WATER CHEMISTRY

B.Tech. First Year Chemistry

Dr. Paul Douglas

Syllabus
• Water Chemistry
• Sources of Water – Impurities and their influence of living
systems – WHO Limits – Hardness and its Determination
– Boiler Troubles and their removal – Water Softening
Methods – Lime-Soda, Zeolite and Ion Exchange -
Municipal Water Treatment-Break Point Chlorination –
Desalination of Sea Water – Reverse Osmosis Method,
Electro-dialysis.
 Water is one of the most 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.
 80
70%
70
% of total water used

60
50
40
30 22%
20
8%
10
0
Agriculture Domestic Industry
Water uses
 66% of the human body
is made up of water.

 At just 2% dehydration
your performance
decreases by around  80% of all illness in
20%. developing countries is
caused by water related
 We should drink at least diseases.
1½ litres of water a day.
 90% of wastewater in
developing countries is
discharged directly into
rivers and streams
without treatment.
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 drainage) 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
Impurities 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
Impurities Contd…
• 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
Effects of Impurities in natural water
on Living Systems
 Colour
 Taste and odour
 Turbidity and sediments
 Micro-organisms
 Dissolved minerals matters
• (a) hardness
• (b) Alkalinity
• (c) Total solids
• (d) corrosive Materials
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.

• Other metal ions such as Fe2+, Mn2+, Al3+ also

contributing to hardness, but they are present in
water only in traces
Soap as a Testing Tool
• 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)
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.
Permanent hardness (non-carbonate
hardness)
• This is due the presences of chlorides and sulphates of
calcium, magnesium, iron and other heavy metal ions.

CaSO4 CaCl2
MgSO4 MgCl2
Total Hardness
• Temporary Hardness – Ca(HCO3)2 + Mg(HCO3)2
• Permanent Hardness – CaCl2 + MgCl2 + CaSO4 + MgSO4
• TOTAL HARDNESS = Temporary Hardness + Permanent
Hardness
• Methods of Softening:
• Boiling:
• Ca(HCO3)2 CaCO3+H2O+CO2
• Mg(HCO3)2 Mg(OH)2+2CO2

• Chemical Treatment for Both Temporary and Permanent

Hardness
Units of Hardness
• Milligrams per litre (mg/l): It is defined as the number
of milligrams of CaCO3 equivalent hardness present in
one litre of water.
• 1 mg/L = 1 mg of CaCO3 equivalent hardness present per
litre of water.

• Parts Per million (ppm): It is defined as the number of

parts by weight of CaCO3 equivalent present in per million
(106) parts by weight of water.
• 1 ppm = 1 part of CaCO3 equivalent hardness in (106)
parts of water.
• It can be easily proved that 1mg/L = 1 ppm, for water
• Weight of 1 litre of water = 1kg = 103g = 106mg
• = 1000*1000g= 106 mg
• 1mg/L = 1mg of CaCO3 equivalent hardness per 106 parts
of water.
• 1mg/L = 1 part of CaCO3 equivalent hardness per
106 parts of water.
• 1mg/L = 1ppm
• Degree Clark (ºCl): It is defined as the parts of
CaCO3 equivalent hardness per 70,000 parts of water or it
is number of grains (1/7000lb) of CaCo3 equivalent
hardness per gallon (10lb or 70,000 grains) of water.
1º Clark = 1 part of CaCo3 per 70,000 part of water

