Water

Syllabus: Introduction; hardness of water: causes, types, units,

disadvantages of using hard water for domestic and industrial
purposes (e.g., scale and sludge formation in boilers, caustic
embrittlement, boiler corrosion, etc.); softening of hard water (lime-
soda, permutit and ion-exchange processes); chemical analysis of
water- estimation of free chlorine, total alkalinity, hardness and
dissolved oxygen. Numericals on hardness.
 Introduction: General information
 Water is one of the abundant commodities in nature, but is also the most misused one.
 Earth is a blue planet, 71% of our planet is covered by water. But, 97.5% of it is locked in
the oceans, which is too saline to drink and other uses. 2.4% water is trapped in polar ice
caps and giant glaciers, from which only 1% water is used by human for various
development, industrial, agricultural and domestic purposes.

 Water is essential for survival of all the living beings on earth that is man, animals and
plants. Water is not only essential for the survival of life, but it is also used for the
operation in a large number of industries as coolant, solvent , for steam generation etc.
water is also used for all domestic purpose like bathing, drinking, washing, sanitary,
irrigation etc.
Sources of water
Surface Water:
(i) Flowing water e.g. rivers and streams (Moorland surface drainage)
In general river water contains dissolved minerals from soil such as chlorides,
sulphates, bicarbonates of sodium, calcium or magnesium, iron and organics
matters derived from decomposition of plants, small particles of sand and rocks in
suspensions.

(ii) Still waters e.g. lakes, ponds and reservoirs ( Lowland surface drainag
Lake water has more constant chemical composition.

Underground Water: water from shallow and deep spring and wells

Rain water: It is probably the purest form of natural water

Sea Water: It is probably the most impure form of natural water

3
Types of Impurities Present in water
Dissolved impurities:
(a) Inorganic salts e.g.
(i) Cations: Ca2+, Mg2+, Na+, K+, Fe+2, Al+3, Zn2+, Cu2+
(ii) Anions: Cl-, SO42-, NO3-, HCO3-, F-, NO2-
(b) Gases: CO2, O2, N2, NH3, H2S
(c) Organics salts
Suspended impurities:
(a) Inorganic e.g. clay and sand
(b) Organics e.g. oil globules, vegetable and animal matters
Colloidal impurities:
Clay and finely divided silica colloidal partials of 10-4 – 10-6 mm
size
Micro-organisms:
Bacteria, Fungi, algae and other forms of animal and vegetable life
4
Effects of Impurities in natural water
 Colour
 Taste and odour
 Turbidity and sediments
 Micro-organisms
 Dissolved minerals matters
(a) hardness
(b) Alkalinity
(c) Total solids
(d) corrosion

5
 Hardness of water
Hardness of water is originally defined as the soap consuming
capacity of a water sample. The soap consuming capacity of water
is mainly due to the certain salt of calcium, magnesium and other
heavy metals dissolved in it.
The soap is generally consists of sodium salts of fatty acids such as
Oleic acid, palmetic acid and stearic acid. Calcium and magnesium
React with the sodium salts of long chain fatty acid present in the
soap to form insoluble scums of calcium and magnesium soaps.
2 C17H35COONa + CaCl2 (C17H35COO)2Ca + NaCl
(Sodium stearate) (Insoluble)

2 C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4

(Sodium stearate) (Insoluble)

Other metal ions such as Fe2+, Mn2+, Al3+ also contributing to hardness, but
they are present in water only in traces
6
 Temporary hardness (carbonate hardness)
Temporary hardness is caused by the presences of dissolved
bicarbonate of calcium and magnesium and other heavy metal ions
Temporary hardness is mostly destroyed by boiling of water. During
boiling bicarbonate are decomposed in the insoluble carbonate and
hydroxide, which are deposited at the bottom of the vessel.
Heat
Ca(HCO3)2 CaCO3 + CO2 + H2O
(Insoluble)

Heat
Mg(HCO3)2 MgCO3 + 2 CO2
(Insoluble)

Permanent hardness (non-carbonate hardness)

