Department of Civil Engineering

Experiment No

Aim : To determine the acidity of various water samples.

Definition : The capacity of the sample to donate protons or the capacity of the sample in
neutralizing an alkali of known strength.

Causative Factors : Unionized portion of weekly-ionized acids (Carbonic, tannic, etc) and hydrolyzing
salts of Fe3+ and Al3+. Mineral acids to contribute to the acidity when the pH<
4.5.
Significance : Corrosiveness of the sample.

Expression of the result: Mg/l CaCO3

Titrant : N/50 or 0.02 N NaOH
Indicator : Methyl Orange: End point, Faint Orange: Characteristic of pH 4.5,
Phenolphthalein: End, Pink: Characteristic of pH 8.3.
Procedure : Add a drop of indicator suitable for the pH of the sample to 50ml aliquot and
titrate against N/50 NaOH so as to attain an appropriate end point.
Calculation : 1000 ml of 1N NaOH = 50gm CaCO3
1ml of 0.02 = 1 mg CaCO3
Total acidity mg/1 CaCO3 = Vol. of NaOH x 1000
ml of sample
Reactions : Mineral acidity / Organic acid + NaOH ÆNa-salt of
mineral acid (pH4.5) or Na-salt of Organic acid (pH8.3)

Result : Acidity of the water samples was found as follows :

S. No. Source Acidity of the sample

Conclusion : The given sample of water is acidic / corrosive / non – corrosive.

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Experiment No

Aim :To determine the alkalinity of various water samples.

Definition :The capacity of the sample to donate ‘OH’ ions or accept ‘H+’ ions or to
neutralize an acid of known strength.
Theory : Alkalinity of water is its acid neutralizing capacity. It is the capacity of water
to donate OH+ i.e. hydrate ions or accept H+ ions or hydrogen ions. It has the
significance in many ways and treatment of neutral water and waste water.
Alkalinity measurements are used in the interpretation of water and waste
water treatment process.

Causative Factors : Salts of weak acids, weak or strong base, bicarbonates,

carbonates, borates, silicates, phosphates, hydroxides etc.

Significance : Buffering capacity in accommodating H+ and OH- ions in

order to maintain the neutrality.

Standard : Nil
Expression of the : mg/l CaCO3
Result
Titrant : N/50 of 0.02 N H2SO4
Indicator : Phenolphthalein: End Point – Red to colourless. Characteristic
of 8.3 pH.
Methyl orange: End point – Yellow to Orange. Characteristic
of 4.5 pH.

Procedure : Take 50 ml of given sample in a conical flasks. Add 2 - 3 drops of

Phenolphthalein indicator and titrate with 0.02 N H2SO4 till the colour
changes to colorless solution. This is the ‘P’ end point indicating pH 8.3.
Note the burette reading.( If the pink colour does not appears after addition
of phenolphthalein indicator , the ‘ P’ end point is absent. In this case, add

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methyl orange indicator directly and get it complete). Now add 2-3 drops of
methyl orange indicator to the same sample and titrate with 0.02 N H2SO4 till
the yellow colour changes to orange i.e. pH 4.5 indicating ‘ T ’ end point.
Note the total volume of H2SO4 used.
1ml of 1N H2SO4 = 50 mg CaCo3
... 1ml of 0.02 N H2SO4 =1mg CaCo3
Formula:
{ml of H2SO4(0.02N) required
to get ‘P’ end pt. x 1000 }
Phenolphthalein Alkalinity or ‘P’ alkalinity (mg/l CaCo3) =
ml of water sample

{ml of H2SO4(0.02N) required

to get ‘T’ end pt. x 1000 }
Methyl orange alkalinity or
total alkalinity (T) (mg/l CaCo3) =
ml of water sample

Measurement of Individual Alkalinities:

SN Result of OH-alkalinity CO3-2 alkalinity HCO3- alkalinity

Titration mg/l CaCO3 mg/l CaCO3 mg/l CaCO3
1 P=0 0 0 T
2 P<1/2 .T 0 2P T-2P
3 P=1/2 .T 0 2P 0
4 P>1/2 .T 2P-T 2(T-P) 0
5 P=T T 0 0

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Reactions:
OH- + H+ --Æ H2O Phenolphthalein end pt. PH = 10
CO3 2-+ H+ --Æ HCO3 Phenolphthalein end pt. PH = 8.3
HCO3+ H+ --Æ H2CO3 Methyl Orange end pt. PH = 4.5
H2O + CO2 --Æ H2CO3 PH = 4.5pH
H2 CO3--Æ H++ HCO3- PH = 4.5 to 8.3
(Conjugate base exhibit alkali as well as acid characteristics)
HCO3- --Æ H++ CO3 2- PH = 8.3 to 10 pH
Or
2HCO3 --Æ CO3 2- + H2O + CO2 pH = 10 {Algal action )

CO3 + H2O --Æ CO2 + 2OH-

Observation Table:
S.N Initial Burette reading Final Burette reading Average value
1
2
3

Calculations of ‘ P’ and ‘ T ’ alkalinity of the given samples

S.N. ‘P’ alkalinity ‘ T ‘ alkalinity

Result: The P & T Alkalinities of the water sample was found as :

(i) P Alkalinity -------
(ii) T Alkalinity ----------

Conclusion : The given water sample possess high / low alkalinity.