• Degree of French (ºFr): It is defined as the parts of

CaCO3 equivalent hardness per Lac (100000) parts of
water.
• 1ºFr = 1 part of CaCO3 equivalent hardness per (105)
parts of water.
• Milli equivalent per litre (meq/L): It is defined as the
number of milli equivalents of hardness present per litre.
• 1 meq/L = 1 meq of CaCO3 per L of water
• = 10-3 * 50g of CaCO3 eq. per litre of water
• = 10-3 * 1000 * 50 mg of CaCO3 eq. per litre of water
• = 50mg of CaCO3 eq. per litre of water
• = 50mg/L of CaCO3 eq. per litre of water = 50 ppm
• = 50mg of CaCO3 eq. per 106 litre of water
• = 1 mg of CaCO3 eq. per 106 /5 mg litre of water
• = 1 part of CaCO3 equivalent per 20,000 parts of water.
Relationship between different units of
hardness:
• 1 ppm = 1 part per 1000000 parts of water
• 1 ºFr = 1 part per 100000 parts of water
• 1 ºCl = 1 part per 70000 parts of water
• 1 mg/L = 1 part per 1000000 parts of water
• 1 meq/L = 1 part per 20000 parts of water
• Hence: 1000000 ppm = 100000 ºFr = 700000Cl = 1000000
mg/L = 20000 meq/L
• = 100 ppm = 10ºFr = 7ºCl = 100mg/L = 2 meq/L
• 1 mg/L = 1 ppm = 0.1ºFr = 0.07ºCl = 0.02 meq/L
• 1ºCl = 14.3 ppm = 1.433 ºFr = 14.3 mg/L = 0.286 meq/L
• 1ºFr = 10 ppm = 10 mg/L = 0.7 ºCl = 0.2 meq/L
• 1 meq/L = 50 mg/L = 50 ppm = 5 ºFr = 0.35 ºCl
Calcium Carbonate Equivalents
• Hardness is expressed in terms of equivalent of calcium
carbonate because it is the most insoluble salt that can be
precipitated in water treatment.

Wt.of Hardness causing Substance  100

Equivalent of CaCO3=
Molecular weight of hardness causing substance

Wt.of Hardness causing Substance  50

Equivalent of CaCO3=
Eqivalent weight of hardness causing substance
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
Problem 1:
• Calculate the temporary hardness and permanent
hardness of a sample of water containing: Mg(HCO3)2
= 7.3 mg/L; Ca(HCO3)2 = 16.2 mg/L; MgCl2 = 9.5 mg/L;
CaSO4 = 13.6 mg/L
• Molecular weights: Ca(HCO3)2=162; Mg(HCO3)2=146;
CaSO4=136; MgSO4=120; MgCl2=95; Al2(SO4)3=114
Problem 2:
• Three samples A, B and C were analyzed for their
salts contents:
• Sample A was found to contain 168 mg of magnesium
carbonate per L
• Sample B was found to contain 820 mg of calcium
nitrate and 2 mg of silica per L
• Sample C was found to contain 2 g calcium carbonate
per 500 ml
• Determine the hardness in all above three sample in
ppm
• Molecular weights:
• Ca(NO3)2 = 164; MgCO3=84; CaCO3= 100
List of basic water quality parameters
 Determination of Hardness
• 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
• After precipitation of all the hardness causing ions present
in water, further addition of soap gives lather
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)
EDTA Method
NaOOCH2C CH2COONa

N
Hard water N CH2 CH2
HOOCH2C CH2COOH
+
M
EBT Indicator

OOCH2C CH2COO
+
N CH2 CH2 N
10 pH buffer solution
NaOOCH2C CH2COONa

Ca/Mg

O O

NaO3S N N

O2N
 Water for Industrial and Engineering
Applications
• Hydroelectric Power – • Paper & Pulp Industry –
• Thermal Power – • Diary Industry –
• Nuclear Power – • Steel / Metal Industry -
• Brewery Industry – • Hospitals –
• Civil Construction – • Food –
• Oil Refineries – • Aquaculture –
• Textile Industry – • Sugar Factories –
• Agriculture – • Cement Factories –
• Pharmaceuticals- • Electronic Industry –
• Washing purpose – • Petroleum Industry –
• Cooling Purpose • Salt -
Boiler
Boiler Troubles
• Scale
• Sludge
• Priming
• Foaming
• Carryover
• Caustic Embrittlement
• Boiler Corrosion
Internal Treatment
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
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
Lime-Soda Process
• LIME-SODA PROCESS- Principle:: Calculated quantity
of lime & soda are added to hard water to convert soluble
impurities into insoluble one which are easily removed by
filtration.
 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