This is due the presences of chlorides and sulphates of calcium,
magnesium, iron and other heavy metal ions.
7
Hardness is expressed in terms of equivalent of calcium carbonate
because it is the most insoluble salt that can be precipitated in water
treatment.
Mass of hardness producing substances x 50
Equivalent of CaCO3 =
Chemical equivalent of hardness producing substances

Dissolved Molar Chemical Multiplication factor for

salt Mass equivalent converting into equivalent
of CaCO3
Ca(HCO3)2 162 81 100/162
Mg(HCO3)2 146 73 100/146
CaSO4 136 68 100/136
CaCl2 111 55.5 100/111
MgSO4 120 60 100/120
MgCl2 95 47.5 100/95
MgCO3 84 42 100/84
8
Estimation of hardness: Hardness are usually determined by two methods

Soap solution methods:-

soaps gives lather with hard water only after sufficient quantity of soaps is
added to precipitate all the hardness causing metal ions present in water

2 C17H35COONa + CaCl2 or MgCl2 (C17H35COO)2Ca or Mg + NaCl

(Sodium stearate) (Insoluble)

2 C17H35COONa + MgSO4 or CaSO4 (C17H35COO)2Mg or Ca + Na2SO4

(Sodium stearate) (Insoluble)

After precipitation of all the hardness causing ions present in water, further addition
of soap gives lather

9
EDTA Method:- NaOOCH2C CH2COONa

N CH2 CH2 N
HOOCH2C CH2COOH

Hard water
+
EBT Indicator M
+
10 PH buffer solution
OOCH2C CH2COO

N CH2 CH2 N
NaOOCH2C CH2COONa

Ca/Mg
H
H
OO O
O O
O

NaO3S N N
NaO3S N N
NaO3S N N

O2N
O2N
O2N

10
 WATER SOFTENING

 removal of hardness
» Hardness is?...
primarily Ca, Mg, plus Fe, Mn, St, Al

 How is Softening done?...

Precipitation of Ca and Mg, or
Ion exchange of Ca / Mg with ion such as Na

11
 Why bother?

 Hardness in 300-500 mg/l as CaCO3

range considered excessive
high soap consumption
scaling in heating vessels and pipes
 Even > 150 mg/l may result in
consumer objection
 60-120 mg/l as CaCO3 is considered a
moderate amount

12
 Lime-Soda process
In this process, all the soluble hardness-causing impurities are converted
into insoluble precipitates which may removed by setting and filtration .
In the lime soda process, calculated amount of lime Ca(OH)2 and soda
Na2CO3 is added in the hard water. The soluble calcium and magnesium
salts in water are converted into insoluble compound such as calcium
carbonate and magnesium hydroxide which may removed by setting and
filtration.
(i) Lime removes the temporary hardness:
Ca(HCO3)2 + Ca(OH)2 2 CaCO3 + 2 H2O
Mg(HCO3)2 + 2 Ca(OH)2 Mg(OH)2 + CaCO3 + H2O

(ii) Lime removes the permanent magnesium hardness:

MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2

MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4

13
(iii) Lime removes the dissolved iron and aluminum salts:
FeSO4 + Ca(OH)2 Fe(OH)2 + CaSO4

Al2(SO4)3 + 3 Ca(OH)2 2 Al(OH)3 + 3 CaSO4

(iv) Lime removes free mineral acids:
CaCl2 + H2O
2 HCl + Ca(OH)2

H2SO4 + 3 Ca(OH)2 CaSO4 + H2O

(v) Lime removes dissolved CO2 and H2S:

CO2 + Ca(OH)2 CaCO3 + H2O

H2S + 3 Ca(OH)2 CaS + 2 H 2O

(vi) Soda removes all calcium permanent hardness:

CaCl2 + Na2CO3 CaCO3 + NaCl

CaSO4 + Na2CO3 CaCO3 + Na2SO4

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Now the 100 parts by mass of CaCO3 are equivalent to : (i) 74 part
of Ca(OH)2 and (ii) 106 parts of Na2CO3

Lime required for softening:

74 [ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+)

=
100 + CO2 + H+ (HCl or H2SO4) + HCO3-]

Soda required for softening:

106 [ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or

=
100 H2SO4) - HCO3-]

15
Cold lime soda process:
Calculated quantity of lime and soda are mixed with water at
room temperature the precipitates formed are finely divided, so
they do not settle down easily. Therefore, It is essential to add
small amounts of coagulants (like alum, aluminum sulphate,
sodium aluminates etc).

