Introduction

For the existence of all living beings (human, animals and plants), water is
very crucial. Almost all human activities —domestic, agricultural and
industrial, demand use of water although water is nature’s most wonderful
land abundant compound but only less than1% of the world’s water
resources are available for ready use. Hence it is required to use it
carefully and economically. This chapter deals with the hardness of water
and various methods of softening of water for industrial water supply.

Sources of Water
The main sources of water are:
(i) Surface water: It includes flowing water (streams and rivers) and
still water (lakes, ponds and reservoirs).
(ii) Under groundwater: It includes water from wells and springs.
(iii) Rainwater
(iv) Seawater

Impurities of Water
The impurities present in water may be categorised into following categories:
(A) DissolvedImpurities
(a) Dissolvedgases: O2, CO2, H2S etc
(b) Inorganicsalts:
(i) Cations:Ca++,Mg++,Na+,K+,Fe++,Al+++etc.
(c) Anions: CO3-, Cl-, SO4-, NO3- etc.
(d) Organic salts.
(B) Suspended Impurities
(a) Inorganic: Clay and sand.
(b) Organic: Oil globules, vegetables, and animal material.
(C) Colloidal Impurities
Finally divided clay and silica Al(OH)3 , Fe(OH)3 , organic waste
products, colouring matter, amino acids etc.
 (D) Microscopic Matters
Bacteria, algae, fungi etc.

Sources of Impurities in Water

Following are the sources of impurities in water:
(i) Gases(O2, CO2etc.)are picked up from the atmosphere by rainwater.
(ii) Decompositionofplantsandanimalsremainsintroduceorganicimpuritiesi
nwater.
(iii) Waterdissolvesimpuritieswhenitcomesincontactwithground,soilorroc
ks.
(iv) Impuritiesarealsointroducedinwaterwhenitcomesincontactwithsewag
eor industrial waste.
Hardness of Water
“Hardness in water is that characteristics, which prevents the lathering of
soap”. In other way we may define it as “soap consuming capacity of
water”.

Causes of Hardness
Hardness is due to presence of certain salts of Ca2+, Mg2+ and other heavy
metal ions like Al3+, Fe3+ and Mn2+ in water.

Mechanism of cause of hardness

It can be explained by the reaction of soap in soft and hard water.

Reaction of Soap in Soft Water

Whensoftwateristreatedwithsoap,latherisproducedaccordingtothefollowingre
action:

C17H35COONa + H 2O → C17H35COOH + NaOH

 Reaction of Soap in Hard Water
A sample of hard water, when treated with soap (sodium or potassium salt
of higher fatty acid like oleic, palmitic and stearic acid), doesnot produce
lather, but on the other hand forms insoluble white scum or precipitate
which do not possess any detergent action. This is due to the formation of
insoluble soap of calcium and magnesium. Typical reaction of
soap(sodium stearate) with calcium chloride and magnesium sulphate are
shown below.

2 C17H35COONa + CaCl2 → (C17H35COO)2Ca + 2NaCl

Sodium stearate Calcium stearate (insoluble)

2C17H35COONa + Ca(HCO3)2 → (C17H35COO)2Ca+ NaHCO3

Actually hardness is due to presence of Cl-, SO42-, CO32- and HCO32- of Ca2+,
Mg2+ and other heavy metal ions like Fe++, Al+++ and Mn++

Types of Hardness
It is of following types:
1. Temporary Hardness
(a) Temporary hardness is caused by the presence of dissolved
bicarbonates of calcium, magnesium and other heavy metals and
the carbonates of iron and other metals also. Thus, the main salts
responsible for temporary hardness are Ca(HCO3)2 and
Mg(HCO3)2.
(b) Temporary hardness can be largely removed by more boiling of
water, when bicarbonates are decomposed, yielding in soluble
carbonates or hydroxides, which are deposited as a crust at the
bottom of vessel.
Boiling
Ca(HCO3)2 → CaCO 3 + H2O + CO2
Boiling
Mg(HCO3)2 → Mg(OH) 2 + 2CO2
(c) Temporaryhardnessisalsoknownascarbonatehardnessoralkalinehard
ness.
(d) Alkaline hardness is due to the presence of bicarbonates,
 carbonates and
hydroxidesofthehardnessproducingmetalions.Thisisdeterminedbyt
itration with HCl using methyl orange as indicator.
2. Permanent Hardness
(a) It is due to the presence of dissolved chlorides and sulphates of
calcium, magnesium, iron and other heavy metals. Hence, the
salts responsible for permanent hardness are CaCl2,
MgCl2,CaSO4,MgSO4,FeSO4,Al2(SO4)3etc.
(b) Unlike temporary hardness, permanent hardness is not destroyed
on boiling.
(c) It is also known as non-carbonate or non-alkaline hardness.
(d) The difference between total hardness and alkaline hardness
gives the non- alkaline hardness.

