Module 1 and 2

Water Technology

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 Hardness of Water
Hardness of water is the characteristic of preventing lather formation of
water with soap. Generally salts like chlorides, bicarbonates and sulfates
of Ca2+, Mg2+ and Fe2+ make water hard.

This hard water on treatment with soap which is stearic or palmitic acid
salts of sodium or potassium causes white precipitate formation of
calcium or magnesium stearate or palmitate.

Thus the cause of hardness is the precipitation of the soap and hence
prevents lathering at first. When the hardness causing ions are removed
as insoluble soaps, water becomes soft and forms lather.
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 Types of Hardness

The hardness is of two types:

(i) Temporary hardness is due to the bicarbonates of Ca2+ and Mg2+ and
carbonate of Fe2+. Temporary hardness can be destroyed by mere
boiling of water, when bicarbonate decomposed, yielding insoluble
carbonates or hydroxides, which are deposited as crust at the bottom of
vessel

(ii) Permanent hardness is due to the presence of chlorides and sulfates of

Ca, Mg, Fe, etc. Permanent hardness cannot be removed easily on
boiling.

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 Units of Hardness
Both temporary and permanent hardnesses are expressed in ppm as
CaCO3. The choice of CaCO3 is due to the fact that its mol. wt. is 100
and equivalent weight is 50 and it is the most insoluble salt in water.
Equivalent of CaCO3

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 Units of Hardness
Hardness is principally expressed in ppm unit. Other limits include
French degree of hardness, English degree of hardness or Clark, USA
degree of hardness and German degree of hardness.

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 Disadvantage of hardwater

• In domestic use
– Washing: Hard water, when used for washing purposes, does
not lather freely with soap. Instead it produces sticky precipitates
of calcium and magnesium soaps. Similar problem exists in
bathing.

– Cooking: Due to the presence of dissolved hardness producing

salts the boiling point of water is elevated. Consequently more
fuel is and time are required for cooking.

– Drinking: Hard water causes bad effect on our digestive system.

The possibility of forming calcium oxalate crystals in urinary
tracks is increased (Kidney stones).

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 Disadvantage of hardwater
• In Industrial use
– Textile industry : Hard water cause much of the soap to go as waste.
Precipitate of calcium and magnesium soaps adhere to the fabrics.
These fabrics, when dyed latter on, do not produce exact shades of
colour.
– 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
deliquescent
– Concrete making : Water containing chlorides and sulphates, if used
for concrete making, affects the hydration of the cement and the final
strength of the hardened concrete.

• In steam generation in boilers

– If the hard water is fed directly to the boilers, which led to the many
problems such as (i) scale and sludge formation
(ii) corrosion (iii) priming and foaming and (iv) caustic embrittlement

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Sludge and Scale

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 Scale and Sludge formation in boilers
• Sludge is a soft, loose and slimy precipitate formed within the boiler.

• Sludge can be easily scrapped off with the wire brush.

• It is formed comparatively colder portions of the boiler and collects in the

bends where the flow rate is slow

• Sludges are formed by substanes which have greater solubilities in hot

water than in cold water, e.g., MgCO3, CaCl2, etc.

Disadvantage of sludge formation

• Sludges are poor conductor of heat, so they tend to waste a portion of heat.

• Excessive sludge formation disturbs the working of the boiler. It settle at the
bends thereby causing blocking

Prevention of sludge formation

By using well softened water and by frequently blow down operation
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 Scales
Decomposition of calcium bicarbonate

• Scales are the main source of boiler troubles. Scale composed

chiefly of calcium carbonate is soft and is the main cause of scale
formation in low-pressure boilers.

Scale

• But in high-pressure boilers, CaCO3 is soluble.

CaCO3+ H2O Ca(OH)2 (Soluble) + CO2

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 Decomposition of calcium sulphate

• The solubility of calcium sulphate in water decreases with increase

of temperature.

• The solubility of CaSO4 is 3,200 ppm at 15°C and it reduces to

55 ppm at 230°C and 27 ppm at 320°C

• CaSO4 gets precipitated as hard scale on the heated portion of the

boiler. This is the main cause of scales in high-pressure boilers.

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 Hydrolysis of magnesium salts

Dissolved magnesium salts undergo hydrolysis forming magnesium

hydroxide precipitate which forms a soft type of scale

MgCl2 + 2H2O Mg(OH)2 + 2HCl

Presence of Silica

presence of silica in small quantities deposits as calcium silicate

(CaSiO3) or magnesium silicate (MgSiO3). These deposits stick very
firmly on the inner side of the boiler surface and are very difficult to
remove

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 Disadvantage of scale formation

• Low thermal conductivity

Thickness of scale in 0.325 0.625 1.25 2.5 12

(mm)
Wastage of fuel 10% 15% 50% 80% 150%

• Lowering boiler safety

• Decrease in efficiency

• Danger of explosion

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 Removal of Scales

• By giving thermal Shock if they are brittle (heating the boiler and
then suddenly cooling with cold water)

• If they are adherent and hard dissolving them with help of

chemicals.
– Calcium carbonate scales can dissolved by using 5-10% HCl.
– Calcium Sulphate scales can be dissolved by adding EDTA (ethylene
diamine tetra acetic acid) with which they form soluble complex.

