1

Unit – III Ch.- 4 Water Treatment

Water is very important for living beings after air for their survival. It is abundantly available on
earth and almost 3/4th part of earth is occupied by water. Water may be in different forms viz.
Solid, ice, fresh, Salty liquid.

Sources of Water:-

There are four main sources of water: (i) Surface water (ii) Underground water (iii) Atmospheric water,
and (iv) Oceanic water. In our daily life we use only surface water and underground water.

(A) Surface water -Water found on the surface is called surface water.The large part of surface
water is found in rivers, riverlets, ponds and lakes. Remaining water flows into the seas,
oceans.. About two – third of the total surface water flows into three major rivers of the
country – Indus, Ganges and Brahmaputras. The water storage capacity of reservoirs
constructed in India so far is about 17400 billion cubic metres. At the time of independence,
the water storage capacity was only 180 billion cubic metres. Hence water storage capacity
has increased about ten times.

(B) Underground water- Rain water percolates into the earth’s surface and becomes
underground water. The process of percolation also take place from the surface water. Large
amount of water gets collected under the Earth’s surface by these two methods. This is
called underground water. According to Central Underground Water Board renewable
underground water capacity in India (1994-95) was about 4310 billion cubic metre per year.
Out of this about 3960 billion cubic metre water is available for use.
Specification of Water:-Specification of water means the properties of water to be specified prior to its
use for a particular purpose:

S.No. Purpose Specification Remark

1. Drinking & Free from pathogenic bacteria & floating Free from infections,
cooking impurities, optimum TDS (120ppm) Free from heavy metal ions.
2. Cooling system Must not promote the growth of algae, Chock the cooling system,
least amount of dissolved gases Corrosion of cooling system.
3. Textile industry Free from hardness, Precipitates the basic dye,
free from Fe and Mn salts. Uneven dye
4. Paper Mills Free from SiO2 SiO2 produces cracks in
paper
5. Boilers Free from hardness, Free from alkalies. Scale & Sludge formation,
Caustic embrittlement etc
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Analysis of Water:- It includes the determination of different constituents in water to ascertain

the quality of water for specific use, and the treatment to which it should be subjected prior to
its use. In water analysis following properties is determined:-

1. Hardness
2. Alkalinity
3. Residual chlorine
4. Dissolved oxygen(BOD,COD)
5. Dissolved CO2
6. Silica
7. Total dissolved solids(TDS)
Out of these we discuss some important properties like Hardness
Alkalinity and Residual chlorine.
1. Hardness or soap consuming capacity:- the water which does not form lather with soap
and is hard to wash is called hard water and this property of water is known as
hardness. Hardness is also known as soap consuming capacity of water.
On the other hand, the water which form quality lather will be termed as soft water.
Cause of hardness: the presence of calcium and magnesium salts which furnish Ca+2 and
Mg+2 ions .These ions precipitate soap as:

2C17H35COONa + CaSO4 ----------------→ (C17H35COO)2Ca + Na2SO4

2C17H35COONa + MgCl2 ----------------→ (C17H35COO)2Mg ↓ + NaCl

Types of hardness:- It is of two types:

(a) Temporary hardness
(b) Permanent hardness

(a) Temporary hardness: It is due to the presence of bicarbonate salts of calcium and
magnesium {Ca(HCO3)2 & Mg(HCO3)2} and known as temporary or carbonate
hardness. It is also known as alkaline hardness because with hardness it also impart
alkalinity to water. The temporary hardness can be removed by boiling only or adding
calculated amount of lime.
Ca(HCO3)2 OR Mg(HCO3)2 ---BOIL-----→ CaCO3↓ / Mg(OH)2 ↓ + H2O + CO2
Ca(HCO3)2 + Ca(OH)2 -------------→ 2CaCO3↓ + 2H2O
Mg(HCO3)2 + Ca(OH)2 -------------→ MgCO3 + CaCO3↓ + H2O
MgCO3 + Ca(OH)2 -------------→ Mg(OH)2 ↓+ CaCO3↓ + H2O
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(b) Permanent hardness: It is due to presence of chlorides , sulphates & nitrates salts of
calcium and magnesium(CaCl2, CaSO4 , MgCl2, MgSO4 etc.). It is also known as non-
carbonate hardness and cannot be removed by simple boiling only but requires some
special processes (discussed later)
Hardness in terms of CaCO3 equivalent: The hardness of all different salts is expressed in
terms of calcium carbonate (CaCO3) equivalents because:
(i) Molecular weight of CaCO3 is exactly 100 and eq. wt. is 50 which makes
calculations easier.
(ii) It is most insoluble salt in water which is precipitated in most of water treatment
processes.
(iii) It is never present as hardness producing substance(most insoluble salt).

𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑯𝒂𝒓𝒅𝒏𝒆𝒔𝒔 𝑝𝑟𝑜𝑑𝑢𝑐𝑖𝑛𝑔 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 (𝐻.𝑃.𝑆.)

Equivalents of CaCO3 = x eqvt. wt. of CaCO3
𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑯𝒂𝒓𝒅𝒏𝒆𝒔𝒔 𝑝𝑟𝑜𝑑𝑢𝑐𝑖𝑛𝑔 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒
𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝐶𝑂3
Equivalents of CaCO3 = x weight of H.P.S.
𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑯.𝑷.𝑺.
𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝐶𝑂3
Multiplication Factor (M.F.) = 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑯.𝑷.𝑺.
Equivalents of CaCO3 = Multiplication Factor (M.F.) x Weight of H.P.S.