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Experiment No

Aim : To determine the chloride content (Avgentometric method) in the given water
samples.

Theory : Chloride in the form of chloride Cl – ions, is one of the major inorganic anions in
water and waste water. The chloride concentration is higher in the waste water than
the water because of sodium chloride ( NaCl), a common ingredient of diet and
passes unchanged through the digestive system. At the sea coast, chloride may be
present in high concentration because of leakage of salt water into the sewage system.
It may be also increased by industrial process. High chloride content may harm metal
pipes and structures as well as growing plants.

Principle : In neutral or slightly alkaline solution K2CrO4 indicates the end of silver chloride gets
quantitatively precipitated before red silver chromate is formed.

Reagents : i) Chloride free water: Deionized water

ii) K2CrO4 indicator: Dissolve 50 gm in distilled water. Add AgNO3 solution till a
definite red precipitation is formed. Allow to stand for 12 hours filtration. Dilute the
filtrate to 1 liter Deionised water.
iii) Standard AgNO3 (0.0141 N): Dissolve 2.395 gm in distilled water and dilute to 1
Liter. 1ml of standard silver nitrate (0.0141 N) is equivalent to 500µg Cl-
iv) Standard NaCl (0.0141 N): Dissolve 824.1 mg water and dilute to 1 lit. 1ml of this
solution is equivalent to 500µg Cl-.
Procedure: : i) Use 100ml or a suitable aliquot diluted to 100ml with distilled water.
ii) If the sample is coloured, add 3ml Al(OH)3 wash. Combine the filtrate
and washing.
iii) Check the pH and adjust it to near neutrality.
iv) If sulphide, sulphite or thiosulphate is present, make the water alkaline
by Phenolphthalein with NaOH. Add 1ml H2O2, stir, neutralize with
H2SO4.

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v) Titrate the sample with AgNO3 after adding 1ml K2CrO4 to the sample
till orange red color appears.
vi) Run the blank taking distilled water as the sample.

Calculation :
1000ml of 1N AgNO3 = 35.45gm Cl-
... 1 ml of 0.0141 AgNO3 = 35.45 x 0.0141mg Cl-
= 0.499mg Cl- or say 500µg Cl- or 0.5mg Cl-

Formula :
(A-B) x 0.5 x1000
-
Mg/l Cl =
ml of sample

Where A = ml titrant of sample

B = ml titrant for blankV

Reaction: Cl- + AgNO3 --Æ AgCl+ NO3 –

K2CrO4 + 2AgNO3 --Æ Ag2CrO4 + 2KNO3

If pH> 8.3 - Ag (OH) 2, is precipitated,

If pH < 7 – Cr2 O7, is precipitated.

Ksp AgCl = 3 x 10-10, Ksp Ag2CrO4 = 5x 10-12

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Result Table :

S.N Type of sample (A-B) x 0.5 x1000

Mg/l Cl- =
ml of sample

Result : The chloride Content in the given water sample was found to be ------------ mg/l

Conclusion : The chloride content is ( high ---- may be due to --------)

( Well within specified limit)

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Experiment No

Aim : To determine the optimum coagulant dose for the removal of maximum
turbidity (generally a residual turbidity of 20 units is preferred) .
Generally carried out with the help of Jar test Apparatus in the given water samples.
Procedure: : Take 500 ml of water samples of which the turbidity is predetermined are placed in
several beakers. Different concentrations of coagulant solution (1 ml of coagulant = 10
mg) are then added to the turbid solution. Contents of the beakers are then mixed
rapidly at a speed of 100 rpm (flash mixing) for a period of 5 seconds to achieve an
intimate contact between the coagulant and the turbid waters. After the flash mixing,
contents are flocculated at a very low speed of 20-30 rpm (conditioning) for ½ an hour
and afterwards allowed to stand for one hour. The clarified supernatant is then decanted
and analyzed for residual turbidity. Plots the graph of applied dose of coagulant against
residual turbidity and form it an optimum dose of coagulant giving a residual turbidity
of 20 units is found out.
Reactions: - i) Al2 (SO4)3 H2O Æ 2Al3+ + 3SO4+
4.5 pH 7.5 pH
3+ -
ii) Al + 3OH Å------------ Al (OH)2 Å------------- H+ + AlO2- + H2 O
---------Æ ---------Æ + H2O
4.5pH 7.5pH
iii) Al3+ + Colloid Æ Al –colloid. De stabilization
iv ) Al2 (SO4)2 + 6H2O Æ 2Al (OH)3 + 3H2SO4+ 3Ca (HCO3)2 + 3H2SO4
Æ 3CaSO4 + 6CO2 + 6H2O
= Al2 (SO4)3 + 6H2O + 3Ca (HCO2) + 3HSO Æ 2Al (OH)3 + 3H2SO4
+ 3CaSO4 + 6CO2 + 6H2
Result : The optimum coagulant dose for removal of maximum turbidity was found out to be ---

Conclusion : It was found that the dose of -- mg/l was optimum, for removal of turbidity in a given
sample.
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Experiment No

Aim : To determine Biochemical oxygen demand ( B.O.D.) of given

Water / wastewater samples (BOD5)
Theory : BOD is the amount of O2 required by microorganisms for stabilizing
biologically decomposable organic matter in water/ wastewater sample under
aerobic condition. It is mainly used to determine pollution load of the waste
water, degree of pollution in lake or stream and the efficiency of waste water
treatment system.
Principle : : The method consist of sampling in airtight bottle of specified size overflowing
with sample and incubating at specified temperature for five days. Dissolved
oxygen ( D.O.) of blank and sample is measured and BOD is calculated using
the formula. It is necessary to provide standard condition such as nutrients, pH,
temp and mixed group of organisms as seed for determination of BOD.
Temperature is controlled at 20O C. The test is conducted for 5 days as 70 to 80
percent BOD is stabilized during the period.
Apparatus : Specially prepared BOD glass bottles provided with exactly fitting round glass
stoppers and surrounding well to accommodate 5 ml of water so as to exclude
exchange of gases. BOD incubator set at 200C.

