Water treatment

❑ Sources of Water
- Rain water
- Sea water
- River water
- Lake water
- Underground water
❑ Effect of water on rock
- dissolution
- hydration
- oxidation
- action of carbon dioxide
❑ Hardness of water
- the characteristic of preventing lather formation of water with soap.
- Types of hardness
– Temporary hardness (due to the bicarbonates of Ca2+ and Mg 2+ and
carbonate of Fe2+ ) heat
Ca (HCO3 )2 CaCO3 + H2 O + CO2
insoluble

- Permanent hardness (due to the presence of chlorides and sulfates of Ca,

Mg, Fe, etc.)
- Units of hardness – ppm as CaCO3 or mg CaCO3 equivalent per liter
1 part of hardness
- 1 ppm = = 1 mg/l
106 parts of water
❑ Disadvantages of hard water
(a) in domestic uses: washing and bathing, cooking, drinking
(b) in industrial uses: textile and dyeing industry
- For steam generation in boilers, hard water creates many problems
i. scale formation, ii. corrosion, iii. priming and foaming
and iv. caustic embrittlement

❑ Sludge and Scale Formation in Boilers

When hard water is used for boilers, on continuous evaporation, the salts present in the
hard water gets saturated and are finally deposited in the area where the flow is slow.
When these precipitates are loose and slimy in nature, it is called sludge.
❑ Removal of sludge – i. using soft water for boiler operation ii. Removing the concentrated
salty water from time to time
Determination of hardness – (i) from the given dissolved chemicals in water
(ii) from sample water by using EDTA method
(i) from the given dissolved chemicals in water
molecular weight of CaCO3
Conversion factor =
molecular weight of dissolved salts

Example 1 The following chemicals are dissolved in a liter of water. Calculate the
hardness of this sample of water.
CaSO4 = 20.0 mg Mg(HCO3)2 = 14.6 mg MgCl2 = 12.5 mg
mol. wt of CaSO4 = 40+32+(16x4) = 136 g/mol
mol. wt. of Mg(HCO3)2 = 24+(2x1)+(2x12)+(2x16x3) = 146 g/mol
mol. wt of MgCl2 = 24+(35.5x2) = 95 g/mol mol. wt of CaCO3 = 40+12+(3x16) = 100 g/mol
Conversion factor CaCO3 equivalent
CaSO4 20.0 mg 100 / 136 20.0 x 100 / 136 = 14.7 mg/L
Mg(HCO3)2 14.6 mg 100 / 146 14.6 x 100 / 146 = 10.0 mg/L
MgCl2 12.5 mg 100 / 95 12.5 x 100 / 95 = 13.2 mg/L
Total hardness of water = 14.7 + 10.0 + 13.2 = 37.9 mg/L = 37.9 ppm
❑ Scales – hard deposits on the inner surface of the boilers which difficult to remove.