Multiplication Factor’s (M.F.s) of some important compounds:

S.No. Salt Molar Wt. n-Factor Eq. Wt. Multiplication Factor
(M.F.)
1. Ca(HCO3)2 162 2 81 50/81
2. Mg(HCO3)2 146 2 73 50/73
3. CaCO3 100 2 50 50/50
4. CaSO4 136 2 68 50/68
5. CaCl2 111 2 55.5 50/55.5
6. MgCO3 84 2 42 50/42
7. MgSO4 120 2 60 50/60
8. MgCl2 95 2 47.5 50/47.5
9. Mg(NO3)2 148 2 74 50/74
10. Al2(SO4)3 342 6 57 50/57
11. FeSO4.7H2O 278 2 139 50/139
12. NaAlO2 82 1 82 50/82
13. HCO-3 61 1 61 50/61
14. CO3 2- 60 2 30 50/30
15. - OH 17 1 17 50/17
16. H+ 1 1 1 50/1
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Example: Calculate the temporary, permanent and total hardness of a water sample
containing
Mg(HCO3)2= 73mg/L, Ca(HCO3)2= 162mg/L, = 95mg/L, CaSO4=136mg/L.
Solution: calculation of CaCO3 equivalents:
S.No. Constituent Amount Multiplication factor(M.F.) CaCO3 equivalents
1. Mg(HCO3)2 73 mg/L 50/73 50 mg/L
2. Ca(HCO3)2 162 mg/L 50/81 100 mg/L
3. MgCl2 95 mg/L 50/47.5 100 mg/L
4. CaSO4 136 mg/L 50/68 100 mg/L

Temporary hardness of water due to Mg(HCO3)2 and Ca(HCO3)2 =

= 100 + 50 = 150 mg/L or ppm.
Permanent hardness of water due to MgCl2 and CaSO4 =
= 100 + 100 = 200 mg/L or ppm.
Total hardness of water= 50+100+100+100=350 mg/L or ppm

Units of hardness:
1. Parts per million (ppm): It is the number of parts of HPS(hardness producing
substance) per 106 parts of water.
2. Milligrams per litre(mg/l): it is the number of milligrams of HPS of per litre of water.
1 mg/l = 1 ppm
3. Clarke’s Degree (°Cl):- It is equal to number of parts of HPS per 70,000 parts of water.
4. Degree French (°Fr):- It is the number of parts of HPS(hardness producing
substance) per 105 parts of water.

Relation between various units of hardness:-

1ppm = 1mg/L = 0.1 °Fr = 0.07 °Cl

Determination of Hardness of water by EDTA Method:-

Principle:- It is based on complexometric titrations in which EDTA (Ethylene Diamine
Tetra Acetic Acid) forms 1:1 complex with metal ions (Ca2+ and Mg2+ ions). If amount of
EDTA used is known than amount of metal ions can be determined because complex is
1:1.
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Theory:- Hardness is determined by titrating hard water against EDTA using EBT (Eriochrome
Black T) as the indicator. EDTA is a hexadentate ligand and can form 4 or 6 dative bonds with
metal ions (Ca2+ and Mg2+ ions) thus a clourless EDTA-Metal ion complex is formed. The EDTA-
Metal ion complex is generally highly stable and soluble in water. The stability of EDTA-Metal
ion complex is further increases by increasing pH ( 9-10). The indicator EBT (Eriochrome Black T)
also has tendency to form complex with metal ions (Ca2+ and Mg2+ ions).The EBT-Metal ion
complex is wine red coloured and comparatively less stable than EDTA-Metal ion complex.
Reactions:-

(i) Mg2+/Ca2+ + EBT -----→ [Mg2+/Ca2+- EBT]

Blue EBT-Metal ion complex (wine red)
(ii) Mg2+/Ca2+ + EDTA -----→ [Mg2+/Ca2+ - EDTA]
EDTA-Metal ion complex (Colourless)
(iii) [Mg2+/Ca2+- EBT] + EDTA -----→ [Mg2+/Ca2+ - EDTA] + EBT
Colourless Blue

Procedure: It consists of three steps:

i Standardization of EDTA solution:- EDTA Vs Standard hard water(SHW)
EDTA is a secondary standard solution so exact strength of EDTA (in burette)is
determined by titrating it against Standard Hard Water [SHW] solution(in titration
flask) using EBT as indicator in presence of 10-12 ml buffer solution (pH = 9-10). The
end point is wine red to blue, volume of EDTA used is noted.
ii Determination of total hardness: Std. EDTA Vs Given sample of hard water
It is determined by titrated standard EDTA (in burette) against given sample of hard
water(in titration flask) using EBT as indicator in presence of 10-12 ml buffer solution
(pH = 9-10). The end point is wine red to blue, volume of EDTA used is noted.
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iii Determination of permanent hardness :- 250 ml of the given hard water sample is
taken in a 500 ml beaker and boiled till the volume reduces to about 50 ml. , so that
the temporary hardness is removed in the form of precipitates. The precipitates are
filtered off and the volume of the filtrate is again made 250 ml. by adding
distilled water. This hard water is titrated against the standard EDTA solution.
Std. EDTA Vs Given sample of hard water after boiling
It is determined by titrated standard EDTA (in burette) against given sample of hard
Water after boiling (in titration flask) using EBT as indicator in presence of 10-12 ml
buffer solution (pH = 9-10). The end point is wine red to blue, volume of EDTA used is
noted.

Observations:
Let volume of water taken for each titration = 50 ml
Volume of EDTA solution used when titrated against Standard Hard Water (SHW) = V1 ml
Volume of EDTA solution used when titrated against given sample of hard water = V2 ml
Volume of EDTA solution used when titrated against water having permanent hardness = V3 ml
Calculations:
i Standardization of EDTA solution:-
Let 1 ml of standard hard water(SHW) contains = 1 mg of CaCO3
50 ml of SHW contains = 50 mg of CaCO3
Volume of EDTA consumed for 50 ml of SHW = V1ml
V1 ml of EDTA is used for = 50 mg of CaCO3
1 ml of EDTA is used for = 50/V1 mg of CaCO3
Or strength of EDTA solution = 50/V1 mg/ml of EDTA
ii Determination of total hardness:
Volume of EDTA used for 50 ml of given sample of hard water = V2 ml
50 ml of given sample of hard water = V2 ml
( 1 ml of EDTA = 50/V1 mg of CaCO3)
Hence, 50 ml of given sample of hard water = 50/V1 ×V2 mg of CaCO3
1000 ml of given sample of hard water = 50×V2/V1 ×1000/50
Total hardness = V2×1000/V1 mg or ppm
iii Determination of permanent hardness :-
Volume of EDTA used for 50 ml of given sample of hard water after boiling = V3 ml
50 ml of given sample of hard water after boiling = V3 ml
( 1 ml of EDTA = 50/V1 mg of CaCO3)
Hence, 50 ml of given sample of hard water after boiling = 50/V1 ×V3 mg of CaCO3
1000 ml of given sample of hard water after boiling = 50×V3/V1 ×1000/50
Permanent hardness = V3×1000/V1 mg or ppm
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iv Determination of temporary hardness :-

