1.

Hardness of water

Water which does not produce lather with soap is termed as hard water. The hardness is usually
expressed in terms of Ca & Mg salts like bicarbonate, carbonate, sulphate, chloride etc.

Formation of Hard water:

Hard water is formed due to presence of minerals like Ca and Mg. they are not removed or
separated by sedimentation or filtration. When hard water reacts with soap (sodium salt of
stearic acid or pametic acid) gives curdy precipitate.

2C17H35COONa + CaCl2 17H35COO)2

2 C17H35COONa + MgSO4 17H35COO)2 2SO4

In above reaction hard water react with sodium salt of stearic acid to form calcium stearate or
magnesium stearate which being insoluble and separate out without producing lather.

2. Types of hardness

a) Temporary hardness:
Temporary hardness of water is caused by Ca and Mg bicarbonate. This can be removed
by simply boiling of water. Due to boiling bicarbonate is converted into carbonate
(insoluble precipitate)

Ca(HCO3)2 3 2O + CO2

Mg(HCO3)2 2 2

Temporary hardness can also be removed by adding hydrated lime to precipitate

insoluble carbonate.

Ca(HCO3)2 + Ca(OH)2 2CaCO3 2H2O

Mg(HCO3)2 + Ca(OH)2 2 2CaCO3 2O

b) Permanent hardness:
Permanent hardness is caused by the presence of soluble salt of Ca and Mg other than
bicarbonate such as chloride and sulphate. Permanent hardness cannot be removed by
boiling of water or hydrated lime. It can be eliminate by water softening techniques like
Lime-soda process, Zeolite, Ion-exchange resin, reverese osmosis etc.
 3. Degree of hardness
The unit in which hardness is usually expressed, known as degree of hardness. Degree of
hardness is expressed in terms of calcium carbonate (CaCO 3) equivalent because CaCO 3
have molecular weight 100 and it is easily precipitate. Degree of hardness may be
expressed as follows-

Equivalent of CaCO3 =

OR

Equivalent of CaCO3 =

Unit of hardness:

i) Parts per million (ppm): it is the number of equivalent part CaCO 3 present per
million (106) part of water by weight.
ii) Milligram per litre (mg/lit): it is the number of milligram of CaCO 3 present in
one litre of water.
iii) Degree Clarke ( oCl): it is the number of equivalent part of CaCO 3 present per
70,000 part of water.
iv) Degree French (oFr): it is the number of equivalent part of CaCO 3 present per 105
part of water.

Correlation between ppm, mg/lit, oCl and oFr:

[1ppm= 1mg/lit=0.07 oCl= 0.1 oFr]

4. Boiler Trouble
Boilers are used in industries and power station to generate steam. During conversion of
water into steam in boiler, the dissolve and suspended solids are not removed. All the
impurities are deposited in form of scale and sludge within the boiler and causes boiler
troubles.
a) Scales formation:
Scales are hard deposits, which stick on the inner wall of the boiler. These are formed
by CaCO3, CaSO4, Ca(HCO3)2, Mg(OH)2 etc. in hot portion of boiler.

b) Sludge formation:
Sludge form loose, slimy and soft precipitate in the colder area of the boiler. The
sludge formed by the CaCl2, MgCl2, MgCO3, MgSO4 etc.

Problems caused in boilers:

i) Scales and sludge is poor conductor of heat & therefore prevent effective transfer
of heat to water.
ii) In this condition excessive heat is required which increase fuel consumption.
iii) Scale often crack due to their uneven expansion allowing the water to come
immediately in contact with overheated metal. This suddenly result in the
formation of large quantity of steam which in turn leads to excess pressure and
then to explosion.

5. Boiler trouble removal by internal treatment

Internal treatment:

i) Sludge formation can be removed by blow down operation. In this case impurities
can be removed by an outlet present at the bottom of boiler.
ii) Scale formation can be prevented by internal treatment that involve addition of
chemical to the boiler water either to ppt the scale forming impurities in the form
of sludge so that they can be removed by blow down method or to convert them
into soluble compounds.
a) Calgon treatment:
Calgon is sodium meta hexa phoaphate, which can be used to covert CaSO4 into
soluble complex.
Na2[Na4(PO3)6] + 2CaSO4 Na2[Ca2(PO3)6] + 2Na2SO4
Calgon soluble
b) Phosphate treatment:
Scale formation can be removed by adding sodium phosphate, which reacts with
hardness of water and form soft sludge of Ca and Mg phosphates which can be
removed by blow-down operation.