Reagents
i) Distilled water of highest purity and thoroughly aerated so as to saturate
with DO at a lowered temp. of 200C.
ii) Phosphate buffer solution – 8.5 gm KH2PO4 , 21.75 gm
K2 HPO4, 33.4 gm Na2 HPO4.
iii) Magnesium sulphate solution–22.5gm MgSO4H2O dissolved in 1-1 of
distilled water.
iv) Calcium chloride solution – 27.5 gm anhydrous CaCl2 dissolved in 1-1
distilled water.

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v) Ferric chloride solution – 0.25 gm FeCl3, 6 H2O in 1-1 distilled water,
All other regents are similar to those in Do measurement.

Preparation of dilution water: Place required amount of aerated distilled water at 200C. Add 1 ml each of
phosphate buffer, magnesium sulphate, calcium chloride and ferric chloride
per liter of water, Seed the dilution water, if necessary by adding 1 to 10 ml
of settled sewage (24 to 36 hours old) per liter (seed should not exert more
then 0.5 mg/l of depletion of DO in the blank). Seeded dilution water
should be used the same day it is prepared..

Dilution of sample : When the BOD value is expected to be more than 5.0 mg/l, dilution of the
sample is necessarily neutralized at pH 7.0. Sample should be free from
residual chlorine. If it contains chlorine then sodium sulphide should be
added . Make several dilutions of the prepared solution for DO. Depletion in
DO should not be less than than 2 mg/ L and dissolved oxygen should not be
less than 1 mg/L after 5 days. Generally following dilutions suggested
0.1 to 1 % for strong trade waste
1 to 5 % for raw and settle waste / sewage
5 to 25 % for oxidized effluent
25 to 100 % for polluted river water

Procedure for BOD set up : Select a definite volume of sample (less than 300 ml), add to BOD bottle and
fill completely with dilution water. All concentrations should be in duplicate.
Keep one bottle of each concentrate in the BOD incubator for 5 Days at 200C
and subject the duplicate of that concentration to do determination of D.O. on
the same day. That will be zero Day D.O. Similarly put one or two bottles for
finding out the depletion of DO in blank (Seeded dilution water only) in
incubator and find out D.O. of these samples after 5 days. Find out the
difference between O day Do and 5 day DO values.

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Calculations : BOD5 = p [ (DO1 – DOf) – (B1 – Bf) f ], where

p = dilution factor
B1, Bf = initial and final DO concentrations of the seeded diluted
water (blanks)
f = ratio of seed DO in sample to seed in blanks
= % seed in DO1
% seed in B1

Reaction : CnHaObNc + (n+a/4 – b/2 – 3/4C)O2 - CO2 + (a/2 – 3/2C) H2O +

NH3

Result : The BOD5 of the given sample was found to be ------- mg/l

Conclusion : The BOD5 value of the sample is high / well within permissible limit of disposal.

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 Department of Civil Engineering

Experiment No

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

Theory : The COD is used to measure oxygen equivalent of organic matter content in a sample i.e.
susceptible to oxidation by a strong chemical oxidant. This is determined by refluxing the
sample with an excess of potassium dichromate in a highly acidic conditions and
estimating by titration the amount of dichromate used. A reducing agent like ferrous
ammonium sulphate is used. COD can be related empirically to BOD, organic carbon or
organic matter. The test is useful for monitoring and controlled after correlation has been
established. The dichromate reflux method is preferred to other oxidizing agents because
of superior oxidizing ability.
Principle : Most types of organic matters are oxidized by the boiling mixtures and chromic &
sulphuric acid . A sample is refluxed in strong acid solution with the known excess
amount of potassium dichromate. After digestion the reamaining unreduced K2Cr2O7 is
treated with ferrous ammonium sulphate (FAS ) to determine the amount of K2Cr2O7
consumed and oxidisable organic matter is calculated in terms of oxygen equivalent .
Mercuric sulphate is added to remove inference of chlorides. Silver sulphate is added as
catalyst as it catalyses oxidation of long chain aliphatic compounds.
Interference: Chlorides – 1mg/l Cl- exerts 0.23 mg/l of COD. Therefore correction as mg/l Cl- x 0.23
should be applied the COD of Cl- from the total COD. Nitrite exert COD of 1.1 mg/mgN.
Limitations: Amino nitrogen gets converted to ammonia nitrogen. All organic compounds with few
exceptions (e.g. aromatic hydrocarbons, straight aliphatic compounds and pyridine) are
oxidized by this procedure.
Reagents:
i) Standard potassium dichromate 0.25 N
ii) Conc. H2SO4 (A.R. Grade)
iii) Ferroin Indicator – Dissolve 1.485gm 1-10 phenanthroline monohydrate together with0.695
gm ferrous sulphate (FeSO4, 7H2O) in distilled water and dilute to 100 ml.