• Frequent blow down operation

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 Prevention of scale formation
• External Treatment
– Removing hardness-producing constituents of water
(will be discussed later)

• Internal Treatment
– Colloidal Conditioning
– Phosphate conditioning
– Carbonate conditioning
– Calgon conditioning
– Treatment with sodium aluminate

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 Caustic Embrittlement
• Its a kind of boiler corrosion, caused by using highly
alkaline water in the boiler
Na2CO3 + H2O NaOH +CO2

This causes embrittlement of

boiler parts particularly
stressed parts (bends, joints,
rivets, etc.)

Sodium Ferrate
+ __

Iron at Conc. Dil. Iron at

stressed NaOH NaOH plane
parts solution solution surfaces

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 Caustic embrittlement can be avoided

• By using sodium phosphate as softening reagent instead of sodium

carbonate

• By adding tannin or lignin to boilers water, since it blocks the hair-

cracks, thereby preventing infiltration of caustic soda

• By adding sodium sulphate to boiler water – It also blocks the hair-

cracks and preventing infiltration of caustic soda.

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 Boiler Corrosion
• It’s a decay of boiler material by chemical or electro-
chemical attack by its environment

(1) Dissolved oxygen in water at high temperature attack boiler material.

Fe + 2H2O + O2 Fe(OH)2

Fe(OH)2 + O2 2[Fe2O3.2H2O]
(Ferrous hydroxide) (Rust)

Removal of dissolved oxygen

By adding calculated quantity of sodium sulphite or hydrazine or sodium sulphide

Na2SO3 + O2 2Na2SO4
N2H4 + O2 N2+ 2H2O
Na2S + 2O2 Na2SO4
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 Removal of dissolved oxygen by de-aeration

Water spraying in a perforated plate-fitted tower, heated from sides and

connected to Vacuum pump. High temperature, low pressure and large
exposed surface reduces dissolved oxygen in water

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 Dissolved Carbon dioxide
H2CO3 is carbonic acid which has corrosive effect on the boiler material

Removal of CO2

By adding calculated quantity of ammonia

2NH4OH + CO2 (NH4)2CO3 + H2O

Acids from Dissolved Salts

Water containing dissolved magnesium salts liberate acids on hydrolysis

MgCl2 + 2H2O Mg(OH)2 + 2HCl

The liberated acid reacts with iron of the boiler in chain-like reactions
producing HCl again and again. As a result presence of even a small
amount of MgCl2will cause corrosion of iron to a large extent.

Fe + 2HCl FeCl2 + H2

FeCl2 + 2H2O Fe(OH)2 + 2HCl 20

Priming
• When a boiler is steaming rapidly some particles of the liquid water are
carried along- with the steam - priming.

– Presence of large amount of dissolved solids

– Sudden boiling
– Improper boiler design

Foaming

• production of persistent foam or bubbles in boilers, which do not break

easily. due to the presence of oil. Priming and foaming occur together

Priming can be avoided by

Fitting mechanical steam purifier

avoid rapid change in steaming rate

Foaming can be avoided by

adding anti foaming agent like castor oil

Removing oil from boiler water by adding compounds like sodium aluminate
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 Softening methods
• The process of removing the hardness producing substance
from the water is called softening of water
• In Industry three main methods are employed for softening of
water
– Lime soda process
– Zeolite process
– Ion exchange process

Lime-Soda process

Dissolved salts – insoluble ppts

lime [Ca(OH)2]
Soda [Na2CO3].

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Lime Soda Process - Reactions of Lime and Soda

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Cold lime-soda process
• Occurring at room temperature

• precipitate formed are finely

divided hence do not settle
down easily

• It is essential to add small

amount of coagulant (alum,
sodium aluminate)

• Coagulant hydrolyse to form

gelatinous ppt. and entraps the
fine ppt.