3CaCl2 + 2Na3PO4 Ca3(PO4)2

MgSO4 + 2Na3PO4 Mg3(PO4)2 2SO4
 6. Techniques for water softening (External treatment)

a) Zeolite process

Zeolite is a three-dimensional silicate. The chemical formula of zeolite is hydrated

sodium aluminum silicate represented as Na 2OAl2O3.xSiO2.yH2O (x = 2-10 & y = 2-
6). Zeolites are capable exchanging ions with sodium ions. So it is capable of
exchanging hardness producing icons present in water. This process also called as
permutit process. Zeolite can be written as Na 2Ze The two Na+ icons is replaced by
one Ca2+ or Mg2+ ions.
Na2Ze + Ca2+ CaZe + 2Na+
Process:-
The apparatus is made of cylindrical metallic vessel several beds are made inside it
where zeolite salt is kept. Raw water is poured inside the apparatus through inlet that
passes through beds and thus chemical ion exchange reactions are takes place. After
the use of this process for a certain time, Zeolite is exhausted i.e all Na + ions are
replaced by Ca 2+ or Mg2+ and therefore this will not be used for soften the water.

Na2Ze + CaCl2/CaSO4/ Ca(HCO3)2 CaZe + 2NaCl/Na2SO4/2NaHCO3

Regeneration:

Exhausted zeolite can be regenerated by treating it with brine solution (10% NaCl
solution)
(Ca2+/Mg2+) Ze + NaCl Na2Ze + CaCl2 (or) MgCl2
Exhausted Zeolite on washing with cold water, CaCl2 & MgCl2 can be removed and
regenerated zeolite is this ready to be reused.
b) Ion-exchange resin:
In this process cations and anions are completely removed by passing impure water
into two different columns. First column contain sulphuric acid resin with acidic
group SO3H. This column is known as cation exchange resin because it exchange
only cations like Ca2+, Mg2+, Na+ etc.

Resin SO3H + Na+ resin- Na+ + H+

2Resin SO3H + Ca2+ (resin- 2Ca + 2H+

2Resin SO3H + Mg2+ (resin- 2Mg + 2H+

Whereas, second column contain resin with basic group like . It is known
as anion exchange resin because it exchanges anions like etc.

resin + resin +

The removal of H+ ions from the first column and ions from the second column
react to form water.

Regeneration:

when both the column are exhausted, then first and second column are treated with
dilute sulphuric acid or HCl (generate H+ ions) and aqueous NaOH (generate OH
ions) respectively. So, they have to be regenerated.

(resin- 2Ca + 2H+ 2Resin SO3H + Ca2+

(resin- 2Mg + 2H+ 2Resin SO3H + Mg2+

 c) Lime-soda process:

In this process, hydrated lime & sada ash use to remove hardness from water.

i) Hydrated lime:

Hydrated lime is used to remove temporary hardness of water. It react with Ca(HCO 3)2 &
Mg(CO3)2 to form insoluble precipitate of calcium carbonate and magnesium hydroxide
respectively.

Ca(HCO3)2 + Ca(OH)2 2CaCO3 2O

Mg(HCO3)2 + 2Ca(OH)2 Mg(OH)2 3 2O

Hydrated lime is also used to remove permanent hardness (magnesium salt impurities
only) from water. It reacts with MgSO 4 & MgCl2 to form insoluble precipitate of
magnesium hydroxide.

MgCl2 + Ca(OH)2 Mg(OH)2 2

MgSO4 + Ca(OH)2 Mg(OH)2 4

In above reaction calcium based impurities like CaCl2 & CaSO4 also form, which are
soluble in water. Therefore calcium based impurities (CaCl2 & CaSO4) are not removed
by lime treatment.

ii) Soda ash:

Sodium carbonate (Na2CO3) is used to remove permanent hardness of water which
caused by MgSO4 & MgCl2 or CaCl2 & CaSO4.
CaCl2 + Na2CO3 CaCO3
CaSO4 + Na2CO3 CaCO3 2SO4
MgCl2 + Na2CO3 MgCO3
MgSO4 + Na2CO3 MgCO3 2SO4

The amount of lime-sada required for the softening of hard water can be calculated
by following formula-

Lime requirement = [temporary hardness of Ca + 2 temporary hardness of

Mg + permanent hardness of Mg in terms of CaCO3 equivalents]

Soda requirement = [permanent hardness of CaCl2 + CaSO4 + MgCl2 + MgSO4

in terms of CaCO3 equivalents]

d) Reverse osmosis:
The minimum excess pressure yhat has to be applied on the solution to prevent the
entry of the solvent molecule (pure water) into solution through semi permeable
membrane is known as osmotic pressure (lower concentration to higher
concentration).

If a pressure higher than the osmotic pressure is applied on the solution, the solvent
(pure water) will flow reverse, higher concentration solution to low concentration
solution, the process is known as reverse osmosis.

Reverse osmosis process can also be used in purification of sea water, for this purpose
sea water is delivered under pressure through the semi-permeable membrane where
water permeate the minute pores of the membrane & is delivered as purified water.