Use of sodium aluminate as coagulant also helps the removal of

silica as well as oil if present in water..

NaAlO2 + 2H2O NaOH + Al(OH) 3

Al2(SO4)3 + 3Ca(HCO3)2 2Al(OH)3 + 3CaSO4 + 6CO2

16
 Continuous cold lime soda softener

Chemicals
Hard water
(soda+lime
feed
+coagulant)
feed
Softened
water
Wood fiber
filter

Stirrer
paddles

Sedimented sludge (CaCO3,

Mg(OH)2

17 17
Hot lime soda process:
Calculated quantity of lime and soda are mixed with
water at 80 to 1500C.

Advantages of high temperature:

The reaction proceeds faster.

Softening capacity is increased.
No coagulant needed as the precipitate and sludge formed settle
down rapidly.
Much of the dissolved gases are driven out of water.
Viscosity of soften water is lower, so filtration of water becomes
easier.
This process produces water of comparatively low residual
hardness 15 to 30 ppm.
Continuous Hot Lime
Soda Process
Advantages of lime soda process:
It is very economical.

If the process is combined with sedimentation/coagulation

lesser amounts of coagulants shall be needed.

The process increases the pH of the treated water thereby

corrosion reduced.

In addition to the removal of hardness, the quantities of minerals

in the water are reduced.

 Due to alkaline nature of treated water amount of pathogenic

bacteria in water is considerably reduced.
Disadvantages of lime soda process:
For efficient and economical softening, careful operation and
skilled supervision is required.

Disposal of large amount of sludge poses a problem.

This can remove hardness up to 15 ppm which is not good for

boilers.
 WATER SOFTENING
Ion exchange or deionization or demineralization
process: Ion-exchange resins are widely used in different separation,
purification, and decontamination processes. The most common examples are
water softening and water purification.
Ion-exchange resins are insoluble, cross linked, long chain organic
polymer with micro porous structure and the functional groups
attached to the chains are responsible for the ion exchange
properties.

Cation Resin after

exchange Resin treatment
Resins containing acidic functional groups (-COOH, -SO3H) are
capable of exchanging their H+ ions with other cations which comes
in their contacts, known as a cation exchange resins (RH+).

e.g. styrene-divinyl benzene copolymer, which on sulphonation and

carboxylation, become capable to exchange their hydrogen ions with
the cations in the water.
Resins containing basic functional groups (-NR2+OH-) are capable of
exchanging their anions with other anions which comes in their
contacts, known as a Anion exchange resins (ROH-).

They are styrene divinyl benzene or amine-formaldehyde

copolymerization which contains quaternary ammonium or quaternary
phosphonium or tertiary tertiary sulphonium groups as an integral part
of the resin matrix. These after treated with dil NaOH becomes
capable of exchanging their OH- ions with anions of water.
Process:- The hard water is passed first through cation exchange
column, which remove all the cations from it and equivalent amount of
hydrogen ions are released from this column to water:

2RH+ + Ca2+ R2Ca2+ + 2H+

2RH+ + Mg2+ R2Mg2+ + 2H+

After cation exchange column the hard water is passed through anion
exchange resin column, which remove all the anions from it and
equivalent amount of hydroxide ions are released from this column to
water :
ROH- + Cl- RCl- + OH-
2ROH- + SO42- R2SO42- + 2OH-

H + + OH- H2O
Thus water coming out from the exchange is free from cations as well as
anions.
 Ion exchange purifier or softener