(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

• i) Removal of temporary hardness-
• Ca(HCO3)2 +Ca(OH)2→2CaCO3↓+2H2O [1:1L]
• Mg(HCO3)2 + Ca(OH)2 →
2Mg(OH)2↓+2CaCO3↓+2H2O [1:1L]
• ii)Removal of permanent hardness-
• CaCl2+Na2CO3 →CaCO3↓+2NaCl [1:1S]
• MgCl2+ Ca(OH)2 →Mg(OH)2↓+CaCl2
CaCl2+Na2CO3 →CaCO3↓+2NaCl [1:1L:1S]
• CaSO4+Na2CO3 →CaCO3↓+Na2SO4 [1:1S]
• MgSO4+ Ca(OH)2 →Mg(OH)2↓+CaSO4
CaSO4+Na2CO3 →CaCO3↓+Na2SO4 [1:1L:1S]
• MgCO3+ Ca(OH)2 →Mg(OH)2↓+CaCO3↓ [1:1L]
• iii)Neutralization free acids-
• 2HCl +Ca(OH)2 →CaCl2+2H2O
CaCl2+Na2CO3→CaCO3↓+2NaCl
[2:1L:1S]
• H2SO4+Ca(OH)2→CaSO4+2H2O
CaSO4+Na2CO3→CaCO3↓+Na2SO4
[1:1L:1S]
• 2HNO3+Ca(OH)2→Ca(NO3)2+2H2O
CaNO3+Na2CO3→CaCO3↓+2NaNO3
[2:1L:1S]
• iv) Removal of salts-
• FeSO4+Ca(OH)2→Fe(OH)2+CaSO4
CaSO4+Na2CO3→CaCO3↓+Na2SO4 [1:1L:1S]
• 2Fe(OH)2+1/2O2+H2O→2Fe(OH)3↓
• Al2(SO4)3+3Ca(OH)2→2Al(OH)3+3CaSO4
CaSO4+Na2CO3→CaCO3↓+Na2SO4 [1:3L:3S]
• AlCl3+3Ca(OH)2→2Al(OH)3+3CaCl2 [1:3L:3S]
CaCl2+Na2CO3→CaCO3↓+2NaCl
• v) Removal of gases-
• CO2+Ca(OH)2→CaCO3↓+2H2O [1:1L]
• H2S+Ca(OH)2→CaS↓+2H2O [1:1L]

• vi) Removal of bicarbonate-

• 2NaHCO3+Ca(OH)2→CaCO3↓+2H2O+Na2CO3
[1:1L:-1S]
• 2HCO3+Ca(OH)2→CaCO3↓+2H2O+CO2 [2:1L]
• vii) Reaction with coagulant-
• NaAlO2+2H2O→NaOH+Al(OH)3
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-]
Calculate the amount of lime required for softening 50,000 litre of
hard water containing CaCO3=25ppm; MgCO3=144ppm; CaCl2=111
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-]
Calculate the amount of lime and soda required for softening 50,000 litre
of hard water containing Ca(HCO3)2= 8.1 mg; Mg(HCO3)2 = 7.5 mg;
CaSO4 = 13.6 mg; MgSO4 = 12.0 mg; MgCl2 = 2.0 mg; NaCl = 4.7 mg.
Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95

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+) + H+ (HCl or
=
100 H2SO4) - HCO3-]
Explain with chemical equation and calculate the amount of lime
And soda needed for softening 1,00,000 litrs of water containing
Following:
HCL = 7.3 mg/L; Al2(SO4)3 = 34.2 mg/L; MgCl2 = 9.5 mg/L;
NaCl = 29.25 mg/L
Purity of lime is 90% and that of the soda is 98%.
Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95;
Al2(SO4)3 = 114
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+) + H+ (HCl or
=
-
A water sample on analysis gave the following data:
Ca2+ = 30 mg/L; Mg2+ = 24 mg/L; CO2 = 24mg/L; K+ = 10 mg/L
Calculate the quantities of lime (90%) and soda (94%) required
to soften one million litres of water sample.
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+) + H+ (HCl or
=
100 H2SO4) - HCO3-]
A water sample have the following impurities : Ca2+ = 20ppm;
Mg2+ = 18 ppm; HCO3- = 183 ppm; SO42- = 24 ppm. Calculate
the amount of lime and soda needed for softening.

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

 53

Continuous cold lime soda softener

Chemicals Hard water feed

(soda+lime+coagul
ant) feed
Softened water

Wood fiber filter

Stirrer paddles

Sedimented sludge (CaCO3, Mg(OH)2

Hot lime soda process:
Calculated quantity of lime and soda are mixed with
water at 80 to 150 0C.