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iv) Catalyst –Silver Sulfate (for 8 straight chain sulphatic compounds) mercuric sulphate (for Cl-).
v) Sulphomic acid – Required only if the interference of NO2 is to be eliminated. Add 10 mg
sulphamic acid/mg NO2 – N if present, in the refluxing flask. (Do not forget to add in blank
also in this case)
Procedure: Place 50 ml sample or aliquot diluted to 50 ml with distilled water in a 300 ml capacity
round bottom refluxing flask with ground glass joint. Add 25 ml K2Cr2O7 and 75 Conc. H2SO4
gently shake. Attach refluxing condenser and reflux the mixture for 2 hr. After refluxing wash
the condenser with distilled water. Cool the mixture. Dilute the mixture with distilled water.
Titrate with ferrous ammonium sulphate (0.25 N) with ferroin indicator till the red colour
appears after the intermediate green colour
Note: -
1. While refluxing if the colour changes to green discard the mixture as potassium
Dichromate is not sufficient to oxidize the solution.
2. For small volumes i.e. 10, 20, 30, 40 ml of samples, proportionate reduction of
potassium Dichromate & sulphuric acid may done)
Calculation:
COD mg/l = (A-B) N x 8000 / V , where
A = Volume in ml. Ferrous ammonium sulphate for blank
B = Volume in ml. Ferrous ammonium sulphate for Sample
V = Volume of sample
N = Normality of ferrous ammonium sulphate

Result : The COD of the given sample was found to be ------- mg/l

Conclusion : The COD value of the sample is high / well within permissible limit of disposal.
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Experiment No

Aim : To determine the pH of given samples

Theory : It is the logarithm of the hydrogen ion concentration with a negative sign [pH = - log (H) + ]
Water does not show any reaction with acid or alkali when the dissociation products of it are in
equilibrium (HOH Æ H+ + OH-. H+ = OH- = 10-7). pH at this point is 7. When (H+)
concentration increases, water becomes acidic and when decreases water becomes alkaline pH
scale –
|
| 7
0 acidic 7 Neutral 14 alkaline

Method: The determination shall be carried out either by the electrometric method, using glass and
calomel electrodes or by the indicator method. In case of dispute the electrometric method shall
be considered as the accurate method.
Electrometric pH Measurement: The pH meter is the most widely used electrical method for finding out
the hydrogen ion concentration of a sample. pH is defined as the logarithm of hydrogen ion
concentration with negative sign. In this case a Glass Electrode and a Reference Electrode are
inserted in a solution and the electric potential or voltage across these electrodes is taken as a
measure of the hydrogen ions in the solution. Reference Electrode is generally the Calomel
Electrode.
With ordinary glass electrode pH can be measured in a range of 2 to 10 pH only as the glass is
made up of sodium silicate which gets affected by pH beyond this range. Special glass
electrode called the Universal Glass Electrode can be used to detect pH in the full range of 0 to
14.
Indicator Method:
Reagents – Series of indicators and buffer solutions are required for this method or an universal indicator
(0.05 g methyl orange, 0.15 g methyl red 0.3 g bromothymol blue 0.35 of phenolphthalein in
one liter of 66% alcohol). Colour changes shown by universal indicator are as follows-

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pH Up to 4 5 6 7 8 9 10 11
3

Colour Red Orange orange yellow yellowish greenish blue violet reddish
- red green blue violet

Indicators
(Individual indicators for different pH ranges)

Sr. Name of Indicator pH Pange Color Change

No.

(1) (2) (3) (3)

i) Thymol blue (acid range) 1.2 to 2.8 Red to yellow

ii) Bromophenol blue. 3.0 to 4.6 Yellow to blue violet.
iii) Bromocresol Green 3.8 to 5.4 Yellow to blue.
iv) Methyl Read. 4.2 to 6.3 Red to yellow
v) Bromocresol Purple 5.2 to 6.8 Yellow to blue violet.
vi) Bromothymol blue 6.0 to 7.6 Yellow to blue
vii) Phenol Red 6.8 to 8.4 Yellow to red
viii) Cresol Red 7.2 to 8.8 Yellow to red
ix) Thymol blue (alkali range) 8.0 to 9.6 Yellow to blue
x) Thymolphthalein 9.3 to 10.5 Colourless to blue
xi) Thymol violet 9.0 to 13.0 Yellow to Green to violet

Result : The pH of the given sample of water is found out to be -----

Conclusion : The pH was found out to be alkaline / acidic / in the neutral range. The pH is in / not in the limit
of acceptable standards.
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Experiment No
Aim : To determine the turbidity of given water samples
Definition : Absorption coefficient of a liquid or it is the expression of the optical property of a
sample which causes light to e scattered and absorbed rather than transmitted in
straight line through the sample.
Causative Factor: Non-settleable suspended matter (Colloidal) e.g. clay, silt, finely divided inorganic
and organic matter or plankton.
Expression of Result : Nephelometric Turbidity Unit NTU as an electrometric indication

Procedure : Place standard turbidity solution tubes of 10 NTU, 100 NTU, 1000 NTU turbidity. Put
the tubes in nephelometer and calibrate it at these ranges. Remove the tube of standard
calibration and now put the tube containing sample for which the turbidity has to be
measured. The turbidity value will be displayed at the screen of the nephelometer. Note the
value, replace the tube with another one containing the sample.