Determination of hardness of water

EDTA Method: EDTA method is the most accurate method for determination of hardness
of water. EDTA (Ethylene diamine tetra acetic acid) has the following structure.

EDTA acts as a complexing agent. It forms complexes with Ca2+and Mg2+ ions
as well as with many other metals cations, in aqueous solutions. In hard water
sample, the total hardness can be determine by titrating the Ca 2+ and Mg2+
present in an aliquot sample with Na2 EDTA solution using NH4Cl-NH4OH
buffer solution of pH10 and Eriochrome Black-T as the indicator. At the end
point, the colour changes from wine red to blue.
Na2H2Y → 2Na+ + H2Y2-
Disodium EDTA in soln.

Mg2++ HD2- → MgD- + H+

Blue wine red
Permanent hardness can be determined by precipitating the temporary
hardness by boiling water for about 30 minutes followed by titration with
EDTA solution. The difference in the titre values corresponds to the temporary
hardness of the water solution.

Units of Hardness and their Inter-relations

i) Parts per million (ppm): It is defined as the number of parts by weight

of calcium carbonate per million (106) parts by weight of water.

1 ppm = 1 part of CaCO3 equivalent hardness in 106 parts of water.

ii) Milligrams per litre (mg/L): It is defined as the number of milligrams

of CaCO3 present in one litre of water.

iii) Degree Clarke (oCl): It is defined as the parts of CaCO3 equivalent

hardness per 70,000 parts of water.

iv) Degree French (oFr): It is defined as the parts of CaCO3 equivalent

hardness per 105 parts of water.

Relationship between various units of hardness

As, 1ppm = 1 part per 106parts of water
1oFr = 1 part per 105 parts of water
1oCl = 1 part per 70,000 parts of water

Therefore, 106ppm = 105oFr = 70,000 oCl

Hence,
1 ppm = 0.1 oFr = 0.007 oCl = 1 mg/L
Boiler Feed Water
Water is mainly used in boilers for the generation of steam for industries and
power houses. For such water, all the impurities lead to operational trouble in
boilers are eliminated or kept within the tolerable limit.

Boiler-feed water should correspond with the following composition:

i) Its hardness should be below 0.2 ppm.
ii) Its caustic alkalinity(due to OH-) should lie in between 0.15 and 0.45.
iii) Its soda alkalinity (due to Na2CO3) should be 0.45-1ppm.
Excess of impurities, if present, in boiler feed water generally cause the
problems such as scale and sludge formation, corrosion, priming and foaming,
caustic embrittlement
(A) Scales and Sludges
In a boiler, water is continuously evaporated to form steam. This increases the
concentration of the dissolved salts. Finally a stage is reached when the ionic
product of these salts exceeds their solubility product and hence they are
thrown as precipitate.
If the precipitate formed is soft, loose and slimy, these are known as sludges,
while if the precipitate is hard and adhering on the inner wall, it is called as
scale.

Scales
Scales are hard deposits firmly sticking to the inner surface of the boiler. They
are difficult to remove, even with the help of hammer and chisel. Scales are
major source of boiler troubles. Scales may be formed inside the boiler due to:

i) Decomposition of calcium bicarbonate

Ca(HCO3)2 → CaCO3 + H2O + CO2

ii) Decomposition of calcium sulphate

The solubility of CaSO4 in water decreases with increases in temperature.

