready for titration
 Take a titration flask and add 100ml of reddish-brown solution
 Titrate it against 0.025 N Sodium Thiosulphate must be drop wise. Color
appears to pale yellow
 Add 1ml of Starch solution. Pale Yellow Color change to violet
 Again, titrate it with Sodium Thiosulphate and color will disappear
 Note the volume of Sodium Thiosulphate as A1
 Repeat the same procedure for remaining 200 ml of R.B solution
 These readings come A1, A2 and A3
6. Observation and calculations:

Sr.no. Sample Volume of sodium thiosulfate solution used

For 1 100 ml (a1) For 2nd 100ml (a2)
st
For 3rd 100ml (a3)
1 Tap water 2.4 2.5 2.5
2 Aerated 4.2 4.3 4.2
3 Lab Sample 0 0 0

A
DO
Sample (A1+A2+A3)
(mg/l)
(ml)
Tap water 7.4 4.983
Aerated 12.7 8.552
Lab Sample 0 0

7. Comments:
 Formation of white color precipitates on addition of manganese sulphate and
Alkali azide means water have zero DO.
 On addition of organic waste in water, microbes present in water will utilize
oxygen and as a result dissolved oxygen level decrease.
 The DO of Aerated sample is more than Tap Water.

27 | P a g e
 M. Qamar Habib (2018-CIV-73)

Experiment No. 7:
DETERMINATION OF BIOCHEMICAL OXYGEN
DEMAND (BOD) FOR WASTEWATER

1. Objectives:
To determine the biological oxygen demand of a given sample.
2. Significance:
For Aquatic life:
Most of the bacteria in aquatic water are aerobic. It means they use oxygen for
decomposition. However, in most cases, natural levels of oxygen in aquatic
systems are somewhat depleted by bacterial activity. If dissolved oxygen
concentration drops below 5ppm, fish will be unable to live for very long. Other
species such as carp or catfish will also be at risk below 5ppm.
For treatment plants:
BOD tells us about the strength of sewage. The test has wide applications in
measuring waste loading to treatment plants and in increasing the efficiency of
such systems. It is also used to determine the effects of discharges on receiving
waters.
Water quality indication:
BOD indicates the amount of organic matter present in water. Therefore, a low
BOD is an indicator of good quality water, while a high BOD indicates polluted
water.

28 | P a g e
 M. Qamar Habib (2018-CIV-73)

3. Related Theory:
Definition:
It is the amount of oxygen consumed by microorganisms to break down the
organic matter present in the sample (wastewater).
Introduction:
Microorganisms such as bacteria are responsible for decomposing organic waste.
When organic matter such as dead plants, leaves or even food waste is present in a
water supply, the bacteria will begin the process of breaking down this waste.
When this happens, most of the available dissolved oxygen is consumed by
bacteria, robbing other aquatic organisms of the oxygen they need to live. BOD is
a measure of oxygen used by microorganisms to decompose waste as described
earlier. If there is a large quantity of organic waste in the water supply, there will
also be a lot of bacteria present to decompose it. In this case, the demand for
oxygen will be high, so the BOD level will be high.
Principle:
BOD measurement is taken by taking two samples at each site. One is tested
immediately for dissolved oxygen, and the second is incubated at 20°C for 5 days
and then tested for the amount of dissolved oxygen remaining. The difference in
energy levels between the first test and the second test in mg/l is the amount of
BOD.
4. Apparatus:
• 300ml BOD bottles
• Incubator
• Graduated cylinders
• Pipettes
• Beakers
• Burettes
• Flasks
5. Reagents:
• Manganese sulfate solution: Dissolve 480 g MnSO4.4H2O, 400 g
MnSO4.2H2O or 364 g MnSO4.H2O in distilled water, filter, and dilute to
1L. The MnSO4 solution should not give a color with starch when added to
an acidified potassium iodide (KI) solution.
• Alkali-iodide-azide reagent
29 | P a g e
 M. Qamar Habib (2018-CIV-73)

• Sulfuric acid: One mL is equivalent to ~ 3mL alkali-iodide-azide reagent.