❑ Formation of scale – 1. in low pressure, due to the formation of CaCO3 from Ca(HCO3 )2
2. in high pressure, CaCO3 gets converted to soluble Ca(OH)2 . CaSO4 forms hard scale.
The solubility of CaSO4 decreases with increase in temperature.
3. Dissolved Mg salt precipitate as Mg(OH)2 forming soft type of scale.
❑ Removal of scales – 1. wooden scraper or wire brush
2. blow down operations for loose scales
3. giving thermal shocks
4. chemical treatment with 5-10% HCl for carbonates and EDTA treatment for Ca/Mg
salts
❑ Caustic Embrittlement – in steam boiler operation, the chemicals that are believed
to be responsible are NaOH and silica. During softening processes, Na2 CO3 are added
and it gives rise to NaOH at elevated temperature according to the following reaction
❑ Na2 CO3 + H2 O → 2NaOH + CO2
❑ Steam boiler are made by riveting constructions rater than welding and are liable to
damage by caustic alkali solutions.
❑ This cracking is not due to corrosion and the crack appear like brittle fracture (Caustic
embrittlement)
❑ NaOH attacks and dissolves out iron of boiler forming sodium ferrate.
❑ This finally causes the stressed parts like bends, joints, rivets to lead to the boiler
failure.
❑ Prevention – 1. addition of sodium phosphate 2. addition of sodium sulphate 3. addition
of organic agents 4. use of crack-resisting steels.
❑ Corrosion in boilers – occurs by chemical or electrochemical attack of the contents
of water.
❑ 1. Dissolved oxygen – dissolved oxygen ( 8 ml/l at room temperature) is responsible for
corrosion in the boiler. Greater the pressure, higher dissolved oxygen content. The water
is heated in the boiler, DO is liberated and iron is corroded.
❑ 2 Fe + 2𝐇𝟐 O + 𝐎𝟐 → 2 Fe(OH)𝟐
❑ 4 Fe(OH)𝟐 + 𝐎𝟐 → 2[ 𝐅𝐞𝟐 𝐎𝟑 . 2𝐇𝟐 O]
❑ 2. Dissolved 𝐂𝐎𝟐 - water contains some CO2 and the decomposition product of
bicarbonates present in water produces 𝐂𝐎𝟐 . 𝐂𝐎𝟐 dissolves in water forming carbonic
acid which causes local corrosion called pitting.
❑ Fe + 𝐂𝐎𝟐 + 𝐇𝟐 O → 𝐅𝐞𝐂𝐎𝟑 + 𝐇𝟐
❑ 4 𝐅𝐞𝐂𝐎𝟑 + 𝐎𝟐 + 10 𝐇𝟐 O → 4 Fe(OH)𝟑 + 4𝐂𝐎𝟐 + 4𝐇𝟐 O
❑ 4 Fe(OH)𝟑 → 2 𝐅𝐞𝟐 𝐎𝟑 + 6𝐇𝟐 O
❑ 3. Mineral acids – water from industrial areas contains acidic wastes or inorganic salts
which on hydrolysis produce acids.
❑ These acids cause corrosion in boilers. The acids react with iron in chain reactions
producing acids again and again and also produce H2 causing hydrogen embrittlement
which leads to boiler failure.