CaSO4 is soluble in cold water but almost completely insoluble in super-
heated water. This is due to increased ionization at high temperature.
Consequently, CaSO4 gets precipitated as hard scale on the hotter parts of the
boiler. This type of scale causes troubles mainly in high temperature boilers.

iii) Hydrolysis of magnesium salts

Dissolved magnesium salt get hydrolysed (at prevailing high temperature
inside the boiler) forming Magnesium Hydroxide precipitate, which forms a
soft type of scale.
MgCl2 + 2H2O → Mg(OH)2+ 2HCl

iii) Presence of Silica

Even if a small quantity of SiO2 is present, it may deposit as Calcium Silicate

(CaSiO3) or Magnesium Silicate (MgSiO3). These deposits adhere very firmly
on the inner side of the boiler surface and are very difficult to remove.

Disadvantages of Scale formation

i) Wastage of fuel: Scales have a poor thermal conductivity. So, the

rate of heat transfer from the boiler to the inside water is reduced. In
order to provide a steady supply of heat to water, excessive or over
heating is done and this causes increase in fuel consumption.
ii) Decrease in efficiency: Deposition of scale in the valves and
condensers of the boiler, choke them partially. This result is
decreases in efficiency of the boiler.
iii) Danger in explosion: When thick scale crack due to uneven
expansion, the water comes suddenly in contact with over-heated
 portion and large amount of steam is formed instantaneously this
result in development of sudden high pressure which may cause
explosion of the boiler.

Removal of Scale

Scales are removed by mechanical as well as chemical method.

i) If the scales are loosely adhering, they can be removed with the help of
scraper or wire brush.
ii) If the scales are brittle, it can be removed by giving thermal shocks.
iii)If the scales are loosely adhering, they can also be removed by frequent
blowdown operation. (Blow down operation is a partial removal of hard
water through “a tap “at the bottom of the boiler, when extent of hardness
in the boiler becomes alarmingly high.)
iv) If the scales are adherent and hard, they can be removed by adding
chemicals viz. HCl, EDTA etc.

Sludges

Sludge is soft, loose and slimy precipitate formed within the boiler. These are
formed by substances which have greater solubility in hot water than in cold
water. Examples include MgCO3, MgCl2, CaCl2, MgSO4 etc. Sludges are
formed at comparatively colder portions of the boilers and get collected at
places, where the flow rate is slow; they can be easily removed (scrapped off)
with a wire brush. If sludges are formed along with scales, then sludges gets
entrapped in the scale and both get deposited as scale.

Disadvantages of Sludge Formation

i)Sludges are poor conductors of heat , so they tend to waste a portion of heat
generated and thus decreases the efficiency of boiler.
ii) Excessive sludge formation disturbs the working of the boiler. It settles in
the region of poor water circulation such as pipe connections, plug openings,
thereby causing choking of the pipes.

Prevention of sludge formation

i) By using softened water.
ii) By frequently 'blow down operation' (i.e. partial removal of concentrated
water through a tap at the bottom of the boiler, when extent of hardness in
boiler becomes alarmingly high.
(B)Carry Over

The phenomenon of carrying of water along with impurities by steam is called

“carry over”. This is mainly due to priming and foaming. Priming and foaming
usually occur together. They are objectionable because:
i) Dissolved salts or suspended solids in boiler water decrease the efficiency of
boiler.
ii) Dissolved salts may enter the parts of other machines these by decreasing
their life.
iii) Maintenance of the boiler pressure becomes difficult because of improper
judgment of actual height of water column.

Priming
When steam is produced rapidly in the boilers, some droplets of the liquid
water are carried along with steam. This process of wet-steam formation is
called priming. Priming is caused by:
i) The presence of considerable quantities of dissolved solid (mainly due to
suspended impurities and due to dissolved impurities in water).
ii) Steam velocities high enough to carry droplet of water into the steam pipe.
iii) Sudden boiling.
iv) Faulty design of boiler.
Priming can be avoided by

i)Controlling rapid change in steaming velocities.

ii) The proper design of boilers.
iii) Ensuring efficient softening.
iv) Filtration of the boiler - Water carried over to the boiler and blowing off
sludge or scale from time to time.

Foaming
It is the formation of small but persistent foam or bubbles at the water surface
in boilers, which do not break easily. Foaming is caused by the presence of oil
and alkalis in boiler feed water.