• Starch solution: Dissolve 2 g laboratory-grade soluble starch and 0.2 g
salicylic acid as preservative in 100 mL hot distilled water.
• Standard sodium thiosulfate titrant: Dissolve 6.205 g Na2S2O3 .5H2O in
distiller water and add
• 1.5 mL 6N NaOH or 0.4 g solid NaOH and dilute to 1000 mL. Standardize
with bi-iodate solution.
• Standard potassium bi-iodate solution (0.0021M): Dissolve 812.4 mg
KH(IO3) in distilled water and dilute to 1000 mL.
• Standardization: Dissolve e ~ 2 g KI, free from iodate in an Erlenmeyer
flask with 100 to 150 mL distilled water; add 1 mL 6N H2SO4 or a few drops
of conc. H2SO4 and 20.00 mL standard bi-iodate solution. Dilute to 200 mL
and titrate liberated iodine with thiosulfate titrant, adding starch toward end
of titration, when a pale straw color is reached. When the solution is of
equal, mL 0.025M Na2S2O3 should be required. If not, adjust the Na2S2O3
solution to 0.025M.
6. Procedure:
a) Take 11 BOD bottles, note their numbers and arrange them in four groups.
(three groups containing 3 bottles and one group with two bottles)
b) Half fill each of these bottles with dilution media.
c) Add 2ml of wastewater sample in three bottles one from each group (first
three).
d) Add 5ml of wastewater sample in one previous and other two bottles (one
from each group).
e) Add 10ml of wastewater sample in 3 bottles (one from each group)
f) Now fill the bottles completely with dilution media and place the stopper
such that no air bubbles are trapped.
g) Do not throw excess dilution media, it will prevent from any leakage.
h) Now take three bottles from first group and blank 1. Estimate their DO. This
will be DO at 0 day.
i) Place rest of seven bottles in the incubator at 20°C for 5 days.
j) After 5 days, find the DO in all the remaining bottles.
k) Now find the difference of DO at zero day and five day. This will be DO
depletion.
l) Calculate the BOD, using the following relationship;

30 | P a g e
 M. Qamar Habib (2018-CIV-73)

m) BOD5(mg/l) = (DO depletion (mg/l) × 300 (ml)) / (volume of sample in bottle

(ml))
7. Observations and calculations:
(𝑨𝑨𝑨𝑨 + 𝑨𝑨𝑨𝑨 + 𝑨𝑨𝑨𝑨) × 𝐕𝐕 × 𝐞𝐞𝐞𝐞. 𝐰𝐰𝐰𝐰𝐰𝐰𝐰𝐰𝐰𝐰𝐰𝐰 × 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏
𝑫𝑫𝑫𝑫 =
𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗 𝒐𝒐𝒐𝒐 𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔 × 𝐅𝐅

N=0.025N
eq. weight (oxygen) = 8
volume of sample = 300ml
𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗 𝒐𝒐𝒐𝒐 𝑩𝑩𝑩𝑩𝑩𝑩 𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 − 𝒔𝒔𝒔𝒔𝒔𝒔 𝒐𝒐𝒐𝒐 𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗 𝒐𝒐𝒐𝒐 𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓 𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂
𝑭𝑭 =
𝟑𝟑𝟑𝟑𝟑𝟑
𝟑𝟑𝟑𝟑𝟑𝟑 − 𝟑𝟑
𝑭𝑭 = = 𝟎𝟎. 𝟗𝟗𝟗𝟗
𝟑𝟑𝟑𝟑𝟑𝟑

BOD Of Samples
Bottle Bottle Sample added Volume of sample Volume of Na2S2O3 DO volume
no. (ml) (ml) (ml) (mg/L)
1 A1 1 300 9.7 6.47
2 A2 3 300 9.8 6.53
3 A3 5 300 9.6 6.40
4 Blank 1 Blank 300 10.2 6.80

After 5 days:
Sample Mean
Bottle no. Bottle Volume of sample Volume of Na2S2O3 DO volume
added DO

(ml) (ml) (ml) (mg/L) (mg/L)

1 B1 1 300 7.2 4.80
2 C1 1 300 7.3 4.87 4.83

3 B2 3 300 6.9 4.60

4 C2 3 300 7.1 4.73 4.67

5 B3 5 300 6.5 4.33

6 C3 5 300 6.4 4.27 4.30

7 Blank 2 Blank 300 10.1 6.73 6.73

31 | P a g e
 M. Qamar Habib (2018-CIV-73)

Calculations for DO depletion:

Bottle Volume of sample DO at day 0 DO at day 5 DO depletion BOD at day 5
(ml) (mg/L) (mg/L) (mg/L) (mg/L)
A1, B1, C1 1 6.47 4.83 1.64 491
A2, B2, C2 3 6.53 4.67 1.86 186
A3, B3, C3 5 6.40 4.3 2.10 126
Blank 1,2 Blank 6.8 6.78 0.02