Temporary hardness = Total hardness - Permanent hardness
Example: 0.5g of CaCO3 was dissolved in HCl and the solution made up to 500ml with
distilled water. 50ml of the solution required 48ml of EDTA solution for titration. 50ml of
hard water sample required 15ml of EDTA and after boiling and filtering required 10ml of
EDTA solution. Calculate
the hardness.
Solution:
i. Standardization of EDTA:
500ml of SHW = 0.5g or 500mg CaCO3 eq
∴1ml SHW contains = 1 mg CaCO3
Now 48ml of EDTA solution = 50 ml of SHW (complex is 1:1)
48ml of EDTA solution = 50 mg CaCO3
∴1ml of EDTA solution= 50/48 mg CaCO3 eq
ii. Calculation of the total hardness of water:
50 ml of given sample of hard water = 15ml EDTA = 15 x 50/48 mg of CaCO3 eq.
1 ml of given sample hard water = 15/48 = 0.3125 mg of CaCO3 eq.
∴1000ml of hard water= 0.3125 x 1000 = 312.5 mg CaCO3 eq
Hence total hardness= 312.50 mg/L or 312.50 ppm.
iii. Calculation of the permanent hardness of water:
50 ml of given sample of hard water after boiling = 10 ml EDTA
50 ml of given sample of hard water after boiling= 10 x 50/48 mg of CaCO3 eq.
1 ml of given sample of hard water after boiling = 10/48 = 0.208 mg of CaCO3 eq.
∴1000ml of given sample of hard water after boiling = 0.208 x 1000 = 208.33 mg CaCO3 eq
Hence permanent hardness= 208.33 mg/L or 208.33 ppm.
iv. Calculation of the Temporary hardness of water:
Temporary hardness = Total hardness - Permanent hardness
Temporary hardness = 312.50 – 208.33 = 104.17 ppm

Water softening techniques: There are three most common techniques:

1. Lime soda process.

2. Base exchange or zeolite process.
3. Demineralization or ion exchange process.

1. Lime soda process:- In this process calculated amount of lime(Ca(OH)2) and

soda(Na2CO3) are added which convert all soluble hardness causing substances in to
insoluble (ppts) CaCO3 and Mg(OH)2. The chemical reactions involved are:
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A. Reactions with Lime:-

(i) Removal of temporary hardness of Ca2+ and Mg2+:
Ca(HCO3)2 + Ca(OH)2 ----→ 2CaCO3↓ + 2H2O
Mg(HCO3)2 + Ca(OH)2 ----→ 2CaCO3 ↓ + MgCO3 + 2H2O
MgCO3 + Ca(OH)2 ----→ Mg(OH)2↓ + CaCO3
Conclusion:- Ca(OH)2 removes temporary hardness due to Ca(HCO3)2 & Mg(HCO3)2
completely. One equivalent of Ca(HCO3)2 requires one equivalent of Ca(OH)2 while
one equivalent of Mg(HCO3)2 requires two equivalents of Ca(OH)2.
(ii) Removal of permanent Mg2+ hardness:
MgCl2 + Ca(OH)2 ----→ Mg(OH)2↓ + CaCl2
MgSO4 + Ca(OH)2 ----→ Mg(OH)2↓ + CaSO4
Conclusion:- One equivalent of permanent Mg2+ hardness requires one equivalent of
Ca(OH)2 and generates one equivalent of permanent Ca2+ hardness.
(iii) Removal of dissolved iron (Fe2+) and aluminium (Al3+)salts:
FeSO4 + Ca(OH)2 ----→ Fe(OH)2 + CaSO4
2Fe(OH)2 + H2O + 1/2O2 ----→ 2Fe(OH)3↓
Al2(SO4)3 + Ca(OH)2 ----→ Al(OH)3↓ + CaSO4
Conclusion:- One equivalent of permanent Fe2+ and Al3+ hardness requires one
equivalent of Ca(OH)2 and generates one equivalent of permanent Ca2+ hardness.
(iv) Removal of CO2 and H2S:
CO2 + Ca(OH)2 ----→ CaCO3↓ + H2O
H2S + Ca(OH)2----→ CaS↓ + 2H2O
Conclusion:- One equivalent of CO2 and H2S hardness requires one
equivalent of Ca(OH)2 and removed completely.
(v) Removal of free mineral acids:
2HCl + Ca(OH)2 ----→ CaCl2 + 2H2O
H2SO4 + Ca(OH)2 ----→ CaSO4 + 2H2O
Conclusion:- One equivalent of mineral acids hardness requires one equivalent of
Ca(OH)2 and generates one equivalent of permanent Ca2+ hardness.
(vi) Reaction with NaHCO3:
2NaHCO3 + Ca(OH)2 ----→ Na2CO3 + CaCO3↓ + 2H2O
Conclusion:- One equivalent of NaHCO3 requires one equivalent of Ca(OH)2 and
generates one equivalent of Na2CO3 .
(vii) Presence of NaAlO2:
NaAlO2 + 2H2O ----→ NaOH + Al(OH)3↓
Conclusion:- One equivalent of NaOH can be considered as one equivalent of lime
[Ca(OH)2].
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B. Reaction with soda:-