Foaming can be avoided by:

i)The addition of anti-foaming agent, which acts by
counteracting the reduction in surface tension .For example, addition of castor
oil, neutralises the surface tension reduction.
ii) By removing the foaming agent from boiler water.

(C)Boiler Corrosion
The decay of boiler material by is environment is known as corrosion.
The main causes for boiler corrosion:
i) Presence of dissolved oxygen
ii) Presence of dissolved carbon dioxide.
iii) Presence of Some inorganic salts like magnesium chloride.
iv) Formatin of Galvanic cells
v) Acids formed by certain lubricating oil.
vi) Presence of free acids in water.

Corrosion has following disadvantages:

(a) Shortening of boiler life
(b) Leakage of joints & bends
(c) Increase cost of repairs & Maintenance

Main Factors Responsible for Corrosion in Boilers:

(a) Presence of Dissolved Oxygen:

Oxygen dissolved in water is mainly responsible for corrosion in boilers.
Dissolved oxygen in presence of moisture and at high temperature readily
attacks iron of the boiler:

2Fe + 2H2O + O2 → 2Fe(OH)2↓

(ferrous hydroxide)
2Fe(OH)2↓ + O2→ 4Fe(OH)3↓ + 2H2O
(ferric hydroxide)
Ferric hydroxide is called yellow rust corresponds to Fe2O3.H2O

Removal of Oxygen:

(i) Sodium sulphite is suitable for boilers operating at low pressure.

The sulphite reacts with the dissolved O2 to form sulphate:

Na2SO3 + ½ O2 → Na2SO4

This method is very effective for removing oxygen in low

pressure boilers but it can not be used in high pressure boilers
because in high pressure boilers dissolved salt concentration
increases to produce priming & foaming and sodium sulphite
decomposes and liberates SO2.
(ii) Hydrazine, N2H4 (40% aqueous solution) is now
extensively used to remove dissolved oxygen in high pressure
boilers. One of the important advantage of hydrazine treatment
is that, combination with O2 does not produce any salt, N2 and
H2O are the only reaction products obtained:

N2H4 + O2 → N2 + H2O

(b) Presence of Dissolved CO2:

Water containing bicarbonates release CO2 on heating. If CO2 is released

inside the boiler, it will go alongwith the steam and as the steam
condenses, CO2 is dissolved in water forming carbonic acid. This
producing intense local corrosion called pitting.

CO2 + H2O → H2CO3

Carbonic acid
CO2 can be removed by addition of NH3
CO2 + H2O + NH3 → (NH4)2CO3

(c)Presence of Dissolved Inorganic Salts:

Some inorganic salts like MgCl2 and CaCl2 are corrosive agents. MgCl2 on
hydrolysis gives HCl as follows:
 MgCl2 + 2H2O → Mg(OH)2 + 2HCl

CaCl2 also undergoes hydrolysis but to a lesser extent. The HCl thus
formed reacts with Fe of the boiler:

Fe + 2HCl → FeCl2 + H2

FeCl2 +2H2O → Fe(OH)2 + 2HCl

Hence even a small amount of MgCl2 can cause considerable corrosion of

the metal. The amount of HCl is neutralized by the addition of alkali.

(d)Formation of Galvanic Cells:

Corrosion can also occur because of galvanic cell formation between iron
& other metals present in the alloy used in boiler fittings. This can be
prevented by suspending zinc plates which act as sacrificial anodes.

(Galvanic Cell): When two dissimilar metals are electrically connected

and exposed to an electrolyte, the metal higher in electrochemical series act
as anode and undergoes corrosion. This type of corrosion is called galvanic
corrosion. In the above example Zn (higher in electrochemical series)
forms the anode and is attacked and gets dissolved, whereas iron, Fe (lower
in electrochemical series) acts as cathode.

Caustic Embrittlement

• It is the phenomenon during which the boiler material becomes brittle

due to the accumulation of caustic substance.
• This type of boiler corrosion is caused by the use of highly alkaline
water in the high pressure boiler.
• During softening of water by lime soda process, free Na2CO3 is usually
present in small proportion in the softened water.
• In high pressure boilers, Na2CO3 decomposes to give NaOH and CO2
Na2CO3 + H2O → 2NaOH +CO2
• The NaOH makes the boiler Caustic.
 • This water containing NaOH flows into the minute hair cracks always
present in the inner side of the boiler by capillary action.
• Here water evaporates and dissolved caustic soda concentration
increases progressively.
• The caustic soda attacks iron of surrounding area inside the boiler as
sodium ferroate.
Fe + 2 NaOH → Na2FeO2 + H2↑
• At these areas corrosion takes place, causing even failure of the boiler.
• Such a phenomenon is known as caustic embrittlement.