• NaAlO2 + H2O NaOH +

Al(OH)3

• It provides water with a residual

hardness of 50 to 60 ppm

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 Hot lime-soda process

• Occurring at 80 to 150 °C close to the boiling point of the solution

• Reaction proceeds faster

• The precipitate and sludge formed settle down rapidly so no

coagulant needed

• Viscosity of the softened water is lower, so filtration of water

becomes much easier

• Produce water contain the residual hardness of 15 to 30 ppm

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 Advantage of Lime-Soda process

• It is very economical
• This process increases the pH value of the treated-water, thereby
corrosion of the distribution pipes is reduced

Disadvantage of Lime-Soda process

• Disposal of large amounts of sludge poses a problem
• can remove hardness only up to 15 ppm,

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Zeolite and permutit process

Natural Zeolite

Natrolite
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Artificial Zeolite

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 Ion-exchange

• Ion-exchange resins - cross-linked, long chain organic

polymers with a microporous structure and the functional

groups attached to the groups are responsible for the

ion-exchanging properties.

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 ¯H+
SO3¯H+
SO3

¯H+ SO3¯H+
SO3

Styrene-divinyl benzene copolymers, which on sulfonation or

carboxylation, become capable to exchange their hydrogen ions with
the cations in the water
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Styrene-divinyl benzene or amine-formaldehyde copolymers - amino or
quaternary ammonium or quaternary phosphonium or tertiary sulfonium
groups. These after treatment with dil. NaOH solution capable to exchange
their OH¯ ions with the anions in the water
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 Regeneration of cation exchange column

Adv:
can be used to soften highly acidic or alkaline water
produces water of very low hardness (2 ppm)

Disadv:
costly and more expensive chemical are needed
If the water contains turbidity then the output of the process is reduced

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Residual hardness - 1 ppm

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Drinking water or Municipal water

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Removal of micro-organisms

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• By boiling water for 10-15 min.
• By adding bleaching powder

Produces hypochlorous acid (powerful germicide)

CaOCl2 + H2O Ca(OH)2 + Cl2

Cl2 + H2O HCl + HOCl
Germs + HOCl Germs are killed

Disadvantage

Introduces Calcium in water, thereby making it more hard

excess of it gives a bad taste and smell to treated water

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• Chlorination
Chlorine either gas or in concentrated solution form
produces hypochlorous acid, which is a powerful
germicide
Cl2 + H 2O HCl + HOCl

Germs + HOCl Germs are killed

– Factors affecting efficiency of chlorine

– The rate of reaction with increases with temperature
– pH values between 5-6.5
– less contact time is enough

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Advantage

(i) Effective and economical

(ii) used at low as well as high temp.
(iii) most ideal

Disadvantage

(i) should not exceed 0.1 – 0.2 ppm

(ii) less effective in higher pH values
(iii) excess chlorine produces unpleasant taste and
odour.

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Break point chlorination or free-residual
chlorination

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• Chloramine (ClNH2)

Cl2 + NH3 ClNH2 + HCl

(Chloroamine)

ClNH2 + H2O HOCl + NH3

(Disinfectant)

• Disinfection by ozone
3O2 2O3

O3 O2 + [O]
Nascent oxygen

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Desalination of Brackish water

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Reverse Osmosis

Advantages

Removes colloidal silica

Long life
Can be replaced within
few minutes

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 Units of Hardness
Both temporary and permanent hardnesses are expressed in ppm as
CaCO3. The choice of CaCO3 is due to the fact that its mol. wt. is 100
and equivalent weight is 50 and it is the most insoluble salt in water.
Equivalent of CaCO3

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 Units of Hardness
Hardness is principally expressed in ppm unit. Other limits include
French degree of hardness, English degree of hardness or Clark, USA
degree of hardness and German degree of hardness.

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Estimation of Hardness

EDTA method

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EDTA Complex with Calcium

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 Estimation of permanent hardness of water
sample using standard EDTA
• Take 100 ml of hard water sample in a 250 ml beaker.
Boil it to expel temporary hardness. Cool and filter
the solution into a 100 ml standard flask. Makeup the
solution using distilled water

• Pipette out 50 ml of this made up solution into a

clean conical flask and titrate the contents of the
conical flask against standardised EDTA solution as
before.

– Let the volume of EDTA consumed be V3 ml.

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Calculations:

50 ml of standard hard water = V1 ml of EDTA

(1 ml of water contains 1mg of CaCO3)
50 x 1.0 mg CaCO3 = V1 ml of EDTA

1 ml of EDTA = 50/ V1 mg of CaCO3 eq.

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(ii) 50 ml of given water sample = V2 ml of EDTA
= V2 x 50/V1 mg of CaCO3 eq.
1000 ml of given water sample = 1000 x V2 x 50/V1 x 1/50
= 1000 x V2/V1 mg/L

Total hardness = 1000 x V2/V1 ppm

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(iii) 50 ml of boiled water sample = V3 ml of EDTA
=V3 x 50/V1 mg of CaCO3 eq.
1000 ml of water sample = 1000 x V3 x 50/ V1 x 1/50

Permanent hardness = 1000 x V3/V1 ppm

(iv) Temporary Hardness = 1000 {(V2-V3 )/V1} ppm

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