Mean (BOD)5 = 268 mg/L

8. Comments:
• Natural/tap water cannot be used for preparing dilution media in BOD.
• Some samples do not contain sufficient bacteria to oxidize any organic
matter that may be present.
9. Reference:
AWWA, WEF, APHA, 1998, Standard Methods for the Examination of Water and
Wastewater (Method: 4500-O. C. Azide Modification)

AWWA, WEF, APHA, 1998, Standard Methods for the Examination of Water and
Wastewater(Method: 5210B,5-day BOD)

Sawyer, C.N., McCarty, P.L., and Parkin, G.F. 2000. Chemistry for Environmental
Engineering 4th Edition. Tata McGraw-Hill Publishing Company Limited.

32 | P a g e
 M. Qamar Habib (2018-CIV-73)

Experiment No. 8:
DETERMINATION OF CHEMICAL OXYGEN
DEMAND (COD)
1. Objective:
The main objective of this experiment is
 to determine the chemical oxygen demand (COD) of the given wastewater
sample.
 To determine COD value for determining organic strength of solution (Closed
Reflux Method)
2. Scope and significance:
 COD is widely used as a measure of the susceptibility to oxidation of the
organic and inorganic materials present in water bodies and in municipal and
industrial wastes.
 The chemical oxygen demand (COD) is a measure of water and wastewater
quality.
 The COD test is often used to monitor water treatment plant efficiency. This
test is since a strong oxidizing agent, under acidic conditions, can fully oxidize
almost any organic compound to carbon dioxide.
3. Apparatus:
 Reflex condenser
 COD flask
 Titration Flask
 Burette
4. Reagents:
 Standard potassium dichromate digestion solution, 0.01667M: Add to about
500 mL distilled water 4.903 g K2Cr2O7, primary standard grade, previously
dried at 150°C for 2 h, 167 mL conc. H2SO4, and 33.3 g HgSO4. Dissolve,
cool to room temperature, and dilute to 1000 mL.
 Sulfuric acid reagent:
 Ferroin indicator solution: Dilute it by a factor of 5 as required. This indicator
is used to indicate change in oxidation-reduction potential of the solution.

33 | P a g e
 M. Qamar Habib (2018-CIV-73)

 Standard ferrous ammonium sulfate titrant (FAS), approximately 0.10M:

Dissolve 39.2 g Fe(NH4)2(SO4)2.6H2O in distilled water. Add 20 mL conc
H2SO4, cool, and dilute to 1000 mL. Standardize solution daily against
standard K2Cr2O7 digestion solution as follows: Pipet 5.00 mL digestion
solution into a small beaker. Add 10 mL reagent water to substitute for
sample. Cool to room temperature. Add 1 to 2 drops diluted ferroin indicator
and titrate with FAS titrant.
Molarity of FAS solution = [VK2Cr2O7 ×0.1] / (VFAS) (3)
Where: VK2Cr2O7 = volume of K2Cr2O7 (mL); VFAS = volume of FAS (mL)
Sulfamic acid:
 Potassium hydrogen phthalate standard:
5. Related Theory:
Introduction:
For many years, the strong oxidizing agent potassium permanganate (KMnO4) was
used for measuring COD. However, KMnO4 was not able to effectively oxidize all
organic compounds in water, rendering it a relatively poor oxidizing agent for
determining COD. Since then, other oxidizing agents such as ceric sulphate,
potassium iodate, and potassium dichromate have been used to determine COD.
From these oxidizing agents, potassium dichromate has been found most effective,
relatively cheaper, easy to purify, and is able to oxidize almost all organic
compounds.
Definition:
Chemical oxygen demand (COD) is the amount of dissolved oxygen that must be
present in water to oxidize chemical organic materials.
OR
It is the estimate of oxygen required for the portion of organic matter in wastewater
that is subjected to oxidation.
Use of Potassium Dichromate:
Potassium dichromate is a strong oxidizing agent under acidic conditions. Most
commonly, a 0.25N solution of potassium dichromate is used for COD
determination. Although, for samples with COD below 50mg/l, a lower
concentration of potassium dichromate is preferred.

