Module 4

WATER TECHNOLOGY
Sources of water

Surface water – Rain water, River water, Lake water, Sea water, etc.

Underground water – Spring and well water.

Impurities in water

Dissolved gases : carbon dioxide, oxygen, ammonia, sulphur dioxide ,

oxides of nitrogen, etc.

Dissolved solids : Salts of calcium, magnesium, sodium and nitrates,

nitrites, silicates, ferrous and ammonium salts, etc.

Suspended impurities : Two types : Inorganic impurities : clay, silica,

hydroxides of iron and aluminium.

Organic impurities : wood pieces, leaf, decaying vegetable matter, fishes,

bacteria, algae, protozoa, etc.
Hardness of water

Hardness of water is due to the presence of dissolved salts of calcium

and magnesium in water. Hard water is one which does not produce
lather readily with soap. Soft water is one which readily produces lather
with soap.

There are two types of hardness

Temporary hardness – It is due to the presence of bicarbonates of Ca

and Mg in water. It is also called as carbonate hardness. It can be
removed by boiling the water.

Permanent hardness – It is due to the presence of chlorides and

sulphates of Ca and Mg in water. It is also called as non - carbonate
hardness. It cannot be removed by boiling the water. It can be removed
by chemical treatment.

Hardness of water is expressed in PPM (parts per million) of CaCO 3

equivalent.
Water analysis

Determination of hardness of water by EDTA method

Principle

This method involves complexometric titration. Total hardness of water is

determined by titrating a known volume of water sample with EDTA
solution using EBT indicator. The permanent hardness of water can be
determined by titrating water after boiling to remove the temporary
hardness as carbonate precipitate.

Procedure

a) Preparation of standard CaCO3 solution (Standard water)

Weigh accurately about 0.5 g of calcium carbonate into a 250 ml standard

flask. Dissolve the salt with minimum quantity of dilute HCl. Make up the
solution to the mark with distilled water and mix well.
b) Standardisation of EDTA
Pipette out 50ml of standard water into a conical flask. Add 5 ml of
NH4OH-NH4Cl buffer solution, 3-4 drops of EBT indicator and titrate
with EDTA solution (about 0.025M) till the colour changes from wine
red to clear blue. Let the volume of EDTA consumed by standard
water be ‘V’ ml.

c) Estimation of total hardness of water

Pipette out 50 ml of hard water sample into a conical flask. Add 5 ml of
NH4OH-NH4Cl buffer solution, 3-4 drops of EBT indicator and titrate
with EDTA solution till the colour changes from wine red to clear blue.
Let the volume of EDTA consumed be ‘V1’ ml.
d) Estimation of permanent hardness of water

Pipette out 50 ml of hard water sample into a 500 ml beaker and boil
gently for 20-30 minutes. Cool and filter it directly into 250 ml conical
flask. Add 5 ml of NH4OH-NH4Cl buffer solution, 3-4 drops of EBT
indicator and titrate with EDTA solution till the colour changes from
wine red to clear blue. Let the volume of EDTA consumed be ‘V2’ ml.
Calculation
PPM = one part of CaCO3 dissolved in one million parts of H2O =
mg/lt
Weight of CaCO3= W g
Volume of EDTA consumed by 50 ml of standard water (SW) or
CaCO3 solution = V ml.
Volume of EDTA consumed by 50 ml of hard water (HW) = V1 ml.
Volume of EDTA consumed by 50 ml of boiled water (BW) = V2 ml.
Molarity of CaCO3 solution (SW) = MCaCO3 =

wt of CaCO3/molecular wt of CaCO3 = W/100 = X molar

MEDTA = MSW X VSW/Vol of EDTA= X x 50/ Vml = Y molar

MHW = MEDTA X VEDTA/Vol of HW = YxV1/50ml = c molar

MBW = MEDTAX VEDTA/Vol of BW = Yx V2/ 50ml = d molar

Total Hardness of water = MHW X molecular wt of CaCO3
= c X 100 = --- x103 ppm
Permanent Hardness of water = MBW X mol wt of CaCO3
= d X 100 = --- x103 ppm
Temporary Hardness = Total hardness - Permanent hardness
= --- ppm
1) A standard hard water contains 1.0 gm of CaCO3 per litre. 50 ml of this solution
required 45 ml of EDTA solution for titration, while 50 ml of given hard water sample
required 25 ml of EDTA solution and after boiling and filtering required 18 ml of EDTA
solution. Compute the temporary hardness of water sample.