Observation Table :

S. No. Sample (source) / type Turbidity in NTU

Result : The turbidity of given water sample was found out to be ---- NTU.

Conclusion : The turbidity of the sample is in / not in acceptable limit. It need / does not need chemical
treatment.

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Experiment No

Aim : To determine sludge volume index of the given waste water sample

Definition : It is the volume in milliliters occupied by 1 g. of activated sludge after the

aeration and settling for the period of 30 minutes.
Procedure:
i) Collect one liter sample from the outlet of the aeration chamber and keep it standing in Imhoff
Cone or graduated measuring cylinder and observe the volume of sludge occupied by it after
30 minutes.
ii) If settling rate is to be observed take observations of volume occupied by the sludge after a
fixed interval of time for 30 minutes and plot the graph (time versus volume.)
iii) Take the thoroughly mixed sample and find out the suspended solids and report per cent by
weight or mg/l.
Observation Table :

No. Volume Occupied by Sludge in Suspended Solids in

30 minutes mg/l

Calculation:-
% setting by volume
SVI = ------------------------------------
% suspended matter
ml. settled sludge x 1000
or SVI = --------------------------------------
mg/l. suspended matter
Result : The sludge volume Index of the given sample was found to be -----
Conclusion : The sample contain -------- % settleable solids.
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Experiment No

Aim : To determine the sulphate content of the given water sample

Principle : Sulphate ions ( SO4-2 ) is precipitate in an acetic acid medium with barium chloride ( BaCl2) so
as to form barium sulphate (BaSO4) crystals of uniform size. Light absorption of the BaSO4
suspension is measured by photometer and the sulphate concentration is determined by
comparison of reading with standard curve.
Apparatus: 1) Magnetic stirrer
2) Klett summerson colorimeter or spectro photometer
3) Measuring spoon
Reagent:
a) Conditioning reagent – Mix 50 ml glycerol with a solution containing 30 ml
conc. HCL, 300 ml distilled water, 100 ml 95% ethyl alcohol and 75 gm
sodium chloride.
b) Barium chloride crystals ‘AR grade’.
c) Standard Sulphate solution – Prepare by diluting 10.41 ml of the standard 0.02
NH2SO4 to 100 ml with distilled water.
Procedure:
a) Formation of barium sulphate turbidity – Measure 100ml sample or a suitable
aliquot made up to 100 ml into a 250ml Erlenmeyer flask. Add exactly 5 ml
conditioning reagent and mix in the stirring apparatus. While the solution is
being stirred add a spoon full of barium chloride crystals stir
b) Measurements of barium sulphate turbidity – Immediately after the stirring period
is over, pour some of the solution into the absorption cell of the photometer and
measure the absorption at fifth minute. Maximum turbidity is usually achieved
within 2 min. and the reading remains constant there after for 3-10 min.
c) Read mg SO4 present in the sample on the calibration curve prepared by standard
solutions,

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Calculations:

mg / l SO42- = mg SO42- x 1000 / ml sample

Conditioning
Reaction - SO42- + BaCl2 BaSO4
SO4Solution

Result : The sulphate content of the given sample was found out to be -------- mg/l

Conclusion : The sulphate content is within / not in the prescribed limit as per specifications of WHO / CPCB
standards.

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Experiment No

Aim : To determine the hardness of the given water sample

Theory : Originally water hardness was understood to be a measure of the
capacity of water to precipitated soap. Soap is precipitated chiefly by the
calcium and magnesium ions presents and other polyvalent cations may also
presipate soap, buy they obtain in complex form, frequently with organic
constituents and their role in water hardness may be minimal and difficult to
define. Hence the total hardness is define as the sum of calcium and magnesium
concentration, both express as Calcium carbonate in mg / L
Principle : Ethylene diamine Tetraacetic acid ( EDTA) and its calcium salt from
a chelated soluble complex when added to the solution of certain metal cations.
If the dye such as Erichrome Black T is added to an aqueous solution
containing calcium and magnesium ions at pH of 10 +- 0.1 , then solution
become wine red. If EDTA is added as a tritant , then calcium and magnesium
will be complexed and when all calcium and magnesium has been complexed ,
the solution turn from blue to wine red making the end point of titration. At pH
higher than 10 i.e. around 12, magnesium ions ( Mg +2) gets precipited and only
calcium ions remains in the solution. At this stage if ammonium purported is
+2
added it is thenform pink colour. When EDTA titrate is added, Ca gets
complexed and hence there is a colour change from pink to purple .
Causative Factor : Divalent metallization, e.g., Ca2+, Mg2+, Fe2+, Sr2+ etc.

Hardness : Total (Ca2+ + Mg2+) Hardness or TH and Calcium hardness CaH

Expression of the Result: mg/l CaCO3

Titrant: Disodium salt of Ethylene Diamamine Tetraacetric Acid (EDTA) 0.01

N. Dissolve Commercial grade disodium salt of EDTA – 3.723 g in
one liter of distilled water (1 ml of this solution is equivalent to 1 mg
CaCO3.