❑ Priming and Foaming

❑ Priming – during rapid steam production, some liquid water drops are also carried
along with the steam. This wet-steam formation is called priming.
❑ due to presence of large amount of dissolved solids, high steam velocities, sudden
boiling and sudden increase in steam production.
❑ Forming – the production of bubbles and foams which do not break easily. It occurs due
to the presence of oil in the water. (can be reduced by removing oil from boiler-feed
water and adding antifoaming agents)
❑ Softening of Water – the removal of calcium, magnesium, iron salt and similar other
metallic ions, which form insoluble metallic soaps.
❑ Three important industrial methods – 1. cold and hot lime-soda process
2. permutit or zeolite process 3. Ion-exchange or demineralization process

❑ 1. Lime-soda process – by this process, soluble calcium and magnesium salts are
tendered insoluble by adding calculated amount of lime, Ca(OH)2 and soda Na2 CO3
❑ insoluble precipitates of CaCO3 and Mg(OH)2 are removed by filtration.
❑ Temporary and permanent hardness are removed.
❑ The removal of temporary hardness,
❑ Ca(HCO3 )2 + Ca(OH)2 → 2CaCO3 + 2H2 O
❑ Mg(HCO3 )2 + 2Ca(OH)2 → 2CaCO3 + 2H2 O + Mg(OH)2
❑
❑ The removal of permanent hardness,
❑ CaSO4 + Na2 CO3 → CaCO3 + Na2 SO4
❑ MgSO4 + Ca(OH)2 → Mg(OH)2 + CaSO4
❑ CaSO4 + Na2 CO3 → Na2 SO4 + CaCO3
❑ MgCl2 + Ca(OH)2 → Mg(OH)2 + CaCl2
❑ CaCl2 + Na2 CO3 → CaCO3 + 2 NaCl
❑ In the actual process the water is thoroughly mixed with the chemicals and allowed to
react for sufficient time.
❑ Activated charcoal is added as activator, alum etc. are added as coagulants.
❑ To avoid after-precipitation of CaCO3 , sludge of the previous operation is added, which
supplies the nuclei for the precipitation.
Cold lime –Soda process
❑ Hot Lime-Soda Process
❑ Hot lime-soda process consists of three parts-
(a) Reaction tank in which complete mixing of the ingredients takes place.
(b) Ionical sedimentation vessel where the sludge settles down
(c) Sand filter where sludge is completely removed.
❑ Advantages – lime soda process is economical.
the process improve the corrosion resistance of the water.
mineral content of the water is reduced.
pH of the water rises, which reduces the content of pathogenic bacteria.
❑ Disadvantages – huge amount of sludge is formed and disposal is difficult.
due to residual hardness, water is not suitable for high pressure boiler.
❑ Permutit or Zeolite Process
❑ Zeolite – hydrated sodium aluminosilicate capable of exchanging reversiblly its sodium
ions for Ca and Mg cations.
❑ Artificial zeolite used for softening purpose – permutit
❑ Method of softening – hard water is passed through a bed of zeolite at a specific rate at
ordinary temperature; the hardness causing cations are exchanged for Na and it is
converted to CaZe and MgZe.
❑ Regeneration of zeolite – the process is commercially successful since the Ca/Mg
zeolites formed by passing hard water through the bed can be easily regenerated into
Na2 Ze by passing brine through the bed of inactivated zeolite.
❑ CaZe or MgZe + 2NaCl → Na2 Ze + CaCl2 (or MgCl2 )
❑ The washing containing CaCl2 or MgCl2 are washed. The water softened by this
process can be used for laundry purposes.
❑ Softening of hard water by permutit process
❑ Ion Exchange or Demineralization

❑ Ion exchange resins – organic polymers which are crosslinked having microporous
structure and the functional groups are attached to the chains which are responsible for
the ion exchange properties.
❑ Cation exchange resins (𝐑𝐇 + ), Anion exchange resins (𝐑𝐎𝐇 − )
❑ Method - The hard water is passed first through cation exchange resin similar to the
permutit process whereby the cations like Ca𝟐+ , Mg 𝟐+ are removed from the hard
water and exchanged with H + as follows:
❑ 2RH + + Ca𝟐+ → R 2 Ca𝟐+ / R 2 Mg 𝟐+ + 2 H+
❑ After this the hard water is again passed through anion exchange column, which
exchanges all the anions like SO2−
4 , Cl etc. present in the water with OH
− −

❑ ROH− + Cl− → R+ Cl− + OH−

 These H + and OH− combine to form water molecule. Water coming out finally from the
two exchangers is ion free and called deionized or demineralized water.
❑ Regeneration: the inactivated or exhausted cation exchange resin is regenerated by
dil H2 SO4 /HCl.
❑ R 2 Ca2+ + 2H + 2RH + + Ca2+
❑ the exhausted anion exchange resin is regenerated by dil NaOH.
❑ R 2 SO2−
4 + 2 OH− 2ROH− + SO2−
4

❑ The columns are finally washed with deionized water and the washing are discarded.

❑ Mixed Bed Deionizer : a single cylinder containing and intimate mixture of cation
and exchanger and strongly basic anion exchanger.
❑ Treatment of Water for Domestic Use
❑ Requirements for drinking water:
❑ clear and odorless, devoid of any unpleasant taste,
❑ Suspended matter (not exceed 10 ppm)
❑ Devoid of heavy metals and arsenic
❑ pH should be about 8
❑ Content of dissolved salts (not exceed 500 ppm)
❑ Be free from pathogenic microorganism.

