WATER & ITS TREATMENT

12/19/16

Chemical
Acids : released by DDT, high explosives, battery
industries.
It is caused by the presence of CO2, mineral
acids(H2SO4),weakly associated acids.
Acidity is not a specific pollutant. It may be defined
as the power of water to neutralize hydroxyl ions

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HARDNESS OF WATER (mineral matter)

Hardness of water is that characteristic which prevents the lathering of
soap. This is due to presence of certain salts of Ca, Mg & other heavy
metals dissolved in water. This water when treated with soap (Na or K
salts of higher fatty acids like, oleic palmitic, or stearic) forms a white
scum or ppt of insoluble soaps of Ca & Mg
Other metal ions like Fe2+, Mn2+, and Al3+ also react with soap in a
similar manner, thus contributing to water hardness
Hard water is water that has high mineral content (in contrast with "soft
water"). Hard water is formed when water percolates through deposits
of limestone and chalk which are largely made up
of calcium and magnesium carbonates.

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HARDNESS OF WATER
Hardness is expressed in terms of equivalent amount of
CaCO3 (mg/L). It is the most insoluble salt
2C17H35COONa + CaCl2 (C17H35COO)2Ca
2NaCl

2C17H35COONa + MgSO4 (C17H35COO)2Mg +

Na2SO4

The hardness of water is of two types:

1. Temporary or carbonate or alkaline hardness
2. Permanent or non-carbonate or non-alkaline hardness
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Temporary/Carbonate/Alkaline Hardness
Temporary hardness is caused by the less soluble carbonates
and bicarbonates of Ca & Mg & other heavy metals & the
carbonate of iron
Temporary hardness can be removed by boiling water when
bicarbonates are decomposed, yielding insoluble carbonates
or hydroxides

Ca(HCO3)2

Mg(HCO3)2

CaCO3 + H2O + CO2

insoluble

Mg(OH)2 + 2CO2
insoluble

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Permanent/Non-carbonate/Non-Alkaline Hardness
Permanent hardness is due to the more soluble
chlorides, sulfates, nitrates of Ca, Mg, Fe, and other
heavy metals
Permanent hardness cannot be removed by boiling of
water
Softening methods are used

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Disadvantages of using hard water

Domestic use:
i.

Washing : no lather formation ,wastage of soap

ii. Bathing: no lather formation. Also the resulting ppt sticks on

body
iii. Cooking: due to dissolved salts boiling point of water is
elevated, causing unnecessarily wastage of time & fuel.
iv: Drinking: bad effect on metabolic system. Calcium oxalate
stones may develop in urinary tracts, if used regularly. Also it
causes deposition of Ca in the bone joints.

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Industrial use:
i: Textiles: loss of soaps during washing of yarn, & fabrics. Ppt
sticks on fabric & dyeing is not uniform. Also Fe, Mn etc salts
leave colored spots on fabrics
ii. Sugar: crystallization of sugar is affected.
iii: Paper: react with chemicals to provide smooth & glossy
finishing to paper. Iron salts add unwarranted color in paper.
iv. Pharmaceuticals: undesirable products may be produced in
medicines
v. Problems from Boiler feed water (scales and sludge
formation, corrosion, caustic embrittlement etc)
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Determination of Hardness:
Step1: EDTA solution is standardized with standard
hard water
Step2: EDTA is used to titrate unknown hard water
sample

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Treatment of hard water

External: using water softening method
Internal: is a corrective treatment for the removal of some impurities
left out in the external treatment
Internal treatment involves addition of certain chemicals to the boiler
water
The added chemicals either precipitate the scale forming impurities as a
sludge (which can be removed by a blow-down operation) OR the
added chemical convert the scale forming impurities into compounds
that stay in the dissolved form in the boiler thereby causing no harm

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External Treatment
External Treatment ( Softening methods): The
process of removing hardness causing salts from
water is called as softening of water. Mainly the
following three methods are used for softening:
Lime soda process
Zeolite or permutit process
Ion exchange or deionization or demineralization
process