MSHW = Wt of CaCO3 = 1 = 0.01

Mol wt 100

MEDTA = 50 x 0.01 = 0.011

45

MHW = 0.011x25 = 5.5 x 10-3

50
MBW = 0.011x18 = 3.96 x 10-3
50
Total hardness = MHW x mol wt of CaCO3
5.5 x 10-3 x 100 = 0.550 x103 = 550 ppm

Permanent hardness = MBW x 100

= 3.96 x 10-3 x100 = 0.396 x 103 = 396 ppm

Temporary hardness = 550 - 396 = 154 ppm

using EBT indicator. The same 100 ml of water sample after boiling and filtering
required 14 ml of EDTA solution. Compute each type of hardness of water sample.

MHW = 0.015 x 25.6 = 3.84 x 10-3

100

MBW = 0.015 x14 = 2.1 x 10-3

100

Total hardness = MHW x mol wt of CaCO3

= 3.84 x 10-3 x 100 = 0.384 x103 = 384 ppm

Permanent hardness = MBW x 100

= 2.1 x 10-3 x100 = 0.21 x 103 = 210 ppm

Temporary hardness = 384 – 210 = 174 ppm

3) A water sample contains 55.5 mg of calcium chloride per litre. Calculate the
hardness of water sample in terms of CaCO3 equivalent.
( Atomic weight of Ca= 40 , Cl= 35.5 )
[Link]. of CaCl2 = 40 + 2 x 35.5 = 40 +71 = 111
111mg of CaCl2 = 100 mg of CaCO3
55.5 mg of CaCl2 = 100 x 55.5
111
= 50 ppm

4) 1.5 g of EDTA is dissolved in 500 ml of distilled water. 25 ml of hard water

sample consumed 15 ml of the above EDTA solution. Calculate the hardness of
water in ppm.

MEDTA = Weight x 2 = 1.5 x 2 = 0 .0080

[Link] 372.24

Mws = 0.0080 x 15 = 0.0048

25
Hardness of water = 0.0048 x 100 x 103 = 480 ppm
5). 0.25 gm of CaCO3 was dissolved in dil HCl and the solution was made upto
500 ml with distilled water. For titration, 100 ml of this solution required 45 ml of
EDTA solution. 100 ml of given hard water sample required 30 ml of EDTA solution
and the same water sample after boiling and filtering required 14 ml of the same
EDTA solution. Compute each type of hardness of water sample.

6). 100 ml of water sample required 34 ml of 0.01 M EDTA solution for titration
using EBT indicator. The same 100 ml of water sample after boiling and filtering
required 14.5 ml of same EDTA solution. Calculate each type of hardness of
water sample.
 Determination of alkalinity of water by double indicator method

Alkalinity in water is due to the presence of hydroxyl ions (OH-) from sodium or
potassium hydroxide, carbonate ions (CO32-) from sodium or potassium
carbonate and bicarbonate ions (HCO3-) from sodium or potassium bicarbonate.

Principle
Alkalinity is determined by titrating known volume of water sample with
standard acid using phenolphthalein and methyl orange indicators. When
titrated with acid the following reactions take place.

1) OH- + H+ → H2O
2) CO32- + H+ → HCO3-
3) HCO3- + H+ → H2O + CO2

The amount of acid consumed for phenolphthalein end point corresponds to

neutralisation of hydroxide and half of the carbonate. The amount of acid
consumed for methyl orange end point corresponds to half of the carbonate
and complete bicarbonate. The total amount of acid consumed corresponds to
total alkalinity of water.
Alkalinity in water is due to the presence of
▪ only OH-
▪ only CO32-
▪ only HCO3-
▪ combination of OH- and CO32-
▪ combination of CO32- and HCO3-

The combination of OH- and HCO3- does not exist in water because of the
following reaction

