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
1
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

2
 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
3
 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.
4
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
5
6
7
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

8
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

9
 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

10
 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 CaCO is considered a
3
moderate amount
11
 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

12
(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 H2O

(vi) Soda removes all calcium permanent hardness:

CaCl2 + Na2CO3 CaCO3 + NaCl

CaSO4 + Na2CO3 CaCO3 + Na2SO4

13
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-]

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 Calculate the amount of lime required for softening 50,000 litre of
hard water containing CaCO3=25ppm; MgCO3=144ppm; CaCl2=11
MgCl2=95 ppm; Na2SO4= 15 ppm; Fe2O3 = 25 ppm.
Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95
MgCO3 = 84; CaCl2 = 111
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
16
17
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

18
19
 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

20 20
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- H 2O
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 29
 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 sodium ions
32
 Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

33
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 Ca 2+, 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 + 2NaHCO 3
Hardness

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO 3

To remove permanent hardness water

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na 2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl Na 2Ze + CaCl2 (MgSO4)

Used 10% brine Regenerated Washings

Zeolite solution Zeolite drained
34
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 35
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