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Lime soda process

Principle: In this method hard water is treated with
calculated amounts of slaked lime [Ca(OH)2] Soda
ash [Na2CO3] in reaction tanks, so as to convert
hardness producing chemicals into insoluble
compounds which are then removed by settling &
filtration.
Usually 10% extra chemical is added for better
results.
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Lime soda process

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Lime Soda Process

Lime removes hardness due to temporary Calcium &
all types of magnesium hardness.
Lime react with free acids, Fe, Al salts, CO2 gas &
produce extra calcium hardness.
Soda removes all the soluble permanent hardness due
to calcium salts (i.e. that which is present originally
as well as that which is introduced during removal of
Mg2+ , Fe2+ , Al3+ , HCl, H2SO4, CO2 etc by lime )
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Reactions with Lime

Lime removes free acids

2HCl + Ca(OH)2 CaCl2 + 2H2O

H2SO4 + Ca(OH)2 CaSO4 + 2H2O
Lime removes temporary hardness
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O

Lime removes permanent hardness

MgCl2/MgSO4 + Ca(OH)2 Mg(OH)2 + CaCl2/CaSO4

Lime removes dissolved iron and aluminium salts

Al2(SO4)3 + 3Ca(OH)2 2Al(OH)3 + 3CaSO4
FeSO4 + Ca(OH)2 Fe(OH)2 + CaSO4

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Reactions with Soda

Removes all soluble permanent hardness due to Ca salts
CaCl2 + Na2CO3 CaCO3 + 2NaCl
CaSO4 + Na2CO3 CaCO3 + Na2SO4
The method discussed is called Cold Lime Soda Process

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 Amount of Lime required = 74/100 [temp Ca

hardness + (2 temp. Mg hardness) + perm Mg
hardness + Salts like Fe, Al + CO2 + Acids + HCO3- NaAlO2 ] volume of water 100/ % purity
Amount of Soda = 106/100 [perm Ca hardness +
perm Mg hardness + Salts like Fe, Al + Acids HCO3- ] volume of water 100/ % purity

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The chemical reactions taking place during lime

soda treatment are slow & ppt of CaCO3 &
Mg(OH)2 are fine & produce super-saturated
solution. As a result after deposition occurs in
pipes, boiler tubes etc clogging the valves &
leading to corrosion. To avoid this;

Thorough mixing of chemicals & hard water.

Sufficient time allowed to complete reactions

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 Accelerators i.e. Substances that bring down the fine

particles of precipitates e.g. Activated charcoal
Coagulants i.e. Substances which help in the
formation of coarse precipitates are added e.g. alum
Proper sedimentation chamber for precipitation to
settle, before filtration being carried out
Process is carried out at room temperature & at
temperature between 500C- 1500C

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Cold lime Soda process

When the chemicals are added at room temperature.
At this temperature the precipitates are finely divided
& do not settle easily, nor they can be filtered. It is
necessary therefore to add coagulants like alum,
sodium aluminate etc
NaAlO2 + 2H2O NaOH + Al(OH)3
This process provides water containing a residual
hardness of 50-to 60 ppm.
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Hot Lime Soda Process

When the chemicals are added at higher temperature

80 0C to 150 0C the process is known as Hot process.
At higher temperature reactions are fast
precipitation is more complete
settling rate & filtration rates are increased
So less amount of chemicals are needed.
Hot-Lime soda process produces water of
comparatively lower residual hardness of 15-30 ppm

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Advantages of Soda lime process

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Very economical
pH is increased , there by corrosion is reduced
to a certain extent iron & manganese are also
reduced.
Disadvantages:
Hardness after Cold process is about 50 ppm & 30
ppm by Hot process. These values are high for
pressure boilers.
Careful operation & skilled supervision is required

Zeolite Permutit Process

Hydrated sodium alumino silicate Na2O.Al2O3.x
SiO2.yH2O
Zeolites is capable of exchanging reversibly their
sodium ions for hardness producing ions in water.
Natural Zeolites : are non-porous more durable & are
derived from green sands.
Synthetic Zeolites : porous & possess gel structure &
have higher exchange capacity per unit weight.
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 Theory: When hard water is passed over a bed

of sodium zeolite , Ca2+ , Mg2+ ions are taken
up by the zeolite simultaneously releasing
equivalent Na+ ions in exchange for them.