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Standard Solution : Calcium Carbonate: 1 g anhydrous CaCO3 dissolved in 1+1 HC 1 (just
enough) and add 200 ml distilled water. Boil to expel CO2 Cool and
add Methyl Red indicator and adjust to the intermediate orange color by
adding 3 N NH4 OH or 1+1 HCL, -Dilute to 1 liter.
Indicators: a) CaH – Ammonium purpurate or Murexide Color/Change: Purple
(Original) – Pink – purple or Violet.
b) TH – Eriochrome Black T Color Change: Blue – wine
Red-Blue.
Procedure Take EDTA in a burette. Take 10 ml of Std solution of CaCO3 in a
conical flask. Add few ml of NaOH in it. To increase the pH Add
murexide to it as a oxide as an indicator. Tritrate till the colour changes
from pink to purple.
For Total Hardness : Take 50 ml of sample in a conical flask. Add few ml of buffer solution
to it to maintain pH . Add 2-3 drops of EBT and tritrate with std.
solution EDTA till wine red colour turn blue. Note down the reading.
For Calcium Hardness : Hardness due to magnesium is removed by increseing pH of the sample
more than 10 , so that magnesium ions gets precipited. For this purpose,
add few ml of NaOH to 50 ml sample in the conicasl flask and add
murexide as an indicator. Tritrate with Std. solution EDTA till pink
colour changes from pupple. Note down the reading.

Reactions: NaOH
CaH: Murexide indicator (Purple) + Ca2 (part) -----------Æ Indicator Cachelate.
PH > 10
Excess Ca2+ + EDTA Æ EDTA – Ca chelate.
EDTA + Indicator – Cachelate Æ EDTA – Ca chelate + Indicator (purple)

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Buffer
TH: Eriochrome Black T + [Ca2+ + Mg2+] part ---------Æ
± 10
Eriochrome Black T-(Ca + Mg) chelate
EDTA + Ca2+ + Mg2+ excess Æ EDTA – Ca + Mg chelate
EDTA + Eriochrome Black T – Ca + Mg chelate Æ EDTA
(Ca+Mg) chelate + Eriochrome Black T (Blue)
TH – CaH = MgH

Result : The Hardness of the given water sample was found to be ----------- mg /l

Conclusion : The given water is Hard / Soft . The hardness is within / above the acceptable limit of drinking
water.

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Experiment No

Aim To prepare filter sand from the stock sand and determine effective size and
uniformity coefficient
Theory Natural run –of – bank sand may be too coarse or too fine for a projected filter.
Within economical limits, specified sizing and uniformity can be obtained by
screening out coarse grains and washing out fines. To get the purified water , the
sand should have specific properties i.e. D10 , D60.
Formula :
Pusable = 2 ( P60.- P10 )
Ptoo fine = {P10 – 0.2 (P60.- P10 ) }
Ptoo coarse = {P10 + 1.8 (P60.- P10 )}

Procedure Wash the sand and then filter the stock sand by arranging the various seives. Shake
the seives for the 20-30 minutes and the measure the wt of sand retained on each
sieve. From the data calculate the % retained on each sieve . Plot the graph by taking
% finer on ‘Y’ axis and diameter of grain size on ‘ X’ axis. From the graph find out
the value of D60 and D10. Assume the value of coefficient of sand ( CU) in the range
of 1.3-1.8. Calculate the Pusable, Ptoo fine , Ptoo coarse ..

Result : Pusable =
Ptoo fine =
Ptoo coarse =

From the plotted graph, the D10 and D60 for the sand are ---------------------------

Conclusion : Thus the D60 and D10 parameters for the sand are obtained from the given sample.

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Experiment No

Aim : To determine the Available Chlorine and Residual Chlorine in a Given Water
Sample
Theory :
Chlorine determination includes:
a) Available chlorine in case of chlorine solution, bleaching powder or chlorine tablets.
b) Chlorine demand (assessment of the requirement of the quantity of chlorine to be added).
c) Residual Chlorine- i) Free residual during Break Point chlorination, ii) Total combined during Break
point Chlorination.
Apparatus: Chlorine Determination Kit (Colour Comapatometer)
a) Available Chlorine (Bleaching Powder):
Reagents:
ii) Bleaching powder solution: Make a paste of 1 g. bleaching powder (CaCl, OCL, H2O) in minimum
water and dilute the paste with distilled water to a volume of 100 ml. Take care to see that the
paste is transferred tot eh volumetric flask quantitatively.
iii) 0.025N sodium Thisulphate: 6.25 g. Na2S2O3, 5H2O is dissolved in 1 liter of distilled water.
iv) Glacial acetic acid.
v) Potassium iodide crystals.
vi) 0.1 N potassium iodate solution: 812 mg dissolved in 250 ml. distilled water.
vii) Starch indicator: 5 g soluble starch mixed with little water and ground in a pestle and mortar so as
to prepare a paste. Paste is than transferred quantitatively to 1 liter of boiling water. Mixture is then
allowed to settle overnight and the supernatant is used.

Procedure:
i) Take 10 ml of bleaching powder solution in a conical flask and add to it KI crystals. Sufficient
distilled water and approximately 2 ml of glacial acetic acid mix.
ii) Titrate the sample till dark amber colored solution turns to pale straw color.
iii) Add starch indicator and Mix.
iv) Titrate till the blue colored starch iodide complex becomes colorless.