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.
 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
58
 Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

59
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
60
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 61
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
 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 reversibly, 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 (-R2N+OH-) are capable of
exchanging their anions (OH- ) with other anions which comes in their
contacts reversibly, known as a Anion exchange resins (ROH-).
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 free water is known as deionized or demineralised water.
 67
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
 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)
Boiler Feed Water
• Water Quality : 0.1 ppm
Boiler Troubles
• The concentration of the substances present in the water
inside the boiler increases.
• Precipitation takes when ionisation product increases the
solubility product
• 1. Scale
• 2. Sludge
• 3. Priming
• 4. Foaming
• 5. Carryover
• 6. Caustic Embrittlement
• 7. Boiler Corrosion
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
 85

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 also

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

Principle: High tempt and low pressure

favors lower solubility of gases in water O2 To vacuum
(Henry’s law)

Steam jacket

Perforated
plate

Deaerated
water
(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 MgCl2 will cause
(ii) By mechanical de-aeration water is sprayed in a perforated plate-
fitted tower, heated from sides and connected to vacuum pump.
Community/ Household Water
Treatment
• Drinking water sources can become contaminated,
causing sickness and disease from waterborne germs,
such as Cryptosporidium, E. coli, Hepatitis A, Giardia
intestinalis, and other pathogens.
• Drinking water sources are subject to contamination and
require appropriate treatment to remove disease-causing
agents. Public drinking water systems use various
methods of water treatment to provide safe drinking
water for their communities. Today, the most common
steps in water treatment used by community water
systems (mainly surface water treatment) include:
• Coagulation and Flocculation Coagulation and
flocculation are often the first steps in water
treatment. Chemicals with a positive charge are
added to the water. The positive charge of these
chemicals neutralizes the negative charge of dirt and
other dissolved particles in the water. When this
occurs, the particles bind with the chemicals and form
larger particles, called floc.
• Sedimentation During sedimentation, floc settles to
the bottom of the water supply, due to its weight. This
settling process is called sedimentation.
• Filtration Once the floc has settled to the bottom of
the water supply, the clear water on top will pass
through filters of varying compositions (sand, gravel,
and charcoal) and pore sizes, in order to remove
dissolved particles, such as dust, parasites, bacteria,
viruses, and chemicals.
• Disinfection After the water has been filtered, a
disinfectant (for example, chlorine, chloramine) may
be added in order to kill any remaining parasites,
bacteria, and viruses, and to protect the water from
germs when it is piped to homes and businesses.
• The most common types of household water treatment systems consist of:
• Filtration Systems
• A water filter is a device which removes impurities from water by means of a
physical barrier, chemical, and/or biological process.
• Water Softeners
• A water softener is a device that reduces the hardness of the water. A water
softener typically uses sodium or potassium ions to replace calcium and
magnesium ions, the ions that create “hardness.”
• Distillation Systems
• Distillation is a process in which impure water is boiled and the steam is
collected and condensed in a separate container, leaving many of the solid
contaminants behind.
• Disinfection
• Disinfection is a physical or chemical process in which pathogenic
microorganisms are deactivated or killed. Examples of chemical disinfectants
are chlorine, chlorine dioxide, and ozone. Examples of physical disinfectants
include ultraviolet light, electronic radiation, and heat.
DISINFECTION
 Disinfection
• Boiling – Destroys Micro-organisms and
pathogenic bacteria
• Chlorination:
• a) Bleaching Powder:
• Ca(OH)2 + Cl2  Ca(OCl)2
• Ca(OCl)2 + H2O  Ca(OH)2 + Cl2
• Cl2 + H2O  HCl + HOCl
• HOCl  HCl + [O]
• HOCl  [-OCl] + H+
• b) Chlorine Gas
• c) Chloramines (NH2Cl)
NH3+Cl2  NH2Cl +HCl
NH2Cl +H2O  NH3 +HOCl
• Disinfection by Ozone gas
O3O2+[O]
• UV Disinfection
Desalination
Desalination – Reverse Osmosis
Desalination - Electrodialysis