OH- + HCO3- → H2O + CO32-

Procedure

Pipette out 100 ml of water sample into a conical flask. Add 3 drops of
phenolphthalein indicator and titrate against standard sulphuric acid solution till
the pink colour just disappears. Note down the titre value. Then add 3 drops of
methyl orange indicator to the same solution and titrate further against the acid
solution till pink colour reappers. Note down the titre value.
Calculation

Volume of water sample taken = 100 ml

Normality of sulphuric acid solution = N
Volume of acid required for phenolphthalein end point = V1 ml
Extra volume of acid required for methyl orange end point = V2 ml

Normality of water sample for phenolphthalein alkalinity = V1 x N

100

Phenolphthalein alkalinity of water sample = P= V1 x N x 50 ([Link]. of CaCO3 )

in ppm 100

= P= V1x Nx50x1000
100

Methyl orange alkalinity of water sample = M = (V1+V2) x Nx50x1000

in ppm 100
 Alkalinity OH- ( ppm ) CO32-(ppm) HCO3- ( ppm )

P=0 0 0 M
P = M P=M 0 0
P = ½M 0 2P 0
P < ½M 0 2P M – 2P
P > ½M 2P – M 2 (M-P) 0
1). When a water sample was analyzed for alkalinity, 100 ml of the water sample
required 20 ml of N/50 sulphuric acid for phenolphthalein end point and another 10
ml for methyl orange end point. Determine the type and compute the amount of
alkalinity present.

NWS = 20 x 0.02 = 4 x 10-3 N/50 = 0.02N H 2SO4

for Ph 100

Nws = (20+10) x 0.02 = 6 x10-3

for M.O. 100

P - alkalinity = 4x10-3 x 50 x 103 = 200 ppm

M - alkalinity = 6x10-3 x 50x103 = 300 ppm

P > 1/2 M , OH- and CO32- present

Alkalinity due to OH- = (2 x 200) - 300 = 100 ppm

2). When a water sample was analyzed for alkalinity, 100 ml of the water sample
required 3.7 ml of N/10 HCl for phenolphthalein end point and another 9.2 ml for
methyl orange end point. Determine the type and compute the amount of
alkalinity present.

NWS = 3.7 x 0.1 = 3.7 x 10-3 N/10 = 0.1N HCl

100

Nws = (3.7+9.2) x 0.1 = 0.0129

100

P - alkalinity = 3.7x10-3 x 50 x 103 = 185 ppm

M - alkalinity = 0.0129 x 50 x 103 = 645 ppm

P < 1/2 M , CO32- and HCO3- present

Alkalinity due to CO 2-
= 2P = 370 ppm
3). When a water sample was analyzed for alkalinity, 100 ml of the water sample
required 5.8 ml of N/50 sulphuric acid for phenolphthalein end point and 11.6 ml
for methyl orange end point. Determine the type and compute the amount of
alkalinity present.

NWS = 5.8 x 0.02 = 1.16 x 10-3 N/50 = 0.02N

100
Nws = 11.6 x 0.02 = 2.32 x 10-3

100

P - alkalinity = 1.16 x 10-3 x 50 x 103 = 58 ppm

M - alkalinity = 2.32 x 10-3 x 50 x 103 = 116 ppm

P = 1/2 M , only CO32- present

Alkalinity due to CO 2-
= M = 2P = 116 ppm
4). A water sample is not alkaline to phenolphthalein, however, 100 ml of the
water sample on titration with N/50 HCl required 16.9 ml to obtain the end
point using methyl orange as the indicator. Determine the type and compute the
amount of alkalinity present.

P = 0 , therefore, OH- and CO32- absent .

Only HCO3- present.

NWS = 16.9 x 0.02 = 3.38 x 10-3

100

M - alkalinity = 3.38 x 10-3 x 50 x 103 = 169 ppm

5). 100 ml water sample on titration with N/50 sulphuric acid required 5.0 ml of acid
for phenolphthalein end point. Another 100 ml sample required 5.0 ml of acid for
methyl orange end point. Determine the type and compute the amount of alkalinity
present.

M = P = 5.0 ml

NWS = 5 x 0.02 = 1 x 10-3

100
= 1 x 10-3 x 50 x 103

P=M = 50 ppm

Only OH- present

6). When a water sample was analyzed for alkalinity, 100 ml of the water sample
required 10 ml of N/50 HCl for phenolphthalein end point and 15 ml for methyl
orange end point. Determine the type and compute the amount of alkalinity
present.