34 | P a g e
 M. Qamar Habib (2018-CIV-73)

Benefits of Potassium Dichromate:

Following are the benefits of using potassium dichromate for the determination of
COD;
 Potassium dichromate is a strong oxidizing agent under acidic conditions.
 It is most effective and relatively cheaper than other oxidizing agents.
 It is easy to purify.
 It is able to oxidize almost all organic compounds.
Advantages of estimating COD:
i. COD is widely used as a measure of the susceptibility to oxidation of the
organic and inorganic materials present in water bodies and in municipal and
industrial wastes.
ii. The chemical oxygen demand (COD) is a measure of water and wastewater
quality.
iii. The COD test is used to monitor water treatment plant efficiency.
iv. COD is used to gauge the short-term impact wastewater effluents will have
on the oxygen levels of receiving waters.
6. Procedure:
i. Take a 50ml sample in a COD flask and 6-7 glass beads in it.
ii. If the sample contains chlorides, it will react with Cr2O72- and chlorine will be
produced, which is highly toxic. To avoid this, add a pinch of AgCl or HgCl2.
iii. Then add 20-25ml of H2SO4 in the sample.
iv. Then add 25ml of K2Cr2O7 in it and then add the remaining 50ml H2SO4 in it.
The total volume of the sample will be 150ml.
v. Transfer COD flask to a reflux condenser.

35 | P a g e
 M. Qamar Habib (2018-CIV-73)

vi. High temperature produces oxygen, and that oxygen is assumed to react with
organic matter and decompose it.
vii. After 2hrs, stop heating and leave the COD apparatus for cooling.
viii. Then add 200ml distilled water in it. The total volume will be 350ml.
ix. Add 1ml of ferroin solution as an indicator. A brownish color will appear.
x. Titrate this solution against FAS (0.025N). The brown color will change to
green, then orange, and then again brown. That is the endpoint. Note the
reading of FAS and label it as A.
xi. Repeat the same procedure for the blank solution. In blank, instead of sample,
take 50ml distilled water while the remaining procedure is same.
xii. Note the volume of FAS used for blank and label it as B.
7. Observations and calculations:
𝟖𝟖 × 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏 × 𝑫𝑫𝑫𝑫 × 𝑴𝑴 × (𝑽𝑽𝑽𝑽 − 𝑽𝑽𝑽𝑽)
𝑪𝑪𝑪𝑪𝑪𝑪 =
𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗 𝒐𝒐𝒐𝒐 𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔 (𝒎𝒎𝒎𝒎)
Here,
DF = Dilution factor (if applicable)
M = Molarity of standardized Ferrous Ammonium Sulphate solution
VB = Volume consumed in titration with blank preparation
VS = Volume consumed in titration with sample preparation
Now,
Volume of Ferrous Ammonium Sulphate for sample (VS) = 23.8 ml
Volume of Ferrous Ammonium Sulphate for blank (VB) = 25.6 ml
Dilution factor (DF) = 1 (sample used as it is)

Sr. No. Vol. Of sample Initial volume Final volume Volume used “a”
1 100 0 4.7 4.7
2 100 4.7 9.7 5
3 150 9.7 14.6 4.9
Total volume used
A = 14.6

36 | P a g e
 M. Qamar Habib (2018-CIV-73)

Sr. No. Vol. Of sample Initial volume Final volume Volume used “b”
1 100 0 5.4 5.4
2 100 5.4 10.8 5.4
3 150 10.8 17.6 6.8
Average volume used
B= 17.6

COD (mg/l) = [(17.6-14.6) *0.25*8*1000] / 350

COD (mg/l) = 17.142 mg/L

8. Comments:
 According to W.H.O, the COD value of the wastewater before disposal into
the ocean must be less than 150 mg/l. As our value of COD is coming 17
mg/litre, so sample can be used as recycled wastewater.
 Our sample can be used as a wastewater for irrigation purposes.
 COD value will always be higher than BOD value.
 To remove the interference of chloride ions Ag2SO4 is used.
 COD measurements are commonly made on samples of waste waters or of
natural waters contaminated by domestic or industrial wastes.
9. Reference:
AWWA, WEF, APHA, 1998, Standard Methods for the Examination of Water
and Wastewater (Methods: 5220 C. Closed Reflux Titrimetric Method)

Sawyer, C.N., McCarty, P.L., and Parkin, G.F. 2000. Chemistry for
Environmental Engineering 4th Edition. Tata McGraw-Hill Publishing Company
Limited.

37 | P a g e