Hard
water

Gravel
Cation exchange Resin Anion exchange Resin bed

Injector
Injector

Acid
solution for Wastages to
regeneratio sink Alkaline solution for
n of resin Wastages to
regeneration of resin
sink
pump

Soft water 26
 Regeneration:
Cation exchange column is regenerated by passing a solution of dil
HCl or dil H2SO4. The regeneration can be represented as

R2Ca2+ + 2H+ 2RH + Ca2+

Exhausted anion exchange column is regenerated by passing a

solution of dil. NaOH. The regeneration can be represented as

R2SO42- + 2OH- 2ROH + SO42-

Advantages:
Can be used to soften highly acidic or alkaline waters.

It produces water of very low hardness.

Disadvantages:
The equipment is costly

Expensive chemicals are needed

Output of the process is reduced if water contains turbidity.(turbidity

must be below10 ppm)
 Zeolite (Permutit) method of Softening of
water
Zeolite is a Hydrated Sodium Alumino
Silicate (HSAS), capable of exchanging
reversibly its sodium ions for hardness
producing ions in water.

The general chemical structure of zeolite

is given below Na2O.Al2O3.xSiO2.yH2O (x =
2-10 and y = 2-6)

Micro pores of Zeolite Porous Structure of zeolite

 Porosity or cavity size of synthetic zeolite structures can be

controlled by varying the Si/Al ratio
 Ion-exchange process of zeolite structure is associated with
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sodium ions
 Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

30
Process of softening by Zeolite method
For the purification of water by the zeolite softener, hard water is passed through
the zeolite bed at a specified rate. The hardness causing ions such as Ca2+, Mg2+
are retained by the zeolite bed as CaZe and MgZe respectively; while the
outgoing water contains sodium salts. The following reactions takes place during
softening process

To remove temporary hardness

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3
Hardness

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3

To remove permanent hardness water

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl Na2Ze + CaCl2 (MgSO4)

Used 10% brine Regenerated Washings

Zeolite solution Zeolite drained
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Limitations of Zeolite process
1. If the water is turbid ---- then the turbidity causing particles clogs the
pores of the Zeolite and making it inactive
2. The ions such as Mn2+ and Fe2+ forms stable complex Zeolite which
can not be regenerated that easily as both metal ions bind strongly
and irreversibly to the zeolite structure.
3. Any acid present in water (acidic water) should be neutralized with
soda before admitting the water to the plant, since acid will hydrolyze
SiO2 forming silicic acid

Advantages of Zeolite process

1. Soft water of 10-15 ppm can be produced by this method

2. The equipment occupies less space
3. No impurities are precipitated, hence no danger of sludge formation
in the treated water
4. It does not require more time and more skill 32
Disadvantages of Zeolite process

1. Soft water contains more sodium salts than in lime soda process
2. It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other ions
like HCO3- and CO32- in the softened water (then it may form
NaHCO3 and Na2CO3 which releases CO2 when the water is boiled
and causes corrosion)
3. It also causes caustic embrittlement when sodium carbonate
hydrolyses to give NaOH
Scales and Sludges Formation In Boilers:
In boilers, water evaporates continuously and the concentrations of the
dissolved salts increases progressively. when concentrations of dissolved
salts reach saturation point, they form precipitates in form of loose and
slimy, it is called sludge. On the other hand, if the precipitate matter
form a hard adhering crust/coating on the inner walls of the boiler, it is
called scale.
Disadvantages of sludge formation
 Sludge’s are poor conductor of heat, so they tend to waste a portion
of heat generated.
 Sludge’s get entrapped in the scale and both get deposited as scales.
 Excessive sludge formation, disturbs the working of the boiler. It
settle in the regions of poor water circulation such as pipe
connection etc.