(i) CaCl2 + Na2CO32 ----→ 2NaCl + CaCO3↓
(ii) CaSO4 + Na2CO3 2 ----→ Na2SO4 + CaCO3↓
Note: The chemical reactions taking place during lime soda process are very slow, so the
ppts get deposited in pipes and boiler tubes later. The problem is solved by adding
coagulants like Al2(SO4)3 or NaAlO2 to the treated water.
Calculations:-
(i) Amount of lime required:
Amount of lime = 37/50 [T.Ca+2 + 2 * T.Mg+2 + P.Mg+2 + salts of Fe+2 & Al+3 + CO2 & H2S
+ HCl & H2SO4 + HCO3- - NaAlO2 all in terms of CaCO3 equivalent]
(ii) Amount of Soda required:
Amount of Soda = 53/50 [ P.Mg+2 + salts of Fe+2 & Al+3 + HCl & H2SO4 + P.Ca+2 - HCO3- all in
terms of CaCO3 equivalent]
Example: Calculate the amount of lime (92% pure) & soda (98% pure) required for treatment of
50000 litres of water sample containing:
Mg(HCO3)2= 146 mg/L, Ca(HCO3)2= 40.5 mg/L, MgSO4= 30.0 mg/L, CaSO4= 34.0 mg/L,
CaCl2 = 27.75 mg/L and NaCl = 10.0 mg/L.
Solution: calculation of CaCO3 equivalents:
S.No. Constituent Lime or Amount Multiplication factor(M.F.) CaCO3
Soda req. equivalents
1. Mg(HCO3)2 L 146 mg/L 50/73 100 mg/L
2. Ca(HCO3)2 L 40.5 mg/L 50/81 25 mg/L
3. MgSO4 L+S 60.0 mg/L 50/60 50 mg/L
4. CaSO4 S 34.0 mg/L 50/68 25 mg/L
5. CaCl2 S 111 mg/L 50/55.5 100 mg/L
6. NaCl --- --- --- ---
Amount of lime required:
Amount of lime = 37/50 [T.Ca+2 + 2 * T.Mg+2 + P.Mg+2 + salts of Fe+2 & Al+3 + CO2 & H2S
+ HCl & H2SO4 + HCO3- - NaAlO2 all in terms of CaCO3 equivalent]
Amount of lime = 37/50 [ 25 + 2*100 + 50]
= 37/50 *275 * 50000 * 100/92 mg
= 11059782.6 mg = 11.06 Kg
Amount of Soda required:
Amount of Soda = 53/50 [ P.Mg+2 + salts of Fe+2 & Al+3 + HCl & H2SO4 + P.Ca+2 - HCO3- all in
terms of CaCO3 equivalent]
Amount of Soda = 53/50[ 50 + 25 + 100]
= 53/50*175 * 50000 * 100/98 mg
= 9464285.71 = 9.46 Kg
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Types of Lime-Soda Process :- It is carried out by two different mechanisms:

(a) Cold lime-soda process.
(b) Hot lime soda process.
(a) Cold lime-soda process: This type of lime-soda process is carried out at room
temperature.
The cold lime-soda process is of two types:
(i) Batch process: We have arrangement as shown figure. The process is
discontinuous i.e. carried out in batches.

(ii) Continuous process: In this type of cold lime-soda process we have an

arrangement which makes the process is continuous. The softening unit
consists of three parts-a reaction tank where raw water and chemical are
mixed with the help of a stirrer, a settling tank where the ppts in the form
of sludge settle down and a wood filter to remove any suspended particles
or ppt.
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(b) Hot lime soda process: The hot lime soda process is also of two types
i. Batch process: this is exactly similar to cold process. The only difference is
that in hot lime soda process, heating coils are fitted.
ii. Continuous process: this type of softening unit consists of three parts-a
reaction tank where raw water, chemicals and steam are mixed, a settling
tank where the ppts in the form of sludge settle down and a sand filter
made up of fine sand and course sand to remove any suspended particles
or ppt.

Advantages of hot lime soda process:

1. The reaction time is greatly reduced.
2. Residual hardness is much less.
3. No coagulants are required.
4. Most of dissolved gases like CO2 and O2 are removed.
5. Less chemicals are required.
6. Filtration becomes much easier as viscosity of water becomes low.
Advantages of lime soda process:
1. Highly economical.
2. Ph of water is increased which reduces the distribution pipes.
3. Reduces total mineral content.
4. Also kill the pathogenic bacteria.
Disadvantages of lime soda process:
1. Large quantities of sludge is formed, the disposal of which poses a problem.
2. Careful operation and skilled supervision is required.
3. The water of zero hardness can’t be produced (residual up to 60 ppm)
 12

2. Base Exchange or zeolite process or permit process: A reversible exchange of ions

(cations only) between a liquid phase(hard water) and a solid phase(Zeolite) is termed
as ion exchange. Zeolites are a certain class of naturally occurring alumino silicates
which are solids having pores & capable of exchanging cations . The chemical structure
of a sodium zeolite may be represented as:
Na2Al2O3.xSiO2.yH2O where x= 2-10, y= 2-6
Or Na2Z [ Z = Al2O3.xSiO2.yH2O]
Principle of water softening: when hard water is passed through a zeolite bed of active
granular Na2Z, the Ca2+ and Mg2+ ions of hard water are exchanged for Na+ ions of zeolite.

The various reactions taking place are:

Ca(HCO3)2 + Na2Z ----→ CaZ + 2NaHCO3
Mg(HCO3)2 + Na2Z ----→ MgZ + 2NaHCO3
CaSO4 + Na2Z ----→ CaZ + Na2SO4
MgSO4 + Na2Z ----→ MgZ + Na2SO4
CaCl2 + Na2Z ----→ CaZ + 2NaCl
MgCl2 + Na2Z ----→ MgZ + 2NaCl
Regeneration: when zeolites get exhausted i.e. all its Na+ are exchanged for Ca2+ and Mg2+
ions is generated by first backwashing it and then by brine solution (28% NaCl) through it.
Reactions taking place during regeneration are:
CaZ + 2NaCl ----→ Na2Z + CaCl2
MgZ + 2NaCl ----→ Na2Z + MgCl2
Advantages of zeolite process:
1. Water of very low hardness (about 10 ppm) is produced or even water of zero
hardness can be produced.
 13

2. Occupies less space.

3. No sludge is produced.
4. Requires less skills or expertise.
Disadvantages of zeolite process:
1. It is not suitable for turbid water (pores of zeolite are blocked)
2. Water containing Fe, Mn convert zeolite to iron zeolite which can’t be regenerated
easily.
3. The treated water contains anions (alkaline).