Prevention of caustic embrittlement

i) During softening process, sodium phosphate is used in place of sodium

carbonate.
ii) Tannin or lignin should be added in boiler water which blocks the hair
cracks.
iii) Sodium sulphate should be added in boiler water.

Water Softening
The process whereby we remove or reduce the hardness of water irrespective
of whether it is temporary or permanent is termed as ‘softening’ of water.
Water softening is very essential
since hard water is unsuitable for domestic as well as industrial use. Water can
be made soft by external as well internal treatment.

External treatment can be done by the following method:

i) Lime soda process

ii) Zeolite or permutit Method
iii) Ion-exchange method

Lime soda process

The basic principle of the process is to chemically convert all the soluble
hardness causing impurities into insoluble precipitate which may be removed
by settling and filtration. For this a suspension of milk of lime Ca(OH) 2,
together with a calculated amount of sodium carbonate, Na2CO3 (soda) is
added in requisite amount. Proper mixing of chemicals and water is carried
out. Calcium carbonate and magnesium hydroxide so precipitated are filtered
off.

Lime removes Temporary hardness

Ca(OH)2 + Ca(HCO3)2 → 2CaCO3 ↓+ 2 H2O

(Soluble impurities) (Insoluble ppt.)

Ca(OH)2 + Mg(HCO3)2 → Mg(OH)2 ↓+ 2CaCO3 ↓+ 2 H2O

Lime removes permanent hardness of Magnesium

Ca(OH)2 + MgSO4 → Mg(OH)2 ↓+ CaSO4

Ca(OH)2 + MgCl2 → Mg(OH)2 ↓+ CaCl2

Lime removes some mineral acids present in water

Ca(OH)2 +2HCl → CaCl2 + 2H2O

Ca(OH)2 +H2SO4 → CaSO4 + 2H2O

Lime removes some gases present in water

Ca(OH)2 +H2S → CaS↓ + 2H2O
Ca(OH)2 +CO2 → CaCO3↓ + H2O

Soda removes permanent hardness of Calcium

CaCl2 + Na2CO3 → CaCO3 ↓ + 2NaCl

CaSO4 + Na2CO3 → CaCO3 ↓ + Na2SO4

At room temperature, the precipitates formed are very fine. They do not settle
down easily and causes difficulty in filtration. If small amount of coagulants
like alum K2SO4.Al2(SO4)3.24H2O and aluminium sulphate are added, they
hydrolyse to precipitate of aluminium hydroxide which entraps the fine
precipitate of CaCO3 and Mg(OH)2. Thus coagulant helps in the formation of
coarse precipitates.

Lime soda processes are of two types:

i) Cold lime soda process
ii) Hot lime soda process
Cold lime soda process: In this process, calculated quantities of
lime and soda are mixed with water at room temperature. The precipitate
formed at room temperature is finely divided and does not settle down easily.
They cannot be easily filtered so, it is essential to add a small quantity of
coagulant which
hydrolysis to give flocculent and gelatinousprecipitate of aluminium
hydroxide, thus it entraps the fine precipitate. There are two kind of softeners
used for softening water by this process.
i) Intermittent type softeners, where the softening is done by batch process.
ii) Continuous type softeners.
Hot lime soda process: In this process, water is treated with
chemicals at a temperature of 94-1000C. The softeners used are of intermittent
type or continuous type.