❑ Natural water from river, lakes, canal are treated for domestic purpose:
1.aeration, 2. settling, 3. sedimentation, 4. coagulation (gelatinous precipitates, heavy
flocculant precipitates), 5. Filtration, 6. Sterilization
❑ Sterilization
❑ 1. By addition of bleaching powder
Ca(OCl)Cl + H2 O Ca(OH)2 + Cl2
Cl2 + H2 O HCl + HOCl
❑ By adding chlorine
0.3 – 0.5 ppm chlorine is efficient.

❑ 2. Break-point chlorination
When liquid chlorine is added or chlorine gas is passed through water the consumption
of chlorine makes the available chlorine less and after some time the available chlorine
increases. This is due to the consumption of chlorine in oxidizing some oxidizable
organic matter present in water at first. Then available chlorine again increases due to
decomposition of chloro-organic compounds.
 This free chlorine is responsible for destruction of pathogenic bacteria in water.

 The point at which the residual chlorine begins to appear is known as break point and

at this point water is devoid of bad taste and odors and is bacteria free.

❑ 3. Sterilization by chloramine
when chlorine and ammonia are mixed in the ratio 2:1 of volume chloramine is
formed.
Cl2 + NH3 Cl. NH2 + HCl
chloramine is much more effective than chlorine in its bactericidal action.
Cl. NH2 + H2 O HOCl + NH3
HOCl HCl + [O]
❑ 4. Sterilization by ozonization ( comparatively costly)
❑ Sterilization through Physical Methods
1. Boiling 2. exposure to the sunlight 3. Sterilization with UV light
❑ Dechlorination
 When during chlorination, break point chlorination is reached, it becomes sometimes
necessary to remove the excess chlorine from the treated water, this process is known as
dichlorination. Sulphur dioxide is very common as an antichlor. Other common
antichlor's are: sodium bisulphite, sodium thiosulphate and hydrogen peroxide.

Cl2 + H2 O → HOCl + HCl

H2 O + SO2 → H2 SO3 Cl2 + 2H2 O + SO2 → 2HCl + H2 SO3
HOCl + H2 SO3 →HCl + H2 SO4 H2 O2 + Cl2 → 2HCl + O2
 Dichlorination is needed to avoid the harmful effects of treated water.
❑ Desalination of Brackish Water
❑ The water containing dissolved salts and having very salty taste – brackish water
(like sea water and not suitable for drinking)
❑ The process of common salt from it – desalination
 (1) Electrodialysis - This method involves the removal of ions from the brine solution by

applying direct current and employing pair of plastic membranes through which ions can

pass.

- To make this process more effective, ions sensitive membranes are used that allow the

passage of either specific cations or specific anions. These membranes are selective as

they are made up of materials containing fixed functional groups.

 Electrodialysis
 2. Reverse osmosis - Osmosis describes the flow of solvent from dilute to concentrated

solution through a semipermeable membrane. Whereas reverse osmosis describes the

flow of solvent in opposite direction i.e., from concentrated solution to dilute solution

across a semipermeable membrane by applying hydrostatic pressure in excess of

osmotic pressure.
❑ Chemical Analysis of water
 1. Estimation of free chlorine - The residual free chlorine remaining after the municipal

processing of domestic water is injurious to health and hence estimation of this free

chlorine is essential. The principle is the treatment of water containing free chlorine with

KI solution. The chlorine present liberates an equivalent amount of iodine which can be

estimated with standard thiosulfate solution using starch as an indicator.

Cl2 + 2KI → 2KCl + I2

I2 + 2 Na2 S2 O3 → 2NaI + Na2 S4 O6

I2 + starch → Deep-blue complex

 Method: To 50 ml of water sample in a iodine flask, 10 ml of 10% KI solution added,

shaken and waited for some time in the dark and finally titrated with N/50 sodium

thiosulfate solution using starch solution as indicator towards the end. The end point

indicates a change from deep-blue to just colorless solution.