3. Ion exchange or deionization process (demineralization of water):

In zeolite process during softening of water, only the cations (Ca2+ and Mg2+ ions) are
removed but the anions viz SO42- and HCO3- remain in softened water. However, with
the development of organic synthetic cation & anion exchange resins even the removal
of anions made possible. The process of removal of all ions present in water is called
demineralization and achieved by ion exchange resins.
Ion exchange resins: These are consist of cross linked, long chain organic polymers with
microporous structure.
The resin usually made up of styrene-divinylbenzene copolymer etc.
The functional groups attached to polymeric chains are responsible for ion exchange.
a. Cation exchange resins: These resins contains acidic functional groups like –COOH
& -SO3H. These exchange H+ ions with hardness producing cations(Ca2+ and Mg2+
ions

b. Anion exchange resins: These resins contains basic functional groups like amine,
substituted amine or quaternary ammonium groups as their hydroxides. These
exchange OH- ions with anions(SO42-,Cl- and HCO3- ).
 14

Reactions taking place with cation exchange resins:

2RH+ + CaSO4 ----→ R2Ca2+ + H2SO4
2RH+ + MgSO4 ----→ R2Mg2+ + H2SO4
2RH+ + CaCl2 ----→ R2Ca2+ + 2HCl
2RH+ + MgCl2 ----→ R2Mg2+ + 2HCl
Reactions taking place with anion exchange resins:
ROH + Cl- ----→ RCl + OH
2ROH + SO42- ----→ R2SO42-+ 2OH-
2ROH + CO32-----→ R2CO32- + 2OH-
Process: There are two types of deionizer
a. Separate deionizer.
b. Mixed bed deionizer.

a. Separate deionizer: It consists of separate cation and anion exchangers.

Regeneration: by adding HCl or H2SO4 to cation exchanger and NaOH to anion

exchanger.
R2Ca2+ + H2SO4 ----→ 2RH+ + Ca2SO4
R2Mg2+ + HCl ----→ 2RH+ + MgCl2
b. Mixed bed deionizer: It consists of a single column containing a mixture of cation
and anion exchanger. It is more efficient then separate deionizer and produce water
of 1ppm hardness.
 15

Regeneration: it is regenerated by separating the cation and anion exchangers resins

and adding H2SO4 and NaOH solution respectively.
Advantages:
1. Highly acidic or alkaline water can be softened.
2. Water of very low hardness is produced.(about 2 ppm)
3. Anions as well as cations are removed thereby problems like caustic
embrittlement and corrosion are reduced.
Disadvantages:
1. The equipment is costly.
2. Turbid water decrease efficiency of the process.

1. Alkalinity: It is the measure of ability of water to neutralize the acid. It is normally due
to presence of hydroxide, bicarbonate and carbonate salts of Sodium , Potassium ,
Calcium and Magnesium.
Types of alkalinity:
a. It is of five types (on the basis of type of ions).The alkalinity in water may be due to
presence of the individual ion or ions in possible combinations as:
i. Hydroxide only (-OH)
ii. Carbonate only(CO32-)
iii. Bicarbonate only (HCO3-)
iv. Hydroxide and carbonates (-OH + CO32-) Caustic alkalinity
v. Carbonate and Bicarbonate(CO32- + HCO3-) Bicarbonate alkalinity.
Note: The possibility of –OH & HCO3- together in one solution and also all the three ions in
one solution is ruled out because of the reaction given below.
-OH + HCO - ⇔ CO 2- + H O
3 3 2
Hence all the three ion can’t present together.
b. It is of two types (on the basis of indicators used):
i. Phenolphthalein alkalinity (P).
ii. Methyl orange alkalinity or Total alkalinity (M).
Determination of Alkalinity:
Principle: It is based on acid-base titrations in which alkaline water sample is titrated
against a standard acid making selective use of indicators. The indicators used are –
phenolphthalein and methyl orange.
a) -OH + H+ ----→ H2O
b) CO32- + H+ ----→ HCO3-
c) HCO3- + H+ ----→ H2CO3
 16

• The volume of acid used up to phenolphthalein end point corresponds to the reaction
(a) and(b) i.e. complete neutralization of -OH ions and half neutralization of CO32- ions
to HCO3- and corresponds to phenolphthalein alkalinity (P).
• The volume of acid used methyl orange end point corresponds to the reaction (a), (b)
and (c) i.e. complete neutralization of all ions and corresponds to methyl orange or Total
alkalinity (M.
Thus from the volume of acid used respective strength of various ions can be
determined.
Procedure: A known volume of the alkaline water sample is titrated against a standard
acid, using phenolphthalein as indicator. The end point is disappearance of pink colour.
To the same solution then add methyl orange indicator and again titrate against
standard acid solution. The end point is from yellow to pink.
Observations:
Let volume of water sample taken for titration = 100 ml
Volume of acid used to phenolphthalein end point = V1 ml
Extra volume of the acid used up to methyl orange end point = V 2 ml
Total volume of the acid up to methyl orange end point = (V1 + V2) ml
Normality of acid used for titration = N/50
Calculations:
i. Phenolphthalein alkalinity in terms of CaCO3 equivalents:
N1V1 (acid) = N2V (water)
1/50 * V1 = N2 * 100
N2 = V1/5000
Phenolphthalein alkalinity (P) = N2 * eq. wt. of CaCO3
ii. Methyl orange alkalinity or Total alkalinity (M) in terms of CaCO3 equivalents:
N1 (V1+V2) = N2’V)
1/50(V1 + V2) = N2’ * 100 [N1=1/50]
N2’ = 1/50 * (V1 + V2)/100
Methyl orange alkalinity or Total alkalinity (M) = N2’ * eq. wt. of CaCO3
Boiler feed water & related problems: Water is required in industries for steam
generation and it should be very high quality (purity). So a large number of treatments are
done but elimination of all the impurities is generally not required but only those
impurities are eliminated or kept within the prescribed range which leads to certain
problems in boilers. Untreated water, containing impurities may lead to the following
problems in boilers:
1. Scale and sludge formation
2. Boiler corrosion
3. Caustic embrittlement
 17

4. Priming and foaming

1. Scale and sludge formation: When water containing impurities is used for generating
steam, the concentration of dissolved salts go on increasing progressively because of
evaporation of water. When the concentration dissolved salts reaches beyond the
saturation point, the salts start precipitating out in order of their stabilities, the salt
which is least soluble separate out first.

