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WATER (UNIT-IV)
Introduction
Water is nature’s most wonderful, abundant and useful compound.
Water is not only essential for the lives of animals and plants. But also occupies a unique position in
industries.
Water is also used a coolant in power and chemical plants.
It is widely used in drinking, bathing, sanitary, washing, irrigation, fire-fights, air-conditioning and
also production of industrial materials.

HARDNESS OF WATER
Hardness of water defined as which prevent the lathering of soap.
This is due to presence of in water of certain salts of Ca+2, Mg+2 and other Heavy metals dissolved in
it. Soaps are Sodium or Potassium salts of higher fatty acids like Oleic acid or Palmitic acid or stearic
acids. C17H35COONa Temporary Hardness is mainly caused by Bicarbonates of Calcium, Magnesium
and other heavy metals.
SOAP with HARDWATER REACTIONS
2C17H35COONa+CaCl2 (C17H35COO)2Ca+2NaCl
2C17H35COONa+MgSO4 (C17H35COO)2Mg+Na2SO4
Hardness of water is mainly TWO types
1.Temporary Hardness
2. Permanent Hardness
1. Temporary Hardness mainly caused by the presence of dissolved Bicarbonates of
Calcium, Magnesium and other Heavy metals and the carbonate of Iron.
Temporary hardness of water mainly responsible salts are…
1. Calcium bicarbonate Ca(HCO3)2
2. Magnesium bicarbonate Mg(HCO3)2
When bicarbonates are decomposed a, yielding insoluble carbonates or hydroxides, which are
deposited as a crust at the bottom of vessel.
Temporary Hardness can be largely removed by mere Boiling of water.
Temporary Hardness is also known as….Carbonate Hardness or Alkaline Hardness
Heat
• Ca(HCO3) 2 CaCO3+H2O+CO2
Calcium bicarbonate
Heat
• Mg(HCO3)2 Mg(OH)2+2CO2
Magnesium bicarbonate
2. Permanent harness: It is due to the presence of dissolved Chlorides and sulphates of
Calcium, Magnesium, Iron and other metals
Permanent hardness responsible salts are…. CaCl2, MgCl2, CaSO4, MgSO4, FeSO4, Al2(SO4)3
Permanent Hardness cannot remove by boiling
but it can be removed by the use of chemical agents.
Permanent Hardness also known as…. Non-Carbonate Hardness, Non-Alkaline

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Q No. 1: a. Define Harness of water.

b. Explain the EDTA method for the estimation of temporary hardness of water.
C. 2 liters of water obtained from a bore well in Patencheru near Hyderabad gave the
following analysis for salts. FeSO4 =30.4mg, CaSO4=13.6mg, MgCl2=48mg,
Ca(HCo3)2=32.4 , mg(HCo3)2=14.6mg, NaCl=11.7mg. Find the total hardness of water in
ppm units, giving temporary &permanent hardness assuming the at. Mass of Fe=56,
Ca=40, Mg=24, Na=22.

Answer: a. Hardness of water defined as which prevent the lathering of soap.

This is due to presence of in water of certain salts of Ca+2, Mg+2 and other Heavy metals dissolved in
it. Soaps are Sodium or Potassium salts of higher fatty acids like Oleic acid or Palmitic acid or stearic
acids. C17H35COONaTemporary Hardness is mainly caused by Bicarbonates of Calcium, Magnesium
and other heavy metals.
b. ESTIMATION OF TEMPORARY HARDNESS BY EDTA METHOD:
The hardness of water is not a pollution parameter but indicate the eater quality in terms of Calcium
and magnesium expressed in terms of CaCO3.
The analysis is done by complex metric titration using standard EDTA and EBT as an indicator.
PRINCIPLE: In this complex metric Titration, the water sample is titrated with standard solution of
Di sodium salt of EDTA using EBT indicator.
REACTIONS INVOLVED: EBT indicator when added to hard water at pH = 10, forms weak
complexes with calcium and magnesium present in hard water. It results in the formation of Ca-EBT
or Mg-EBT complexes which is wine-red, these are unstable.
(Ca2+ & or Mg2+ ) + EBT  [Ca – EBT ] complex & or [Mg – EBT] complex
blue wine-red wine-red
During titration with EDTA, calcium first reacts to form relatively stable followed by magnesium to
give Mg-EDTA+2 complex releasing the free indicator(blue) the colour changes from wine-red to blue
at the endpoint.
Metal-EBT + EDTA  Metal – EDTA + EBT
Wine-red blue
Various steps involved in this method are…
1. Preparation of standard hard water: dissolve 1g of pure, dry CaCO3 in minimum quantity
of dil.HCl and then evaporate the solution to dryness on a water bath. Dissolve the residue in
distilled water to make 1 Litre solution. Each mL of this solution thus contains 1mg of CaCO3
equalent hardness.
1 mL hard water solution = 1mg of CaCO3 equalent hardness.
2. Standardization of EDTA solution: Rinse and fill the burette with EDTA solution. Pipette
out 50 mL of standard hard water in a conical flask. Add 10-15 mL of buffer solution and 4 to
5 drops indicator. Titrate with EDTA solution till wine-red colour changes to clear blue. Let
volume used by V1 mL.
3. Titration of Unknown Hard water: Rinse and fill the burette with EDTA solution. Pipette
out 50 mL of unknown sample hard water in a conical flask. Add 10-15 mL of buffer solution
and 4 to 5 drops indicator. Titrate with EDTA solution till wine-red colour changes to clear
blue. Let volume used be V2 mL.
4. Titration of Permanent hardness: take 250 mL of the water sample in a large beaker. Boil it.
Till the volume is reduced to about 50 mL, filter it, wash the precipitate with distilled water,
collecting filtrate and washing in a 250 mL measuring flask. Finally makeup the volume to 250
mL with distilled water. Then, titrate 50 mL of boiled water sample just as in Step (2). Let
volume used by V3 mL.