 Calculation:

Volume of N/50 Na2S2O3 required = V ml

V x 35.5 x 106
Strength of free chlorine = ppm
2500 x 1000
 2. Alkalinity – the alkalinity of water is estimated by estimating (a) OH − and CO2−
3 ions
and (b) HCO−
3 ions.
(a) OH − + H+ → H2 O
CO2−
3 + H+ → HCO−
3
(b) HCO−
3 + H+ → H2 O + CO2
 These estimations are done by (a) titrating against standard acid solution using
phenolphthalein as an indicator and (b) using methyl orange as an indicator.
 Method: 100 ml of water sample is taken in a flask and few drops of phenolphthalein
added and titrated against N/50 H2SO4 solution to colorless end point. The same solution is
further titrated with 2 to 3 drops of methyl orange indicator.

 Calculation: Vol. of acid upto phenolphthalein end point = V1

 Extra volume of acid added to get methyl orange end point = V2 ml.

 Phenolphthalein alkalinity (equivalent CaCO3 )

V1 𝑥 50 𝑥 106
P = ppm
50 𝑥 100 𝑥 1000

➢ Methyl orange alkalinity (equivalent CaCO3 )

(V1 +V2 ) 𝑥 50 𝑥 106

M= ppm
50 𝑥 100 𝑥 1000
 3. Hardness
 (a) Estimation of temporary hardness - Temporary hardness is due to Ca(HCO3)2 and

Mg(HCO3)2 which cause alkalinity in water. Temporary hardness is determined by finding

the alkalinity of water before and after boiling, since temporary hardness is removed on

boiling.
 Problem 5
 Calculate the amount of lime and soda required for softening 50,000 liters of hard water.
 MgCO3 = 144 ppm; CaCO3 = 25 ppm; MgCl2 = 95 ppm; CaCl2 = 111 ppm;
 Fe2 O3 = 25 ppm; Na2 SO4 = 15 ppm
 Molar mass of MgCO3 = 84 g/mol molar mass of CaCO3 = 100 g/mol
 Molar mass of MgCl2 = 95 g/mol molar mass of CaCl2 = 111 g/mol
 Molar mass of Na2 CO3 = 106 g/mol molar mass of Ca(OH)2 = 74 g/mol
Conversion CaCO3 equivalent
factor
MgCO3 144 ppm 100/84 144 x 100/84 = 171.4 ppm

MgCl2 95 ppm 100/95 95 x 100/95 = 100 ppm

CaCl2 111 ppm 100/111 111 x 100/111 = 100 ppm

 (1) MgCO3 + Ca(OH)2 → Mg(OH)2 + CaCO3
 (2) MgCl2 + Ca(OH)2 → Mg(OH)2 + CaCl2
 CaCl2 + Na2 CO3 → CaCO3 + 2 NaCl
 (3) CaCl2 + Na2 CO3 → CaCO3 + 2 NaCl

74
 Amount of lime required = (2 x MgCO3 + CaCO3 + MgCl2 ) x volume of water
100
74
= (2 x171.4 + 25 + 100 ) x 50,000
100
= 17308600 mg = 17.31 kg
106
Amount of soda required = (MgCO3 + MgCl2 + CaCl2 ) x volume of water
100
106
= ( 171.4 + 100 + 100 ) x 50,000
100
= 19684200 mg = 19.68 kg
Problem 11 Calculate the cost of lime and soda required for softening 1 million liters of a
water sample containing. Mg(HCO3 )2 = 73 mg/l; MgSO4 = 120 mg/l; CaSO4 = 68 mg/l;
CaCl2 = 111mg/l.
The cost of lime of 80% purity is Rs. 200 per metric ton and that of soda of 90% purity is
Rs. 12,000 per metric ton.
Molar mass of Mg(HCO3 )2 = 146 g/mol Molar mass of MgSO4 = 120 g/mol
Molar mass of CaSO4 = 136 g/mol Molar mass of CaCl2 = 111 g/mol
Molar mass of CaCO3 = 100 g/mol
Molar mass of Na2 CO3 = 106 g/mol molar mass of Ca(OH)2 = 74 g/mol