A. Scale formation: The scales are strong adhesive coating on the inner walls of boilers.
These stick very firmly to the inner walls of boilers and hence are very difficult to
remove. Scales are formed through:
i. Decomposition of bicarbonates:
Ca(HCO3)2 -----→ CaCO3 ↓+ H2O + CO2
(Soft scale) (Low pressure boilers)
ii. Hydrolysis of Mg salts:
MgCl2 + 2H202 -----→ Mg(OH)2↓ + 2HCl
(Soft scale)
iii. CaSO4 is soluble in cold water but as temperature rises the CaSO4 (hard
scale) gets precipitated.
iv. Presence of silica: Salts like calcium silicate, magnesium silicate are sparingly
soluble in cold water, but are completely insoluble in hot water.
Disadvantages of Scale Formation:
i. Wastage of Fuel: Due to low thermal conductivity of the scale efficiency of
heat transfer decreases.
ii. Bagging: The distortion of boiler material is known as bagging. The super
heating of the boiler leads to the distortion of the boiler material by the
reaction of water and Iron causing thinning of boiler material.
3Fe + 4 H2O -----→ Fe3O4 +4H2
iii. Danger of explosion :- Due to deposition of scale the boiler becomes inelastic
and danger of boiler explosion increases.

Removal of Scales: Soft Scales are removed with the help of scrapper or wire brush.
 18

i. Brittle or Hard Scales can be removed by giving thermal shocks i.e. heating
the boiler and suddenly cooling with cold water.
ii. Scales can be dissolved by 5-10 % HCl.

Preventation of Scales Formation: it can be done by two methods viz:

1. External treatment: It is carried outside the boiler and includes water softening
processes (refer to page no. 5 for lime-soda, Zeolite and ion-exchange method).
2. Internal Treatment:-The internal treatment of boiler feed waters refer to the
treatment of water in the boiler itself. This involves adding certain chemicals directly
to the water to remove scale forming salts, either by precipitating the salts in some
or other form or converting these salts to soluble complexes, which remain
dissolved in water and thus do not form scales. The internal treatment often
referred as “Sequestration”. “Sequestration is a process in which an ion is prohibited
to exhibit its usual properties by either converting it to some other insoluble form or
by forming a complex with other compound”.
Methods used for internal treatment of water:
a. Colloidal conditioning
b. Carbonate conditioning
c. Phosphate conditioning
d. Calgon conditioning
a. Colloidal conditioning: It is done by adding colloidal substances to water like
kerosene, tannin, glue, agar etc. which form protective coating around scale
forming substance and convert them into sludge which can be removed easily by
coagulation method.
b. Carbonate conditioning (Low pressure boilers): It is based on the fact that a salt
can be precipitated if its ionic product is greater than its solubility product. In this
method the salts like CaSO4 can be prevented from precipitation by adding
excess of Na2CO3.
CaSO4 in Soln present as:
CaSO4 -----→ Ca +2 + SO42-
So if we add Na2CO3 in excess the concentration of CO32- ions become higher
than SO42- ion the CaCO3 get precipitated instead of CaSO4.
[Ca2+]*[ CO32-] >>>> [Ca2+]*[ SO42-]
Ca2++ CO32- -----→ CaCO3↓
Note: Na2CO3 can’t be used in high pressure boilers because CO32- ion undergo
hydrolysis to form -OH as:
CO32- + H2O ⇔ -OH + HCO3-
 19

c. Phosphate conditioning (High pressure boilers) : In high pressure boilers Na3PO4

is used instead of Na2CO3. The principle is same as carbonate conditioning.
CaSO4 in Soln present as:
CaSO4 -----→ Ca +2 + SO42-
So if we add Na3PO4 in excess the concentration of PO43- ions become higher
than SO42- ion the Ca3(PO4)2 get precipitated instead of CaSO4.
[Ca2+]*[ PO43-] >>>> [Ca2+]*[ SO42-]

3CaSO4 + 2 Na3PO4 -----→ Ca3(PO4)2↓ + 3Na2SO4

The other phosphates used are:
NaH2PO4 (Sodium dihydrogen phosphate), Na2HPO4 are used depending upon
alkalinity of water.
d. Calgon Conditioning: Calgon is the commercial name of Sodium
hexametaphosphate. It forms the complex with scale forming salts in which Ca2+
and Mg2+are trapped in complex ion. The complex ion formed is soluble in water
and prevents scale formation.
Na2[Na 4(PO3)6] → 2Na+ + [Na4(PO3)6]2-
2CaSO4 + [Na4(PO3)6]2--→ [ Ca2(PO3)6]2- + 2Na2SO4
B. Sludge Formation: When precipitation of dissolved salt takes place in the form of
loose, non- adherent, slimy precipitate, it is called sludge. Sludge are formed by the
substances having greater solubilities in hot water then cold water. e.g. MgCO3,
MgCl2, CaCl2, MgSO4 etc.
Disadvantages of Sludge formation:
i. Wastage of Fuel: Due to low thermal conductivity of the sludge heating
efficiency decreases.
ii. Chocking of pipes
Prevention of Sludge formation:
i. Using soft water for boiler.
ii. By simple “Blow down Process”
Removal of Sludge: Sludge can easily be removed by scrapping off with a brush.
2. Boiler corrosion: It is the decay of boiler material due to attack of certain chemicals
on its surface resulting into formation of compounds such as oxides, sulphides, etc.
The material of boiler rusted and gets dissolved thereby reducing the life of boiler.
Cause boiler corrosion:
i. Presence of dissolved oxygen: At high temp O2reacts with boiler material to
form rust.
2Fe +2H2O + O2 -----→ Fe(OH)2
4 Fe(OH)2 + O2 + 2H2O -----→ 2[Fe2O3 . 2H2O]
 20

Removal of dissolved oxygen by two means:

a. Chemical means
b. Mechanical means
a. Chemical means: oxygen is removed by adding calculated amounts of certain
chemical such as Na2SO3, Na2S and N2H4.