CaCl2 + Na2Z CaZ

+ 2NaCl

MgSO4 + Na2Z MgZ + Na2SO4

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 Regeneration: When Zeolite is completely

converted into calcium & magnesium Zeolites,
it ceases to soften water i.e. it gets exhausted.
It is generated by treating with 10% brine
solution.
CaZe + 2NaCl

Na2Ze + CaCl2

MgZe + 2NaCl Na2Ze

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+ MgCl2

 Process: Hard water enters from top at a specified rate &

passes over a bed of sodium zeolite kept in a cylinder.
Softened water is collected at the bottom of cylinder & is
taken out from time to time.

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Limitations:
Turbid water should not be admitted, otherwise it
will block the pores of zeolite & make them
inactive.
Any colored Fe ions must be removed earlier
because, it is difficult to regenerate it from iron
zeolite.
Mineral acid present in water must be neutralized
earlier with soda otherwise that may destroy
zeolite bed.

Advantages:
Water of about 10 ppm hardness is produced.
Process automatically adjusts itself for
different hardness of incoming water.
Requires less skill in maintenance as well as
operation.

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Disadvantages:

Treated water contains more sodium salts

The method only replaces Ca2+ & Mg2+ ions by

Na+ ions, but leaves all (HCO3 - & CO3 --) in
soft water. Such soft water containing NaHCO3 ,
Na2CO3 etc when used in boilers , NaHCO3
decomposes to give CO2 which cause boiler
corrosion & Na2CO3 hydrolyses to NaOH
causing Caustic Embrittlement.

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Ion Exchange Process

In this process, a reversible exchange of ions occur
between the stationary ion-exchange phase & the
external liquid phase.
Ion exchange resins are insoluble , cross-linked, long
chain organic polymers which are permeable due to
their micro porous structure & functional group
attached to the chain are involved in the ion
exchanging process.

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Cation exchange resins

These are capable of exchanging rapidly
cations like Ca2+ & Mg2+ by H+ ions. E.g.
sulphonated coals, tannins, formaldehyde
resins, amberlite IR-120 etc
RH2 + Ca2+ / Mg2 + RCa/Mg + 2H+

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Anion exchange resins

These are capable of exchanging rapidly
anions (Cl - , SO4 --) by OH- ions e.g. aminoformaldehyde resins, copolymer of styrene &
di vinyl benzene, amberlite-400, Zeolite-FF
etc
R(OH)2 + H2SO4 RSO4 + 2H2O
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Process
Hard water is first passed through cation exchange
bed which removes all cations like Ca2+ , Mg2+ ,
Na+ & release H+ ions. Thus Cl - , SO4 --, CO3-- are
converted into corresponding acids HCL, H2SO4, &
H2CO3
After this the acidic hard water is passed through an
anion exchange bed which removes all anions present
in water & equivalent amount of OH- ions is released
from it to form water.
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 H+ & OH- ions combine to give ion- free

water molecules called De-ionized or Demineralized water.
The water is finally freed from dissolved gases
by passing it through a de- gasifier the water
obtained by this process is very near to distill
water.
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Regeneration
When ion exchange capacities are lost ( resins are
exhausted) the supply of water is stopped. The
exhausted cation exchanger i.e. regenerated by
passing dilute HCl or H2SO4.
RCa or RMg + 2HCl 2RH + CaCl2 or MgCl2
The exchange bed is washed with de-ionized water &
washings( contained Ca2+ , Mg2+ Cl - , SO4 --,) is
passed to sink or drain.
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 The exhausted anion exchanger is regenerated by

treating it with a dilute NaOH solution.

RCl2 + 2NaOH

R(OH)2 + 2NaCl

The exchanged bed is washed with de ionized water

& washings( containing NaCl, Na2SO4 ) is passed to
sink.
The regenerated ion-exchange resins are used again.