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v) Prepare reagent blank using distilled water. Note the volume of thiosulphate required.
Calculations:
1 ml of 1 N Thio = 35.45 mg Cl2
1 ml of 0.025 N Thio = 35.45 x 0.025
= 0.88625 or Say 0.89
ml of thio x 0.89 x 100
∴ Percent available= ----------- x (100 in bleaching chlorine ml of B. P. Solution Powder)

Interference:
Mn, Fe, and NO2 interfere in Iodometric titration. To overcome this interference acetic acid is used in
place of H2SO4 for acidification of the sample.
Reactions:
Ca.OCl.Cl. H2O + 2CH5 COOH Æ (CH3 COO) 2 Ca + 2H2O+ Cl2
Cl2 + 2 KI Æ2 KCI + I2
I2 + StarchÆBlue colored Starch-iodide complex (Qualitative Test)
I2 + 2Na2 S2 O2Æ 2Nal + Na2 S4 O6 colorless (Qualitative Test)

Chlorine Demand:
General:
Disinfection is the unit operation which cannot be missed in the treatment plants from the point of
view of supply of safe water. Chlorine either in the form of gas or bleaching powder, is a universally accepted
disinfectant. In addition to destruction of pathogons, chlorination is also used to achieve oxidation of Fe2+,
NH3 Mn +, H2S removal of taste and odour problems and oxidation of organic compounds in water or waste
waters by forming their chloro-derivatives.
In order to have an effective disinfection by chlorine in water treatment, following points need
scientific thinking viz., determination of chlorine dose so as the have residual chlorine of 0.2 mg/l after a
contact time of 30 min. These points are very well considered in this concept of breakpoint chlorination.

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Principal:
Bleaching powder or chlorine gas when added to the water reacts with organic matter, if present, and kills
pathogens resulting in the formation of chloroderivatives and free residual chlorine. The dose which achieves
this, leaving behind, o.2 to 0.4 mg/l free residual chlorine can be taken as chlorine demand of that water for
the particular contact period, temp. and PH.

Interference:
Unsaturated organic compounds, Fe2+ Mn2+, NO2, organic nitrogen and NH3 are the main interfering
substances.These can be eliminated by changing the sequence of regent additions using break point
chlorination.
Apparatus:
Chlorine determination kit (color comparator) to measure residual chlorine.
Reagents:
1. Orthotolidine: Dissolve 1.35 g orthotolidine dihydrochloride in 500 ml distilled water. Add it
to a mixture of 350 ml distilled water + 150 ml Conc. HCl. Store in a colored bottle.
2. Sod. Arsenite: Dissolve 5 g NaAsO2 and dilute to 1000 ml.
3. Standard chlorine solution: Prepare chlorine solution from bleaching powder and determine its
strength as described in the test for available chlorine. This solution has to be prepared freshly.
Procedure:
1. Take identical aliquots of 100ml well water in 12 conical flasks or bottles (stoppered).
2. Add chlorine solution in increasing quantity to the bottles or flasks to result in a concentration in the
range of 0.1 to 3.00 gm/l. Mix well.
3. Allow to stand for predetermined contact period usually 30 to 60 min.
4. Determine the residual chlorine present in each bottle by OT test as described.
5. Plot chlorine residual Vs chlorine added and determines chlorine required at breakpoint. This will give
the chlorine demand of that specific water.
6. This can also be determined by measuring free residual chlorine left after contact period. The dose
where 0.2 mg/l free residual chlorine is left out will give the amount of chlorine required to disinfect
the water.

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Reaction : Cl OH
| |
i) –C = C – + HOCL Æ - C – C – (unsaturated organic compounds)
| | | |
H H H H

ii) Fe2+Mn2+ /NO2- + HOCL Æ Fe3+ /Mn3+ /NO3- (Reducing

substances)
iii) H2S + 4Cl2 + 4H2O Æ H2SO4 + 8HCl (Reducing substances)
iv) NH3 + HOCl Æ NH2Cl (Monochloramine) + H2O
NH3 + 2HOCl Æ NHCl2 (Dichloramine) + 2H2O
NH2Cl + HOCl Æ NHCl2 + H2O
NH3 + 3HOCl Æ NCl3* (Trichloramine) + 3H2O
NH2Cl + HOCl Æ NCl3* + H2O
NH2 + NHCl2 + HOCl Æ N2O ↑ + 4H2O
NH2Cl + NHCl2 Æ N2* + 3HCl
Formation of chloramines with respect to pH values:
If pH > 8.4, Monochloramines.
If pH is in the range of 4.4 – 5.5, Dichloramines.
If pH < 4.4, Trichloramines
Complete oxidation state of ammonia or the ‘Break Point.’ After this point no more chlorine demand will be
exerted.
At pH in between 5.5 = 8.4 Mono and Dichloramine exist together Relation of these two species of
chloramines is fixed by the pH Value. At pH 7, Monochloramine: Dichloramino = 50: 50.