2Na2 SO3 + O2 → 2 Na2SO4

Na2S + 2O2 → Na2SO4
N2H4 + O2 → N2+2H2O
b. Mechanical means: It is based on Henry’s Law and Dalton’s Law i.e. solubility of
gas is directly proportional to pressure and inversely proportional to
temperature. It is done by passing the water via a heated vacuum chamber
maintained at low pressure.
ii. Presence of dissolved CO2: It forms carbonic acid in presence of water which
has slow corrosive effect on boiler material.

CO2 + H2O → H2CO3

Carbonic acid
Removal of dissolved CO2 by two means:
a. Chemical means
b. Mechanical means
a. Chemical means: CO2 is removed by adding NH4OH and filtering through lime
stone.
2NH4OH + CO2 → ( NH4)2 CO3 + H2O
CaCO3 + H2O + CO2 → Ca(HCO3 )2
b. Mechanical means: It is based on Henry’s Law and Dalton’s Law i.e. solubility
of gas is directly proportional to pressure and inversely proportional to
temperature. It is done by passing the water via a heated vacuum chamber
maintained at low pressure.

iii. Presence of mineral acids: Mineral acids if present in boiler feed water react
with the iron material as:-
Fe + 2HCl → FeCl2+ H2
FeCl2 + 2H2O → Fe(OH)2 + 2HCl
Fe (OH )2 + O2 + 2H2O → 2[Fe2O3. 2H2O]
Removal of acids: Thus,if water is acidic calculated amount of alkali is
added to neutralize it.
 21

3. Caustic embrittlement: It is a special type of boiler corrosion which takes place due
to the presence of highly alkaline water in the boiler. The material of the boiler
becomes corrosive due to the accumulation of caustic substance. The water softening
lime-soda process generates NaOH which travel to the minute hair cracks, riveted
bends and joints. NaOH sets a concentration cell inside the boiler material and causes
corrosion.
Na2CO3 + H2O → 2NaOH + CO2

Conc. Iron at Pores Iron at Plane surfaces Dil.

Cracks/Rivets
NaOH Anode Cathode NaOH

Oxidation occurs at anode i.e. Fe → Fe2+ and the boiler decay starts at rivets.
The embrittlement appears to be favored under the following conditions:-
i. Materials subjected to great stresses beyond their yield point.
ii. High conc. Of NaOH.
iii. Presence of compounds such as sodium nitrate.
Prevention of caustic embrittlement:-
i. Using sodium phosphate instead of sodium carbonate as softening reagent.
ii. Adding liquids to block up the air cracks.
iii. It is observed that water containing sodium phosphate inhibits caustic
embrittlement by blocking the capillaries.
4. Priming and Foaming:
A. Priming: The phenomenon of forming of wet steam or steam containing water
droplets is called priming.
Cause of priming:
i. The high steam velocities.
ii. Very high water level in the boiler.
iii. Sudden stem demands leading to sudden drop of pressure in the steam line.
iv. Faulty boiler design.
v. Presence of impurities.
Disadvantages of priming:
 22

i. A part of dried salts may be carried along with steam farther and deposit on
the engine valves thereby decreasing their life.
ii. Presence of water droplet in the steam may lead to corrosion in the steam-
inlet ends of the super heaters.
Prevention of priming:
i. Keeping the water in the boiler to optimum level .
ii. Reducing steam velocities.
iii. Efficient softening.
iv. Good boiler design.

B. Foaming: The formation of small persistent bubbles at the surface of the boiling
water is called foaming. The air bubbles are formed due to difference in
concentration of solute or suspended matter between the surface film and the bulk
of the liquid. The substance that increases the viscosity of the surface film also
increases foaming formation.
Disadvantages of Foaming:
i. Height of the water column cannot be judged properly due to foaming
thereby making the maintenance of the boiler pressure difficult.
Prevention of foaming:
i. Addition of antifoaming chemicals e.g. Polyamide Gallic acid & Tannic acid.
ii. Removing of foaming agents from boiler by adding coagulants such as
sodium aluminate.

Disinfection of water by Chlorination: chlorine is used in its various forms almost

universally because its low cost, reliable and easy to handle. It removes organic
and inorganic matter also.
Various forms of chlorine used:
i. Chlorine gas/liquid
ii. Bleaching powder/hypochloriles
iii. Use of chlorine tablets
iv. Use of chloroamines
v. Use of ClO2 gas
Disinfecting action of chlorine: When chlorine is added to water it forms hypochlorous
acid or hypochlorite ions which have immediate lethal effect on microorganisms.
Cl2 + H2O -----→ HOCl + HCl (at ph = 5)
The hypochlorous acid is unstable and may dissociate as
HOCl <--> H+ + -OCl
 23

(Hypochlorite ions)
Due to this reason the pH value of water during chlorination is generally maintained
slightly less than 7 so as to prevent dissociation of HOCl. According to the enzymatic
hypothesis the HOCl destroys the enzymes in the cells of bacteria which are essential for
their growth and other metabolic processes so bacteria is killed.
Moreover the HOCl will immediately react with NH3 to form various chloroamines which
act as disinfectants and chlorine reservoirs.
NH3 + HOCl -----→ NH2Cl + H2O
NH2Cl + HOCl -----→ NHCl2 + H2O
NHCl2 + HOCl -----→ NCl3 + H2O
Process of chlorination: it can be divided in four stages.