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 Advantages:
(i) The process can be used to soften highly acidic or
alkaline water,
(ii) Water of low hardness(2 ppm) thus very good for
high pressure boilers.
Disadvantages:
(i) The equipment is costly
(ii) Turbidity should be below 10 ppm

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Drinking Water Purification

Municipalities supply potable water that is safe for human

consumption.

Drinking water should pass the following specifications:

1.

It should be sparkling clear and odorless

2.

It should be pleasant to taste

3.

It should be cool

4.

The total dissolved solids (TDS) should be less than 500 ppm

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Drinking Water Purification

Drinking water should pass the following specifications:

5.

It should be free of H2S gas

6.

It should be free of mineral such as Pb, As, Cr, Mn salts

7.

It should have low alkalinity and a pH value of about 8

8.

It should be reasonably soft and free of disease producing microorganisms

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Drinking Water Purification

Drinking water purification consists of:
A. Removal of suspended impurities: which involves
1) Screening, 2) Sedimentation, 3) Filtration
B. Removal of micro-organisms: which involves following methods
used for destroying the disease causing micro-organisms
1) Boiling, 2) Addition of bleaching powder, 3) Chlorination
4) Addition of Chloramine (ClNH2), 5) Ozonization 6) Desalination
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Drinking Water Purification

B. Removal of micro-organisms:
o

Water on removal of suspended impurities, has a small percentage of

pathogenic bacteria which must be removed before the water can be
used for drinking purposes

The process of destroying or removing of the pathogenic microorganisms from the water and making it safe, is called as
disinfection, and the chemicals or substances used for the
disinfection are called as disinfectants

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Drinking Water Purification

B. Removal of micro-organisms:
o

Methods used for disinfection include:

1.

Chlorination

2.

Ozonization

3.

UV treatment

C. Advanced treatments
1.

Reverse osmosis

2.

Ultrafiltration

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Drinking Water Purification

B. Removal of micro-organisms: (chlorination method of disinfection)
o

Chlorine is most widely used disinfectant throughout the world

The apparatus used for chlorination of water is called a chlorinator

The chlorinator consists of a high tower fitted with a number of baffle

plates to ensure thorough mixing of the chlorine with water

Water and proper quantity of concentrated chlorine solution are

introduced at the top of the tower

During the passage through the tower thorough mixing occurs

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Drinking Water Purification

B. Removal of micro-organisms: (chlorination method of disinfection)
o

The treated water is collected via an outlet at the bottom

For filtered water, about 0.3 0.5 ppm of chlorine is sufficient

Mechanism of chlorine action:

Chlorine reacts with water to form hypochlorous acid (HOCl) which

is a powerful germicide
Cl2 + H2O

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HOCl + HCl

Drinking Water Purification

HOCl dissociates as:

HOCl

H+ + OCl

Hypochlorite ion causes inactivation of enzymes

present in microorganismsleading to death

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Drinking Water Purification

B. Removal of micro-organisms: (chlorination method of disinfection)

Dechlorination:

Excess Cl2 added to water gives an unpleasant taste and odor

These objectionable qualities can be removed by passing the water

over a bed of activated carbon. Alternatively, activated carbon is
added to the water and the water is filtered after a short period of
time

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Action of bleaching
powder
Ca(OCl)2 + H2O Ca(OH)2 + Cl2
Cl2 + H2O HCl + HOCl (hypochlorous acid)
Germs + HOCl Germs killed
Only calculated quantity of bleaching powder (calcium
hypochlorite) should be used, since an excess of it
gives bad taste and smell to treated water

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Drinking Water Purification

B. Removal of micro-organisms: (Ozonization method of disinfection)
Ozone is an excellent disinfectant and is produced by passing an electric
discharge through cold and dry oxygen
(electric discharge)

3O2
2O3
(Oxygen)
Ozone if highly
unstable and breaks down(Ozone)
liberating nascent oxygen
(Decomposition)
O3
O2 + [ O ]
Nascent oxygen
is a powerful oxidizing agent and(Nascent
oxidizesoxygen)
any organic
(Ozone)

matter, as well as destroys the bacteria present in water

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Drinking Water Purification

B. Removal of micro-organisms: (Ozonization method of disinfection)
Ozonization process:

Ozone is injected into water, and the two are allowed to come into
contact for 10 15 minutes in a sterilizing tank