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Residual Chlorine:
Reagents:
i) Orthotolidine: Weigh 1.35 g. Orthololidine dihydrochloride in 50 ml distilled water. Add to this
mixture 150 ml conc. HCl and make this Vol. to 1 liter. Store the solution in brown bottle or in the
dark.
ii) Sodium arserite solution: Dissolved 0.5 g. Na As O2 (Sodium meta arsenate) in 1000 ml of
distilled water. Take care to avoid ingestion since it is toxic.
iii) Copper sulphate solution: Dissolve 1.5 g. copper sulphate in 50 to 60 ml distilled water, add 1 ml
conc-sulphuric acid and make up to 100 ml.
Potassium dichromate solution: Dissolve 0.25 g of potassium dichromate in distilled water, add 1
ml of conc. Sulfuric acid and make up to 1 liter.
Standard color solution: Measure in the 100 ml. Nessler cylinder the volumes of copper sulphate
solution and potassium dichromate solution so as given in Table and dilute to 100 ml with distilled
water. In column 2 of the table are given amounts of chlorine to which the color solutions are
equivalent.

Procedure:
Use three Nessler cylinders and designate then as cylinders A, B and C. In cylinder a add 1 ml of O-tolidine
regent, 100 ml of the sample, mix and add immediately 2 ml of sod. Arsenite solution, mix
and after 5 seconds, compare the color with standard color solution.
This reaction (FR) represents the total of free residual chlorine and of interfering substances.
In cylinder B, add 2 ml of sodium arsenite solution and 100 ml of the sample mix and add immediately
1 ml of orihotolidine reagent. Mix and match the color with standard solutions. This reading (B1) is the blank
for interfering substances after 2 min standing. Also allow it to stand for 5 minutes and record the result. This
reading (B2) is the blank for interfering substance after 5 minutes standing.
In cylinder ‘C’ add 1 ml of O-tolidine reagent and 100 ml of the sample, mix and after 5 minutes
match the color. This reading (TR) gives the total residual chlorine plus interfering substances.

NOTE: Use 0.5 ml Orhotolidine for 10 ml. sample

0.75 ml Orhotolidine for 15 ml. sample

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TABLE : Standing color solutions for residual chlorine determination

Sr. No. Chlorine Copper Sulphate Solution Potassium Dichromate Solution

Mg/l ml Ml

I 0.01 0 0.8

II 0.02 0 2.1

III 0.03 0 3.2

IV 0.04 0 4.3

V 0.05 0.4 5.5

VI 0.06 0.8 6.6

VII 0.07 1.2 7.5

VIII 0.08 1.5 8.2

IX 0.09 1.7 9.0

X 0.10 1.8 10.0

XI 0.15 1.8 15.0

XII 0.2 1.9 20.0

XIII 0.25 1.9 20.0

XIV 0.30 1.9 30.0

XV 0.35 1.9 34.0

XVI 0.40 2.0 38.0

XVII 0.50 2.0 45.0

XVIII 0.60 2.0 51.0

XIX 0.70 2.0 58.0

XX 0.80 2.0 63.0

XXI 0.90 2.0 67.0

XXII 1.00 3.0 72.0

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Calculation:
a) Free residual chlorine (as Cl) mg/l = FR-B1
b) Total residual chlorine (as Cl) mg/l = TR-B2
c) Combined residual chlorine (as Cl) mg/l = (TR-B2) - (FR-B1)
Range:
The method is applicable up to 5 mg/l of chlorine.

Result : The free, Total and combined residual chlorine values found out were ------

Conclusion : The water is sufficiently / super / more than required chlorinated.

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Experiment No.

Aim : Determination of Solids in a given sample of water

Theory :

setting time Settled solids t Dissolved Solid +

(Total solids) -----------Æ Colloidal or suspended solids
Volatile: organic fraction
Dissolved Solids (filtrate) --
Fixed: Residue after burning
At 6000C for 1 hr.
Filter Settled Water -Æ
Volatile: organic fraction
Suspended Solids --
(Retained on filter paper) Fixed: Residue after burning
At 6000C for 1 hr.
Procedure:
Total Solids:
Pipette out 100 ml of well mixed sample in to the clean dry weighing dish and evaporate to dryness at
1050C. Cool the weighing dish at R.T. and weigh.
mg of residue x 1000
Total solids mg/1 =
Ml sample.
Fixed residue:
Ignite the residue obtained in total solids determination or volatile solids determination at 550C to
6000C for one hour in the platinum crucible in the muffle furnace. Cool the crucible and weigh. Find
out the amount of fixed residue in the and contains dissolved nonvolatile as well as suspended

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nonvolatile residue. This is known as ignited residue also.
mg of residue x 1000
Ignited residue, mg/1 = ------------------------------------
Ml sample.
Or fixed residue
Volatile residue = Total solids - Ignited residue
Dissolved Solids:
Pipette out 100 ml of the well mixed sample and filter through a filter paper. Collect the filtrate in a clear and
previously weighed evaporating dish at room temperature and weigh,
mg of residue x 1000
Total dissolved solids mg/1 =
Ml sample.
Suspended matter – It is determined generally indirectly as follows-
Suspended matter mg/ 1 = Total solids mg/1 – Dissolved solids mg/1
If the Glass Fiber filter paper GFC grade (What man make) is available this determination can be done
directly. This paper keeps the consistency not only at 1050C but at 6000C also. While using this filter paper a
separate filter assembly known as Hartley’s Filter assembly is made use of.

Result : The sample of water contain Total Solids -------- mg/l

Suspended Solids : = ---------------- mg/l
Dissolved Solids = ---------------- mg/l.

Conclusion : The sample contain the solids various percentage ------as which are within /beyond the
permissible limits.

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