1st stage: It is seen from the figure that for lower doses of chlorine all the chlorine added
is consumed and there is no Cl2. This is due to fact that initially Cl2 reacts with inorganic
impurities present in water forming chlorides. These chlorides don’t have any residual
oxidising power.
2nd stage: As the amount of applied dose increases there is steady increase in the
amount of residual chlorine. This stage corresponds to the formation if chloroamines i.e.
Cl2 is consumed by NH3. But chloramine responds to the test for estimation of chlorine
in the same way as free chlorine and hence curve represent the chlorine available from
combined residuals.
3rd stage: When dosage of chlorine are further increased , the complete oxidation of
chloroamines and chloro-organic compounds take place utilizing the chlorine and
accordingly free residual chlorine also decreases and reaches a dip when the oxidation is
completed. The dip is known as break point chlorination.”The breakpoint chlorination
ensures complete destruction of organic compounds which give unpleasant taste and
bad odour”.
 24

4th stage: After breakpoint, the amount of chlorine added isn’t used in any reaction and
the residual chlorine agrees fairly well with quantity of chlorine added.
Thus, breakpoint chlorination of water may be defined as chlorination up to an extent
that microorganisms as well as bad taste and odours present in water are also destroyed.

Dechlorination: Excess of residual chlorine is removed by dechlorination, it is done by

using SO2 gas, Na2S2O3, Na2SO3 etc.
SO2 + Cl2 + H2O -----→ H2SO4 + 2HCl
Na2SO3 + Cl2 + H2O -----→ Na2SO4 + 2HCl
Desalination of brackish/salty water:
Brackish/salty water: Water containing high concentration of dissolved solids(> 1000ppm
but < 3500ppm) is known as brackish water.
Desalination of water: The process of removal of dissolved solids from water is known as
desalination. It is done by various methods and some important are:
i. Reverse Osmosis (R.O.).
ii. Electerodialysis.
i. Reverse Osmosis (R.O.): It just reverse of the osmosis process i.e.
Osmosis: It is movement of solvent(usually water) molecules from a less
concentrated solution to high concentrated solution when the two solutions are
separated by a semi-permeable membrane.
Due to this movement of solvent molecules level of solution towards
concentrated side rises and a pressure is developed known as osmotic pressure.
If we want to stop this movement of solvent molecules from a less concentrated
solution to high concentrated solution we have to apply pressure equal to
osmotic pressure and if want to reverse the flow we have to apply pressure
greater than osmotic pressure.
Reverse Osmosis: The process of reversing the flow of solvent molecules by
applying pressure greater than osmotic pressure is known as reverse osmosis.
 25

Advantages of Reverse Osmosis:

a. Purification of ionic, non-ionic, colloidal and solutions containing high molecular
weight compounds can be done by this method.
b. Less energy required( 30% of distillation).
c. Low maintenance cost due longer life of membranes.

ii. Electrodialysis: This process is based on the fact that the ions present in saline
water migrates towards oppositely charged electrodes trough selectively
permeable membranes under the influence of applied electric field.
The arrangement is consist of two electrodes i.e. cathode and anode separated
by selectively permeable membranes. The membranes are arranged in such a
manner that adjacent to cathode there is cationic permeable membrane(CPM)
and adjacent to anode there is anionic permeable membrane(APM) and also
alternatively i.e. APM followed by CPM followed by APM. We get columns of
deionized water and concentrated brackish water alternatively.

Advantages of Electrodialysis:
i. It is a compact unit which is easy to carry and operate.
ii. The cost of Electrodialysis Plant installation is low.
iii. This method is best suited when water of very high purification is not required.
 26

Questions
Q.1 Distinguish between temporary and permanent hardness of water? Or what is meant by
carbonate and non-carbonate hardness of water?
Q.2 How do you express the hardness? What are the units to express the hardness? Or How is
the hardness of water expressed?
Q.3 How do you estimate the total hardness of water?(or) Explain any one method for the
estimation of hardness of water. (or) What is the principle of EDTA method? Explain the
estimation of hardness of water by complexometric method.
Q.4 What are Scales? How are they formed? What are the disadvantages and what are the
methods of prevention of scale formation? Or Explain the factors responsible for the
corrosion of a boiler. Discuss the measures for its prevention.
Q.5. What are external and internal treatments of water?
Q.6 Distinguish between scales and sludges.
Q.7 Write short notes on the following:
(a) Colloidal conditioning (b) Sodium aluminate condition (c) Calgon conditioning
(d) Carbonate conditioning Or Compare Phosphate conditioning with calgon conditioning.
Q.8 What is meant by desalination? Explain the different methods used for the desalination
of brackish water. Or Explain the desalination of water by electro dialysis.
Q.9 Write briefly on caustic embrittlement.
Q.10 What do you understand by hardness?What is its cause?
Q. 12 Why [EDTA-Ca2+/Mg2+ ] complex is more stable than [EBT-Ca2+/Mg2+ ]complex.
Q. 13 Why NH3-NH4Cl buffer is used in EDTA method
Q. 14 What is SODA-LIME process?Give its types, reactions & calculations.
Q. 15 What are Cation & Anion exchange resins? Give chemical rections involved in
ION-EXCHANGE method (softening & regeneration).
Q. 16 Distinguish b/w:
(a) Cold & hot SODA-LIME process.
(b) Softening & Demineralization.
Q. 17 100mL of a sample water required 15mL of 0.01M EDTA and the same sample
After boiling required 8mL of 0.01M EDTA.Calculate all types of hardness.
Calculate amount of LIME & SODA required for treatment of 20000 liters of water Containing:
Ca(HCO3)2=40.5ppm,Mg(HCO3)2=36.5ppm,MgSO4=30ppm,CaSO4=34ppm,
CaCl2=27.75ppm,NaCl=10ppm.
Q. 18 A water sample using FeSO4.7H2O=278ppm as a coagulant ,gave following data:
Ca2+ =240ppm,Mg2+ =96ppm,CO2=44ppm,HCO3=732ppm.
Calculate LIME & SODA required for 250000 Liters of sample.
27