P – alkalinity = 100 ppm M – alkalinity = 150 ppm

P > 1/2 M , OH- and CO32- present

Alkalinity due to OH- = 50 ppm

Alkalinity due to CO32- = 100 ppm

Determination of Dissolved Oxygen by Winkler’s method

Principle

In this method the water sample is treated with manganese sulphate

MnSO4and alkaline potassium iodide solution KI. The dissolved oxygen present
in water sample oxidises divalent manganese to tetravalent manganese. This
basic manganic oxide MnO(OH)2 formed acts as an oxygen carrier to enable the
dissolved oxygen in molecular form to take part in the reaction. Upon
acidification the tetravalent manganese reverts to divalent state with the
liberation of nascent oxygen. This nascent oxygen oxidises KI to I2. The
liberated iodine is titrated against standard sodium thiosulphate solution
(Na2S2O3) using starch indicator.

Reactions
MnSO4 + 2KOH → Mn(OH)2 + K2SO4
2Mn(OH)2 + O2 → 2MnO(OH)2 ( Basic manganic oxide )
MnO (OH)2 + H2SO4 → MnSO4 + 2H2O + [O]
2KI + H2SO4 + [O] → K2SO4 + H2O + I2
I2 + 2Na2S2O3 → Na2S4O6 + 2NaI
Procedure
2 ml of MnSO4 solution and 3 ml of alkaline KI solution are added into the bottle
containing 250 ml of water sample. The bottle is stoppered and shaken well and
allowed to stand for the precipitate to settle. Then 1 ml con. H2SO4 is added,
stoppered and shaken well to dissolve the MnO2 precipitate. 100 ml of the
solution is pipetted out from the bottle into a conical flask and titrated with
standard Na2S2O3 solution using starch as indicator till the discharge of violet
colour.

Calculation
Volume of water sample taken = 100 ml
Volume of Na2S2O3 consumed = ‘V’ ml
Normality of Na2S2O3 solution = ‘Y’ N

Nws = V x Y
100

Dissolved oxygen content in = V x Y x 8( [Link] oxygen) x 1000

Mg/litre or ppm 100
= V x Y x 80 ppm
 Determination of Chemical oxygen demand (COD)

Principle

Chemical oxygen demand is defined as the amount of oxygen used for the oxidation
of total organic impurities present in the water sample using a strong chemical
oxidant, like K2Cr2O7 in acidic medium. It includes both the biologically oxidisable and
biologically inert impurities, as a result of which the value of COD is more than BOD.
It is expressed in terms of mg / litre or ppm.

When the sewage or waste water sample is refluxed with known volume of K2Cr2O7
solution in acid medium and in the presence of Ag2SO4 and HgSO4 , K2Cr2O7 oxidizes
all oxidisable impurities. Ag2SO4 acts as a catalyst in the oxidation of straight chain
organic compounds, aromatic, pyridine and lower fatty acids. HgSO4 avoids the
interference of Cl- ions.

The amount of unreacted or unused K2Cr2O7 is determined by titration with standard

ferrous ammonium sulphate (FAS) solution. The amount of K2Cr2O7 solution
consumed corresponds to the COD of the sewage or waste water sample.
Procedure

Back titration
Pipette out 100 ml of waste water sample into 250 ml conical flask. Add 10 ml of
K2Cr2O7 and two test tube of dil. H2SO4 containing 1gram of Ag2SO4 and HgSO4
each. Add boiling chips to the flask. Attach a reflux condenser and reflux the
mixture for about half an hour. Cool the mixture and titrate against standard FAS
solution using ferroin indicator till the colour changes from blue green to reddish
brown. Note down the titre value as V1 ml.