Advantages of Hot lime soda process:

i) They are more rapid in operation. The time taken for completion is 15
minutes and several hours for hot and cold lime soda processes respectively.
ii) Elevated temperature accelerates the actual chemical reaction and reduces
the viscosity of the water. This increases the rate of aggregation of the particle.
Hence, both the setting rates and filtration rates are increased. Thus the
softening capacity of the hot process is several times higher than the cold
process.

iii) The sludge and the precipitate formed settle down rapidly and hence no
coagulant is needed

iv) Quantity of chemical required for softening is low.

v) At the higher temperature, the dissolved gases such as CO2 are driven out
of the solution to some extent.
Advantages of Lime-soda Process:
i) It is very economical.
ii) Treated water is alkaline and hence has less corrosion tendencies.
iii) It removes not only hardness causing salt but also minerals.
iv) Due to alkaline nature of treated water, amount of pathogenic bacteria in
water is considerably reduced.
v) Iron and manganese are also removed from the water to some extent.
Disadvantages of Lime-soda process:
i) It requires careful operation and skilled supervision for economical and
efficient softening.
ii) Sludge disposal is a problem.
iii) Water softened by this process contains appreciable concentration of
soluble salts, such as sodium sulphate and cannot be used in high pressure
boiler.
iv)This can remove hardness only up to 15 ppm, which is not good for boilers.

Zeolite or permutit Method

Zeolites are of two types:
i) Natural zeolite are non porous e.g. Natrolite Na2O.
Al2O3.4SiO2.2H2O
ii) Synthetic zeolite are porous & possess gel structure. Such zeolites
possess higher exchange capacity than natural zeolites.

Chemical structure of sodium zeolite may be represented as

Na2O. Al2O3.xSiO2.yH2O
 Where x = 2-10 and y = 2-6
Zeolite is hydrated sodium alumino silicate, capable of exchanging reversibly
its sodium ions for hardness producing ions in water. Zeolites are also known
as permutit.
Process
For softening of water by zeolite process, hard water is percolated at a
specified rate through a bed of zeolite, kept in a cylinder. The hardness
causing ions (Ca2+, Mg2+ etc) are retained by the zeolite as CaZe and MgZe
respectively, while the outgoing water contains sodium salts. Reactions taking
place during the softening process are:

Na2Ze + Ca(HCO3)2 → CaZe + 2NaHCO3

Na2Ze + Mg(HCO3)2 → MgZe + 2NaHCO3
Na2Ze + CaCl2 → CaZe + 2NaCl
Na2Ze + CaSO4 → CaZe + Na2SO4
Na2Ze + MgCl2 → MgZe + 2NaCl
Na2Ze + MgSO4 → MgZe + Na2SO4

Regeneration

CaZe + 2NaCl → Na2Ze + CaCl2

(exhausted zeolite) (brine soln) (reclaimed zeolite) (washings)

After sometime, the zeolite is completely converted into calcium and

magnesium zeolites and it ceases to soften water, i.e. it gets exhausted. At this
stage, the supply of hard water is stopped and the exhausted zeolite is
reclaimed by treating the bed with a concentrated (10%) brine (NaCl) solution.
Advantages of Zeolite processes:
i) It removes the hardness almost completely and water of about 10
ppm hardness is produced.
ii) The equipment used is compact, occupying a small space.
iii) No impurities are precipitated, so there is no danger of sludge
formation.
iv) It requires less time, less skills for maintenance.

Disadvantages of Zeolite Process:

i) The treated water contains more sodium salts than in lime soda
process. These sodium salts create problems in boilers like corrosion,
caustic embrittlement etc.
ii) High turbidity water cannot be treated efficiently by this method,
because fine impurities get deposited on the zeolite bed, thereby
creating problem for its working.
Ion Exchange Process
Ion exchange is a process by which ions held on a porous, essentially soluble
solid are exchanged for ions in solution that are brought in contact with it. Ion
exchange resins are insoluble, cross linked, high molecular weight; organic
polymers with a porous structure and the “functional group” attached to the
chains are responsible for the ion-exchange properties.
There are two types of ion-exchange resins:
i) Cation Exchange Resin: They are mainly styrene-divinyl benzene co-
polymers, which on sulphonation or carboxylation become capable to
exchange their hydrogen ions with the cations in the water. Such resins have
acidic functional groups like –SO3H,–COOH or –OH group capable of
exchanging the cationic portion of minerals by their hydrogen ions, hens they
are termed as cation exchanger. For example: Ambalite IR-20 and Dowex-50
are commercially available cation exchanger resins.
ii) Anion Exchange Resin: They are styrene– divinyl benzene or amino
formaldehyde copolymers, which contain basic functional group such as
amino as integral part of region matrix. These after treatment with dilute
NaOH, become capable to exchange their OH anions with anions in water and
therefore they are known as anion exchanger. For example: Amberlite-400 and
Dowex-3 are commercially available anion exchange resins.