Prevention of sludge formation:

 By using well softened water
 By frequently ‘blow-down operation’, i.e., drawing off a portion of
the concentrated water.
Scales are hard deposit, which stick very firmly to the inner surface of
boiler. Scales are very difficult to remove.
Formation of scales may be due to

(1) Decomposition of calcium bicarbonate:

Ca(HCO3)2 → CaCO3 + H2O + CO2 (In low-pressure boilers)

Scale composed mainly from calcium carbonate is soft and is the main
cause of scale formation in low pressure boiler. But in the high pressure
boiler calcium carbonate is soluble.
CaCO3 + H2O → Ca(OH) 2 (soluble) + CO2 (In high-pressure boilers)

(2) Deposition of Calcium Sulphate:

Solubility of calcium sulphate in water decrease with rise of

temperature. Hence CaSO4 gets precipitated as hard scale on the
heated portions of the boiler.
(3) Hydrolysis of magnesium salts:
Dissolved Mg salts undergo hydrolysis forming magnesium hydroxide
precipitate, which forms a soft type of scale
MgCl2 +2H2O → Mg(OH)2 + 2HCl
(Scale)

(4) Presence of silica:

SiO2 even present in small quantities, deposits as calcium silicate

(CaSiO3) and /or magnesium silicate (MgSiO3). These deposits stick on
the inner side of the boiler surface and are very difficult to remove.
 Disadvantages of scale formation
 Wastage of fuel: Scales have a low thermal conductivity, so that rate
of heat transfer from boiler to inside water is greatly decreased
 Lowering of boiler safety: Due to scale formation, over heating of
boiler is done, which causes distortion of boiler tube.
 Decrease in efficiency: Scales may deposit in the valve and
condensers of the boiler and choke them partially.
 Danger of explosion: When thick scales crack, the water comes
suddenly in contact with over heated iron plates.

Removal of scales
With the help of scraper or piece of wood or wire brush.
By giving thermal shocks, if they are brittle.
By dissolving them by adding chemicals, (5-10% HCl, EDTA) if they
are adherent and hard.
By frequent blow-down operation, if the scales are loosely adhering.
Prevention of scales formation
(1) External Treatment: Includes efficient ‘softening of water’
(i.e., removing hardness-producing constituents of water)
(2) Internal Treatment: Accomplished by adding a proper
chemical to the boiler water either:

Internal treatment:
In this process, an ion is prohibited to exhibit its original character by
complexing or converted into other more soluble salt by adding
appropriate reagent.

An internal treatment is accomplished by adding a proper chemical to water

either:
(a)To precipitate the scale forming impurities in the form of sludge, which
can be removed.
(b)To convert them into compounds, which will stay in dissolved form in
water and thus do not cause any harm.
 Important Internal Treatments are:

Phosphate conditioning:
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 phosphate.

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

The choice of salt depends upon the alkalinity of the boiled water
because calcium cannot be precipitated below a pH 9.5.
 Trisodium phosphate is most suitable for treatment when
alkalinity is low
 Disodium phosphate is used when the water alkalinity is
sufficient.
 Monosodium phosphate is used when the alkalinity of boiler
water is too high.
Calgon conditioning:

Its involve in adding calgon (Sodium hexa-meta phosphate (NaPO3)6

to boiler water. It prevents the scale and sludge formation by
forming soluble complex compound with CaSO4.