Blank titration
Repeat the experiment by taking 100 ml of distilled water. Add 10 ml of K2Cr2O7
and two test tube of dil.H2SO4 containing 1gram of Ag2SO4 and HgSO4 each and
titrate against standard FAS solution using ferroin indicator till the colour changes
from blue green to reddish brown. Note down the titre value as V2 ml.
Calculation

Volume of water sample taken = 100 ml

Normality of FAS = ‘Y’ N
Volume of FAS used in back titration = V1 ml
Volume of FAS used in blank titration = V2 ml
Total volume of FAS consumed = (V2 – V1) ml

Nws = NFAS x VFAS

Vws
= Y x (V2 – V1)
100

COD in mg/litre or ppm = Y x (V2 – V1) x 8 x1000

100
COD = Y x (V2 – V1) x 80 mg/litre or ppm
1). In a COD experiment, 25 ml of the effluent sample required 10.5 ml and 20.5
ml of N/4 FAS solution for back and blank titrations respectively. Compute the
COD of the sample.

N/4 FAS = 0.25 N FAS

COD = NFAS x (V2-V1) x 8 x 1000

Vsample

= 0.25 x 20.5 -10.5 x 8000

25
= 0.25 x 10 x 8000
25

COD = 800 mg/litr or ppm

2). 25 ml of effluent sample required 12 ml of 0.02N K2Cr2O7 for complete
oxidation. Compute COD of the sample.

1000ml of 1N K2Cr2O7 = 8 g of oxygen

1ml of 1N K2Cr2O7 = 8 mg of oxygen
12 ml of 0.02 N K2Cr2O7 = 12 x 0.02 x 8 = 1.92 mg of oxygen

25 ml of effluent = 1.92 mg of oxygen

1000 ml of effluent = 1000 x 1.92/ 25

COD = 76.8 mg/litr or ppm

3). 25 ml of effluent required 8.4 ml of 0.005M K2Cr2O7 for complete
oxidation. Compute COD of the sample.

1000ml of 1M K2Cr2O7 = 48g of oxygen

1ml of 1M K2Cr2O7 = 48 mg of oxygen
8.4ml of 0.005 M K2Cr2O7 = 8.4 x 0.005 x 48 = 2.016 mg of oxygen

25 ml of effluent = 2.016 mg of oxygen

1000 ml of effluent = 1000 x 2.016 / 25

COD = 80.64 mg/litr or ppm

 Boiler scales
Boiler scales are hard and sticky deposits formed on the inner surface of boiler.

Boiler sludges are soft and nonsticky precipitate formed in the boiler.

Formation of boiler scales

Decomposition of Ca(HCO3)2
Calcium bicarbonate present in boiler water decomposes at high temperature
forming insoluble calcium carbonate which is deposited as scale.
Ca(HCO3)2 → CaCO3↓ + H2O + CO2↑
Scale
This type of scale is formed in low pressure boilers
In high pressure boilers, calcium carbonate is soluble due to the formation of
calcium hydroxide
CaCO3 + H2O → Ca(OH)2 + CO2↑

Hydrolysis of MgCl2
Magnesium chloride gets hydrolysed at high temperature inside the boiler forming
insoluble magnesium hydroxide which forms scale.
MgCl2 + 2H2O → Mg(OH)2↓ + 2HCl↑
Scale
Deposition of CaSO4
The solubility of calcium sulphate in water decreases with increase in
temperature. CaSO4 is soluble in cold water, but insoluble in super heated water.
Therefore, CaSO4 gets precipitated and deposited as hard scale on the inner
surface of the boiler. This type of scale is very hard and adherent and causes
troubles mainly in high pressure boilers.

Silicate scale
Even if a small quantity of SiO2 is present in boiler water, it forms calcium silicate
CaSiO3 or magnesium silicate MgSiO3 scale. Silicate scales are very hard and
adherent on the inner wall of the boiler.

Ill effects of boiler scales

Wastage of fuel : Scales have a poor thermal conductivity therefore the rate of
heat transfer from boiler to inside water is reduced. In order to provide a steady
supply of heat to water , excessive or overheating is done and this causes increase
in fuel consumption. The wastage of fuel depends on thickness and nature of the
scale.
Boiler safety decreases: Due to scale formation, overheating of boiler is done in
order to maintain a steady supply of steam. It makes the boiler tubes soft and
weak. This makes the boiler unsafe to withstand the pressure of the steam,
mainly in high pressure boilers.

Boiler efficiency decreases: Deposition of scales in the valves and condensers of

boiler, causes decrease in the efficiency of the boiler.