Process
The hard water is first passed through cation exchange column, where all the
cautions like Ca2+, Mg2+are removed from it, and equivalent amount of H+
ions are released from this column to water.
2RH+ + Ca2+ → R2Ca2+ + 2H+

2RH+ + Mg2+ → R2Mg2+ + 2H+

After passing through cation exchange column, the hard water is passed
though anion exchange column, where all the anions like SO2-, Cl-etc. present
in water are removed and equivalent amount of OH- ions are released from
this column to water.

R’OH- + Cl- → R’Cl- + OH-

2R’OH- + SO4-2 → R’ SO4-2 + 2OH-

2R’OH- + CO3-2 → R’ CO3-2 + 2OH-

H+ and OH- ions, released from cation and anion exchanger respectively, get
combined to produce water molecules.

H+ + OH- → H2 O

Thus the water coming out from the exchanges is free from cations as well as
anions. Ion free water is known as de- ionised or de-mineralised water. Thus it
is known as pure as distilled water. Finally, the demineralised water is passed
through a degasifier, a tower whose sides are heated and which is connected
to a vacuum pump. High temperature and low pressure reduces the amount of
dissolved gases like CO2 and O2 in water.
Regeneration: When capacities of cation and anion exchange H+ and OH-
ions respectively are lost, they are said to be exhausted. The exhausted cation
exchange column is regenerated by passing a solution of dilute HCl or
HNO3/H2SO4.The regeneration can be represented as:

R2Ca2+ + 2H+ → 2RH+ + Ca2+

R2Mg2+ + 2H+ → 2RH+ + Mg2+

The exhausted anion exchange column can be regenerated by passing a

solution of dilute NaOH. The regeneration can be represented as:
R’Cl- + OH- → R’OH- + Cl-

R’ SO4-2 + 2OH- → 2R’OH- + SO4-2

R’ CO3-2 + 2OH- → 2R’OH- + CO3-2

Advantages of ion exchange processes:

i) The process is used to soften highly alkaline or acidic water.
ii) It produces water of very low hardness (about 2ppm). So it is very
good for treating water for use in high pressure boilers.

Disadvantages of ion exchange processes:

i) The equipment is costly and more expensive chemicals are needed.
 ii) If water contains turbidity, then the output of the process is reduced.
The turbidity must be below 10 ppm. If it is more, it has to be
removed first by coagulation and filteration.

Internal treatment
In this water softening is done by treating raw water inside the boiler. This
method is known as sequestration. Internal treatment methods are followed
by ‘blow down operation’, so that the accumulated sludge is removed. Some
of the important internal treatment methods are:
i) Colloidal conditioning: Scale formation can be avoided in low pressure
boilers by adding substances like kerosene, tin, agar-agar etc, which get
absorbed over the scale forming precipitates thus giving us non- sticky and
loose deposits,
which can be easily removed by blow-down operation.
ii)Carbonate conditioning: In low pressure boilers, scale formation can
be avoided by adding sodium carbonate to boiler water, when CaSO4 is
converted in to calcium carbonate in equilibrium.

CaSO4 + Na2CO3 → CaCO3 + Na2SO4

Consequently, deposition of CaSO4 as scale does not take place and calcium is
precipitated as loose sludge of CaCO3, which can be removed by blow down
operation.
iii)Phosphate Conditioning: In high pressure boilers, scale formation can be
avoided by adding sodium phosphate, which reacts with hardness of water
forming non adherent and easily removable, soft sludge of calcium and
magnesium phosphates, which can be removed by blow down operation, e.g.,

3CaCl2 + 2 Na3PO4 → Ca3 (PO4)2 ↓ + 6 NaCl

The main phosphates employed are: NaH2PO4, sodium dihydrogen phosphate

(acidic); (b) Na2HPO4, disodium hydrogen phosphate (weakly alkaline) ; (c)
Na3PO4, trisodium phosphate (alkaline)

iv) Calgon conditioning: Calgon is the commercial name of sodium hexa-

metaphosphate. The process involves the addition of sodium hexa-
metaphosphate to boiler water to prevent the scale and sludge formation.
Calgon converts the scale forming impurity like CaSO4 into soluble complex
compound, which are harmless to the boiler.
Na2[Na4(PO3)6] → 2Na+ + [Na4(PO3)6]2-
Calgon