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CALCULATION:
Total hardness of water = 1000 X V2 ppm
V1
Permanent hardness = 1000 X V3 ppm
V1
Temporary hardness = [Total hardness – Permanent hardness]

Temporary hardness = 1000 X (V2- V3) ppm

V1
Advantages of EDTA method:
This method is definitely prep arable to the other methods, because of the
1. Greater accuracy
2. Convenience and 3. More rapid procedure

S.No. Constituent Amount mg/lit MF CaCO3

equivalent
1. FeSO4 30.4 100/152 20
2. CaSO4 13.6 100/136 10
3. MgCl2 48 100/95 50
4. Ca(HCO3)2 32.4 100/162 20
5. Mg(HCO3)2 14.6 100/146 10
6. NaCl 11.7 --- --

Temporary hardness = Mg(HCO3)2 + Ca(HCO3)2

= 10 + 20 = 30 ppm

Permanent hardness = FeSO4 + CaSO4 + MgCl2

= 20 + 10 + 50 = 80 ppm
Total Hardness = Temporary hardness + Permanent hardness = 30 + 80 = 110 ppm

Q.No. 2: a. Define Temporary & permanent hardness of water & give an account of
disadvantages of hard water & mention its units.
Answer:
1. Temporary Hardness mainly caused by the presence of dissolved Bicarbonates of
Calcium, Magnesium and other Heavy metals and the carbonate of Iron.
Temporary hardness of water mainly responsible salts are…
1. Calcium bicarbonate Ca(HCO3)2
2. Magnesium bicarbonate Mg(HCO3)2

2. Permanent hardness: It is due to the presence of dissolved Chlorides and sulphates of

Calcium, Magnesium, Iron and other metals
Permanent hardness responsible salts are…. CaCl2, MgCl2, CaSO4, MgSO4, FeSO4, Al2 (SO4)3

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DISADVANTAGES OF HARDWATER:
1. In Domestic use:
a. WASHING: hardwater, when used for washing purposes, does not producing lather freely
with soap. As a result cleansing quality of soap is decreased and a lot of it is wasted. Hardwater
reacts with soap it produces sticky precipitates of calcium and magnesium soaps. These are
insoluble formations.
b. Bathing: hardwater does not lather freely with soap solution, but produces sticky scum on
the bath-tub and body. Thus, the cleansing quality of soap is depressed and a lot o it is wasted.
c. Cooking: the boiling point of water is increased because of presence of salts. Hence more
fuel and time are required for cooking.
d. Drinking: hardwater causes bad effects on our digestive system. Moreover, the possibility of
forming calciumoxalate crystals in urinary tracks is increased.

2. INDUSTRIAL USE:
a. Textile Industry: Hardwater causes wastage of soap. Precipitates of calcium and
magnesium soaps adhere to the fabrics and cause problem.
b. Sugar Industry: water containing sulphates, nitrates, alkali carbonates. Etc. if used in sugar
refining, causes difficulties in the crystallization of sugar. Moreover, the sugar so produced
may be de-liquescent.
c. Dyeing Industry: The dissolved salts in hardwater may reacts with costly dyes forming
precipitates.
d. Paper Industry: Calcium, magnesium, Iron salts in water may affect the quality of paper.
e. Pharmaceutical Industry: Hardwater may cause some undesirable products while
preparation of pharmaceutical products.
f. Concrete Making: Water containing chlorides and sulphates, if used for concrete making,
affects the hydration of cement and the final strength of the hardened concrete.
g. Laundry: Hardwater, if used in laundry, causes much of the soap used in washing to go as
waste Iron salts may even cause coloration of the clothes.