Na2[Na4(PO3)6] 2Na+ + [Na4P6O18]2-

2CaSO4 + [Na4P6O18]2- [Ca2P6O18]2- + 2Na2SO4

soluble complex ion
(i) Colloidal conditioning: Scale formation can be avoided by adding
organic substances like kerosene, tannin, agar-agar (a gel) etc.,
which get coated on over the scale forming precipitate, thereby,
yielding non-sticky and loose deposits.
(ii) Carbonate Conditioning: In low pressure boilers, scale-formation
can be avoided by adding sodium carbonate to boiler water.
CaSO4 +Na2CO3 → CaCO3 + Na2SO4
(v) Treatment with sodium aluminate (NaAlO2): sodium aluminate
gets hydrolyzed yielding NaOH and a gelatinous of aluminum
hydroxide
NaAlO2 + 2H2O → NaOH + Al[OH]3
Sod.meta-aluminate (Gelatinous ppt.)
Theses sodium hydroxide precipitates some magenisium
MgCl2 + 2NaOH → Mg(OH) 2 + 2NaCl
The flocculent precipitate of Mg(OH)2 and Al[OH] 3 produced inside the
boiler, entraps finely suspended and colloidal impurities, including oil
drops and silica.
(vi) Electrical conditioning: Sealed glass bulbs, containing Hg
connected to a battery, are set rotating in the boiler. when water boils,
mercury bulbs emit electrical discharges which prevents scale forming
particles to adhere/stick together to form scale.
(vii) Radioactive conditioning: Tablets (radioactive salts) are placed
inside the boiler water. Energy radiations emitted by these salts
prevent scale formation
 Priming and Foaming
Priming
When a boiler is steaming rapidly, some particles of the liquid water are
carried along-with steam. this process of wet steam is called Priming.

Reasons for Priming:

 The presence of large amount of dissolved solids
 High steam velocities
 Sudden boiling
 Improper boiler design
 Sudden increase in steam- production rate.
Priming can be avoided by
 Fitting mechanical steam purifiers.
 Avoiding rapid change in steaming rate.
 Maintaining low water levels in boilers.
 Efficient softening and filtration of the boiler-feed water.
Foaming: Production of persistent foam or bubbles in boilers. This is
due to presence of substances (oils) which reduce the surface tension of
water.

Priming and foaming usually occur together. They are objectionable

because
Efficiency reduces as dissolved salts in boiler water get deposited on
super-heater and turbine blades, as water evaporates.
Life of the machinery may decrease as dissolved salts may enter the
parts of other machinery.
Maintenance of the boiler pressure becomes difficult, as actual height
of the water column cannot be judged properly.
Foaming can be avoided by
Adding anti-foaming chemicals like castor oil.
Removing oil from boiler water by adding compounds like sodium
aluminate
BOILER CORROSION
Decay of boiler material due to chemical or electro-chemical attack by its
environment. Main reasons for boiler corrosion are:
(i) Dissolved oxygen: Dissolved oxygen in water, in presence of prevailing
high temperature, attacks boiler material:
2Fe+2H2O + O2 2Fe(OH)2 ↓
4Fe(OH)2 + O2 2[Fe2O3.2H2O] ↓
(Ferrous hydroxide) (Rust)

Removal of dissolved oxygen:

(i) Adding calculated quantity of sodium sulphite or hydrazine
2Na2SO3 + O2 → 2Na2SO4
N2H4 + O2 → N2 + 2H2O
Na2S +2O2 → Na2SO4
2. By mechanical deaeration
It comprises of a tall stainless tower
with different layers capped with
baffles to facilitate multiple
equilibration.

The entire chamber is vacuumized and Water feed

also maintained at high tempt using
perforated heating plates on the walls.

Principle: High tempt and low pressure O2

To vacuum
favors lower solubility of gases in water
(Henry’s law)
Steam jacket

Perforated
plate

Deaerated
47 water
47
(ii) Dissolved carbon dioxide (carbonic acid):
CO2+H2O → H2CO3
CO2 has a slow corrosive effect on the boiler material. Carbon dioxide is also
released inside the boiler.
Mg(HCO3)2 → MgCO3 + H2O + CO2
Removal of CO2
 By adding calculated quantity of ammonia.
2NH4OH + CO2→ (NH4)2CO3 + H2O
 By mechanical-aeration process along with oxygen.
(iii) Acids from dissolved salts: Water containing dissolved magnesium salts
liberate acids on hydrolysis.
MgCl2+2H2O→ Mg (OH) 2↓ + 2HCl
acid reacts with iron (of the boiler) in chain-like reactions producing HCl
Fe +2HCl→ FeCl2 +H2↑
FeCl2 +2H2O→ Fe (OH) 2↓ + 2HCl
Consequently, presence of even a small amount of MgCl 2 will cause corrosion
of iron to a large extent.
(ii) By mechanical de-aeration water is sprayed in a perforated plate-
fitted tower, heated from sides and connected to vacuum pump.