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

Soluble complex

Addition of 0.5-5 of Calgon prevents scale formation in one of the following

ways:

i) At low temperature and pressure, it forms quit stable and soluble complexes
with calcium salts.
ii) At high temperature and pressure, calgon is converted into sodium
orthophosphate which reacts with calcium salts to form calcium
orthophosphates. Calcium orthophosphate appears as loose sludge and this can
be removed by blow down operation.

Alkalinity of Water

Alkalinity is a measure of the ability of water to neutralize the acids. The

alkalinity of water is normally due to the presence of bicarbonates and
hydroxides of sodium, potassium, Ca and Mg. Presence of borates, silicates
phosphates can also
contribute to the total alkalinity to some extent.
Depending upon the anion present, the alkalinity can be classified as:

i) Caustic alkalinity (due to OH-and CO32-ions)

iii) Hydroxide only (OH-)
iv) Carbonates only (CO32-)
v) Bicarbonates only (HCO3-)
vii) Carbonates and bicarbonates (CO32-+ HCO3-)
Degree of Hardness
Althoughhardnessofwaterisneverpresentintheformofthecalciumcarbonate,because
itisinsolubleinwater,hardnessofwaterisconvenientlyexpressedintermsofequivalent
amount of CaCO3.

The reason for choosing CaCO3as the standard for reporting hardness water is the
3
easeincalculationasitsmolecularweightisexactly100.Moreover,itisthemostinsoluble
saltthatcanbeprecipitateinwatertreatment.

EquivalentsofCaCO3=[Amountofhardnessproducingsubstance]×[Chemicalequivalentof
3
CaCO3(=50)]×2 / [Chemicalequivalentofhardnessproducingsubstance]×2
3

= [Amount of hardness producing substance] × 100/ [Chemical equivalent of

hardness
producing substance × 2]
= [Amount of hardness producing substance] × (Multiplication factor) in mg /lit.
or
ppm.

Multiplication Factor
Weight of MgSO4, Mg(HCO3)2, MgCl2 and CaCl2 actually present, may be
converted in termsofweightofCaCO3
bymultiplying100/120,100/146,100/95and100/111respectively.
Factorsusedforsuchconversionarecalledmultiplicationfactor.Itcanbeshownasfollows:
Mg(HCO3)2 = CaCO3

146 = 100
Where, we are comparing hardness due to Mg(HCO3)2 in terms of CaCO3
equivalents. X quantity of Mg(HCO3)2 = X × 100/146 amount of CaCO3 thus the factor
100/146 is multiplication factor (M.F.) for Mg(HCO3)2.
 Multiplication factor =100/ [Chemical equivalent of hardness producing substance × 2]
M.F. for various compounds are shown in Table 1.2.
Table 1.2: Multiplication factors for various compounds

Compounds/Salt/Ions Molar mass Chemical Multiplication factor

equivalent (for conversion into
CaCO3 equivalent )

Ca(HCO3)2 162 81 100/162

Mg(HCO3)2 146 73 100/146

CaCO3 100 50 100/100

MgCO3 84 42 100/84

CaSO4 136 68 100/136

CaCl2 111 55.5 100/111

MgSO4 120 60 100/120

MgCl2 95 47.5 100/95

Mg(NO3)2 148 74 100/148

CO2 44 22 100/44

Ca2+ 40 20 100/40

Mg2+ 24 12 100/24

CO32– 60 30 100/60

H+ 1 1 100/02
–
HCO 61 61 100/2×61 = 100/122
3
OH– 17 17 100/2×17 = 100/34

NaAlO2 82 82 100/64

Al2(SO4)3 342 57 3×100/342 = 100/114 or 100/57

FeSO4.7H2O 278 139 100/278

Ca(NO3)2 164 82 100/164

HCl 36.5 1 100/2×36.5 = 100/73

H2SO4 98 49 100/98