Mg(HCO3 )2 73 ppm 100/146 73 x 100/146 = 50 ppm

MgSO4 120 ppm 100/120 120 x 100/120 = 100 ppm

CaSO4 68 ppm 100/136 68 x 100/136 = 50 ppm

CaCl2 111 ppm 100/111 111 x 100/111 = 100 ppm

 74
 Amount of lime required = (2 x Mg(HCO3 )2 + MgSO4 ) x purity x volume of
100
water
74 100
= (2 x 50 + 100 ) x x 106
100 80
= 185000000 mg = 185 kg
106
Amount of soda required = (MgSO4 + CaSO4 + CaCl2 ) x purity x volume of water
100
106 100
= ( 100 + 50 + 100 ) x x 106
100 90
= 294444444.44 mg = 294.4 kg
 Calculations of The Requirement of Lime and Soda
 Rules for solving numerical problems on lime-soda requirements for softening of hard
water:
1. The units in which the impurities are analyzed and expressed are to be noted.

2. Substances which do not contribute towards hardness (KCl, NaCl,

SiO2, Na2SO4 etc.) should be ignored and explicitly stated.
3. A substances causing "hardness should be converted into their respective CaCO3
equivalents.
4. If the impurities are given as CaCO3 or MgCO3, these should be considered due to
Ca(HCO3)2 and Mg(HCO3)2 respectively and they must only be expressed in terms
of CaCO3 and MgCO3
5. The amount expressed as CaCO3 does not require any further conversion.
However, the amount expressed as MgCO3 should be converted into its CaCO3
equivalents by multiplying with 100/84.
 6. The amount of lime and soda required are calculated as follows.
 Lime= (74/100) {temporary calcium hardness + (2 × temporary magnesium hardness)+
Perm Mg hardness + CO2+ HCl + H2SO4 + 𝑯𝑪𝑶 −
𝟑 + salts of 𝑭𝒆 𝟐+
, 𝑨𝒍 𝟑+
– NaAlO2)
 Soda = (106/100) {Perm Ca hardness + Perm Mg hardness + salts of 𝑭𝒆𝟐+ , 𝑨𝒍𝟑+ + HCl +
H2SO4+ 𝑯𝑪𝑶 −
𝟑 – NaAlO2}

7. If Ca2+and Mg2+ is given, 1 equivalent of lime and 1 equivalent of soda is required

for Mg2+ whereas1 equivalent of soda is required for Ca2+. The ions Ca2+ and Mg2+
are treated as permanent hardness due to Ca and Mg.
8. If the lime and soda used are impure and if the percentage purity is given, then the
actual requirements of the chemicals should be calculated accordingly. Thus, if lime
is 90% pure, then the value obtained in step (6) must be multiplied by 100/90 to get actual
lime requirement. Similarly, if the soda is 95% pure then the value obtained in step (6) is
multiplied by 100/95 to get actual soda requirement.
 9. The value obtained in step (6) is also multiplied by the volume of water which has to

be purified. Thus the final formula for calculating the amount of lime or soda required is

given as

 Lime= (74/100) {temporary calcium hardness + (2 × temporary magnesium hardness)+ Perm Mg

hardness + CO2 + HCl + H2SO4 + 𝑯𝑪𝑶 − 𝟐+

𝟑 + salts of 𝑭𝒆 , 𝑨𝒍
𝟑+ – NaAlO2) x % purity x volume

of water

 Soda = (106/100) {Perm Ca hardness + Perm Mg hardness + salts of 𝑭𝒆𝟐+ , 𝑨𝒍𝟑+ + HCl + H2SO4+

𝑯𝑪𝑶 −
𝟑 – NaAlO2} x % purity x volume of water