Danger of explosion: When thick scales crack due to uneven expansion, the
water comes in contact with overheated portion of the boiler and large amount
of steam is suddenly formed. This results in development of sudden high
pressure which may cause explosion of the boiler.
 Prevention of boiler scales
External treatment : In this method the water is treated before it enters the boilers.

Internal treatment : In this method the conditioning of water is carried out inside the
boiler. It is normally carried out to remove the residual salts which could not be
removed by external treatment.

Hot lime-soda process

This is an external treatment of removing hardness of water.

This process involves the use of lime (Ca(OH)2) and soda (Na2CO3) to remove hardness
from water.

The hard water is treated with calculated amounts of lime and soda at a temperature
of 80-100 0C in a reaction tank. The chemicals and water are thoroughly mixed.

These chemicals convert all hardness causing salts dissolved in water into insoluble
precipitates of CaCO3 and Mg(OH)2 which are then removed by settling and filtration.
The water gets softened.
Reaction with Lime ( Ca(OH)2)
Lime is effective in removing dissolved gases, temporary hardness and
magnesium permanent hardness from water.
CO2 + Ca(OH)2 → CaCO3 + H2O
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O
Mg(HCO3)2 + 2Ca(OH)2 → 2CaCO3 + Mg(OH)2 + 2H2O
MgCl2 + Ca(OH)2 → Mg(OH)2 + CaCl2
MgSO4 + Ca(OH)2 → Mg(OH)2 + CaSO4

Reaction with Soda ( Na2CO3)

Soda is effective in removing calcium permanent hardness from water.
CaCl2 + Na2CO3 → CaCO3 + 2NaCl
CaSO4 + Na2CO3 → CaCO3 + Na2SO4

Advantages of Hot lime soda process

The softening reactions are faster
the ppt and sludge settle rapidly
dissolved gases are removed
viscosity of softened water is less so that filtration is easier.
 Desalination

Process of removal of dissolved salts from sea water to the extent that water
becomes usable is called as desalination.

Desalination by Electrodialysis

Principle

This method is based on the principle that the ions migrate towards oppositely
charged electrodes when an emf is applied. The direction of ions movement is
further made specific by using ion selective membranes.
The cation membranes are permeable only to cations while anion membranes are
permeable only to anions. The process thus yields pure water by decreasing salt
concentration.

The process of decreasing the concentration of salts in saline water using ion
selective membranes under the influence of an applied emf is called as
electrodialysis.
Electrodialysis cell consists of a series of alternative cation and anion permeable
membranes. The anode is placed near the anion permeable membrane and the
cathode is placed near the cation permeable membrane.

A suitable emf depending on the level of salts in saline water is applied across
the two electrodes immersed in saline water. Under the influence of the applied
emf, sodium ions (Na+) move through the cation permeable membrane (C) and
anions (Cl-) moves through the anion permeable membrane (A) from each
compartment of CA.

The net result is the decrease of salt content in the CA compartments and an
increase of salt concentration in compartments AC. The fresh water produced in
compartments CA is collected through the outlet. The concentrated saline water
(brine solution) produced in compartments AC is pumped off.

Compartment CA = Salt concentration decreases = Fresh water

Compartment AC = Salt concentration increases = Brine solution
 SLE

Determination of chloride by mohr’s method

Chloride content in water is determined by titrating known volume of water sample

with standard silver nitrate (AgNO3) solution using potassium chromate (K2CrO4) as
an indicator. Silver nitrate precipitates chloride ions as silver chloride (AgCl). The
end point of the titration is appearance of brick red colour.

AgNO3 + Cl- → AgCl↓ + NO3-

2AgNO3 + CrO42- → Ag2CrO4↓ + 2NO3-

Brick red ppt
 SLE

Prevention of boiler scales by internal treatment

Calgon conditioning

Calgon is sodium hexa meta phosphate. It forms soluble complex with Ca and
Mg salts.

2CaSO4 + Na2[ Na4(PO3) 6] → Na2[ Ca2(PO3) 6] + 2Na2SO4

Phosphate conditioning

Sodium phosphate is added to boiler water. It forms easily removable

precipitates of Ca and Mg phosphates.

3CaCl2 + 2Na3PO4 → Ca3(PO4)2↓ + 6NaCl