3. IN STEAM GENERATION IN BOILERS:

For steam generation, boilers are almost invariably employed. If the hardwater is fed directly to
the boilers, there arise many troubles such as..
a. Scale and sludge formation: the hardness of water fed to the boiler may cause scale and sludge
formation.
b. Corrosion: Hardwater may cause caustic embrittlement which is a type of boiler corrosion.
c. Priming and Foaming: Hardwater used in boiler causes priming and foaming which results in
the formation of wet stream.
d. Caustic embrittlement

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Q.No.3: Write a brief account of lime soda process.

Answer: Water used for industrial purposes such as for steam generation, should be sufficiently pure.
It should, therefore be freed from hardness-producing salts before put to use.
The process of removing hardness-producing salts from water is known as softening of water.
In industry main three external methods employed for softening of water are.
1. Lime-Soda process
2. Zeolite process
3. Ion-Exchange process

LIME-SODA PROCESS: In this method, the soluble calcium and magnesium salts in water are
chemically converted in to insoluble compounds, by adding calculated amount of Lime and Soda.
CaCO3 and Mg(OH)2 so precipitated, these precipitates are filtered off.
Lime soda process mainly two types, they are
1. Cold Lime-soda process
2. Hot Lime-soda process.

COLD LIME SODA PROCESS: In this method, calculated quantity of chemical like lime and soda
are mixed with water at Room temperature. At room temperature, the precipitates formed are finely
divided, so they do not settle down easily and cannot be filtered easily.
Consequently, it is essential to add small amounts of coagulants like alum, aluminum sulphate,
sodium aluminate, etc. Which hydrolyze to flocculent, gelatinousprecipitate of aluminum hydroxide,
and entraps fine precipitates.
Use of sodium aluminate as coagulant also helps the removal of silica as well as oil,
If present in water. Cold L-S process provides water, containing a residual hardness of 50 to 60 ppm.
NaAlO2 + 2H2O  NaOH + Al(OH)3
Al2(SO4)3 + 3Ca(HCO3)2  2Al(OH)3 + 3CaSO4 + 6CO2
.

METHOD: Raw water and calculated quantities of chemicals ( Lime + soda + Coagulants) are fed
from the top into the inner vertical circular chamber, fitted with a vertical rotating shat carrying a
number of paddles. As the raw water and chemicals flow down, there is a vigorous stirring and
continuous mixing, whereby softening of water reaches up. The softened water comes into the outer
co-axial chamber, it rises upwards. The heavy sludge or precipitated floc settles down the outer
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chamber by the time the softened water reaches up. The softened water then passes through a filtering
media this is usually made of wood fibres to ensure complete removal of sludge. Filtered soft water
finally flows out continuously through the outlet at the top. Sludge settling at the bottom of the outer
chamber is drawn of occasionally

HOT LIME-SODA PROCESS:

a. The reaction proceeds faster
b. The softening capacity f hot process is increased to many fold
c. The precipitate and sludge formed settle down rapidly and hence, no coagulants are needed
d. Much of the dissolved gases such as CO2 and air driven out of the water
e. Viscosity of softened water is lower, so filtration of water becomes much easier. this in-turn
increases the filtering capacity of filters, and
f. Hot lime-soda process produces water of comparatively lower residual hardness of 15 to 30
ppm.

Hot lime-soda plant consists essentially of three parts

1. A ‘Reaction tank’ in which raw water, chemicals and steam are thoroughly mixed.
2. A ‘Conical sedimentation vessel’ in which sludge settles down, and
3. A ‘sand filter’ which ensures completes removal of sludge from the softened water.
ADVANTAGES OF LIME-SODA PROCESS:
1. It is very economical
2. If this process is combined with sedimentation with coagulation, lesser amounts of coagulants
shall be needed.
3. The process increases the pH value of the treated-water; thereby corrosion of the distribution
pipes is reduced.
4. Besides the removal of harness, the quantity of minerals in the water is reduced.
5. To certain extent, iron and manganese are also removed from the water.
6. Due to alkaline nature of treated-water, amount of pathogenic bacteria in water is considerably
reduced.
DIS-ADVANTAGES OF LIME-SODA PROCESS:
1. For efficient and economical softening, careful operation and skilled supervision is required.
2. Disposal of large amounts of sludge or insoluble precipitates poses a problem. However, the
sludge may be disposed off in raising low-lying areas of the city.
3. This can remove hardness only up to 15 ppm, which is not good for boilers.

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