The amount of ozone injected is 2 3 ppm

The disinfected water is removed from the top

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Drinking Water Purification

B. Removal of micro-organisms: (Ozonization method of disinfection)
Advantages of ozonization:

Using ozone simultaneously removes color, odor, and taste without

giving any residue

Excess ozone is not harmful since it is unstable and decomposes to

oxygen
(Decomposition)
O3
(Ozone)

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O2

[O]

(Nascent oxygen)

Drinking Water Purification

B. Removal of micro-organisms: (Ozonization method of disinfection)
Disadvantages of ozonization:

The method and the equipment needed to prepare ozone is

expensive. Therefore, the method cannot be used for the large scale
disinfection of the municipal water supply

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Desalination of Water (Reverse Omosis)

Advanced methods

Reverse osmosis is the method used for desalination

Principle of osmosis: when two solutions of unequal concentrations

are separated by a semi permeable membrane (that selectively allows
the diffusion of only the solvent molecules, but not the solute
particles viz. molecules, ions, etc.) the flow of solvent occurs from
the dilute solution side to the concentrated solution side due to
osmosis

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Desalination of Water (Reverse Omosis)

If however, hydrostatic pressure in excess of osmotic pressure is applied on
the concentrated solution side, the solvent flow reverses i.e. the solvent is
now forced to flow from the concentrated solution side to the dilute solution
side across the semi permeable membrane. This process is termed as reverse
osmosis

Thus, in reverse osmosis, instead of removing contaminants from water, the

pure water is separated from impure water and the application of hydrostatic
pressure (in excess of osmotic pressure) makes the water to flow from the
impure side (more concentrated) to the pure side (less concentrated)

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Desalination of Water (Reverse Omosis)

Such type of membrane filtration is often termed as superfiltration or

hyperfiltration

Process: In this process a pressure of the order of 15 20 kg/cm2 is

applied to the impure water (to be treated) to force pure water out
through the semi permeable membrane. This leaves behind the
dissolved solute particles (both ionic as well as molecular)

The semi permeable membrane consists of a very thin film of

cellulose acetate, affixed to either side of a perforated tube

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Desalination of Water (Reverse Omosis)

Process:

More

recently

superior

membranes

made

of

polymethacrylate and polyamide polymers are in use as semi

permeable membranes

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Desalination of Water (Reverse Omosis)

Advantages of Reverse Osmosis:

i.

The process removes both ionic as well as non-ionic, colloidal and high
molecular weight organic polymers

ii.

It removes colloidal silica which is not removed by demineralization

iii. The maintenance cost is low and only involves the replacement of the
semi permeable membrane which takes a few minutes thereby providing
uninterrupted pure water supply. At the same time the membrane cost is
reasonably low and lasts for approx. 2 years
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Purification of Water (Ultrafiltration)

Ultrafiltration like reverse osmosis is a cross flow separation process

It is fundamentally similar to reverse osmosis except for the size of

the molecules it retains

Thus, low molecular weight organics, and ions such as Na+, Ca2+,
Mg2+ and Cl pass through the membrane while high molecular
weight species (macromolecules or supermolecules: 103 106
Daltons) are removed

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Purification of Water (Ultrafiltration)

The stream of liquid that comes out through the membrane is called
permeate and the other side of the liquid stream (which contains the
macromolecules) is called the concentrate as it progressively gets
concentrated with the macromolecules stopped by the membrane

It is suitable for retaining biomolecules, bacteria, viruses, polymers,

colloidal particles and sugar molecules.

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Purification of Water (Ultrafiltration)

The pore sixe of the membrane used

in ultrafiltration is in the range of 0.1
0.001 microns

The type and the amount of species

left over in the permeate depend on
the characteristic of the membrane,
the operating conditions and the
quality of the feed
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Different types of membrane filtrations

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THANKYOU

12/19/16

 mechtechnmims@gmail.com
classrepresentativecs@gmail.com

12/19/16