Sources of water

o Rainwater : It is the purest form of natural water. But unfortunately it water. dissolves the toxic gases like CO2, SO2, NO2 etc. and other solids. etc. solids. o Sea water : It is the most impure form of water containing about 3.5% dissolved salts of which about 2.6% is NaCl. Other salts present include NaCl. sulfates, bicarbonates, bromides of sodium, potassium, magnesium etc. etc. o River water : The sources of river water are the springs (A small stream of water flowing naturally from the earth) and the rainwater. River water while rainwater. flowing through the land collects lots of organic matters from falling trees and nearby habitats and also other soluble and suspended matters from the lands, soils etc. etc. o Lake water : It is much purer than river water, dissolved impurities are less but contains lots of organic matter. matter. o Underground water : The rainwater and other surface water percolate down through the soil and rocks and get filtered and finally collected on rocky surface or again come out as spring. Though it contains less suspended spring. matter but the dissolved mineral content is quite high and is of high organic purity. purity. 2

Impurities in water
Water has different physical, chemical and biological impurities which can cause problems in both domestic and industrial areas. areas. o Physical - Inorganic such as clay, sand - Organic such as oil globules, vegetable/animal matter - Colloidal such as Fe(OH)3, Complex proteins, amines
o Chemical

- Anions such as Cl-, SO42-, CO32-,HCO3-, NO3- of Ca & Mg - Cations such as Ca2+, Mg2+, Na+, K+, Fe3+, Al3+ - Dissolved gases such as O2, N2, CO2, H2S, NH3
o Biological

- Microorganisms such as algae, fungi, bacteria (Pathogenic causing Malaria, diohhrrea, typhoid etc.)
3

Hardness of Water
Hardness of water is the characteristic of preventing lather formation of water with soap. Generally salts like chlorides, bicarbonates and sulfates of Ca2+, soap. Mg2+ and Fe2+ make water hard. hard. This hard water on treatment with soap which is stearic or palmitic acid salts of sodium or potassium causes white precipitate formation of calcium or magnesium stearate or palmitate. palmitate.

Thus the cause of hardness is the precipitation of the soap and hence prevents lathering at first. When the hardness causing ions are removed as insoluble first. soaps, water becomes soft and forms lather. lather. 4

Types of Hardness
o Hardness of water is due to dissolved salts of mainly calcium and magnesium as well as iron and other heavy metals. metals.
o Hardness is two types: types: a) Temporary :
- Due to dissolved bicarbonates of calcium and magnesium and carbonates of iron and other heavy metals. - Can be easily removed by boiling where CO2 gas gets expelled removing the hardness.

b) Permanent:
- Due to dissolved chlorides and sulphates of calcium and magnesium. - Can be removed through zeolite, Lime-soda, ion-exchange processes
5

Disadvantages of hard water

a) In domestic use:
o Washing: Hard water, when used for washing purposes, does not Washing: lather freely with soap. Instead it produces sticky precipitates of soap. calcium and magnesium soaps. Similar problem exists in bathing. soaps. bathing. o Cooking: Due to the presence of dissolved hardness producing Cooking: salts the boiling point of water is elevated. Consequently more fuel elevated. is and time are required for cooking. cooking. o Drinking: Hard water causes bad effect on our digestive system. Drinking: system. The possibility of forming calcium oxalate crystals in urinary tracks is increased (Kidney stones). stones).
6

Disadvantages of hard water

o In Industrial use o Textile industry : Hard water cause much of the soap to go as waste. waste. Precipitate of calcium and magnesium soaps adhere to the fabrics. fabrics. These fabrics, when dyed latter on, do not produce exact shades of colour. colour. o Sugar industry : Water containing sulphates, nitrates, alkali carbonates, etc., if used in sugar refining, causes difficulties in etc. the crystallization of sugar. Moreover, the sugar so produced may sugar. be deliquescent. deliquescent. o Concrete making : Water containing chlorides and sulphates, if used for concrete making, affects the hydration of the cement and the final strength of the hardened concrete. concrete. o In steam generation in boilers o If the hard water is fed directly to the boilers, which led to the many problems such as (i) scale and sludge formation (ii) corrosion (iii) priming and foaming and (iv) caustic embrittlement 7

Measurement of hardness
o

Hardness of water is measured in parts per millions (ppm.) as calcium carbonate equivalents. Reasons for expressing hardness in CaCO3 equivalents:
- its molecular weight is 100 ; equivalent weight is 50. - it is the most common impurity in water.

Units of hardness:
- parts per million in CaCO3 equivalents (1 mg/L is 1ppm.). - if 146 mg/L of MgSO4 is present in water, the hardness of water is 146 ppm. as MgSO4.

When expressed in CaCO3 equivalents, the formula for conversion is: mass of hardness causing substance X 100 (mol. wt of CaCO3) Mol. Wt of hardness causing substance
8

Expressing water hardness

1. Ppm. measurement :
1 part of CaCO3 equiv. in106 parts of water (1 mg/L).

2. Clarks degree:
1 part of CaCO3 equiv. in 70,000 parts of water.

3. French degree:
1 part of CaCO3 equiv. in 105 parts of water.

* Conversion:
1ppm = 1 mg/L = 0.1Fr = 0.07oCl = 0.02 meg/L

Examples of hardness calculations

A sample hard water contains, 8.1 mg/L Ca(HCO3)2 ; 7.5 mg/L Mg(HCO3)2; 13.6 mg/L CaSO4; 12.0 mg/L MgSO4 and 2.0 mg/L MgCl2. To calculate the hardness and express in CaCO3 equivalents: Constituent
Ca(HCO3)2= 8.1 mg/L Mg(HCO3)2 = 7.5 mg/L CaSO4= 13.6 mg/L MgSO4= 12.0 mg/L MgCl2 = 2.0 mg/L

Multiplication factor
100/162 100/146 100/136 100/120 100/95

CaCO3 equivalents
8.1 x 100/162 = 5.0 mg/L 7.5 x 100/146 = 5.14 mg/L 13.6 x 100/136 = 5.0 mg/L 12.0 x 100/120 =10.0 mg/L 2.0 x 100/95 = 2.11 mg/L
10

Disadvantages of hard water

1. Scale and Sludge formation: a) Sludges:
o Soft, loose, slimy precipitates are sludges ~~~~ ~~~~~~~~ ~~~~~ ~ ~ ~ ~~ ~ ~ ~~~~ ~~~~ ~~~~ ~ ~ ~~ ~ ~~ ~ ~ ~ ~~~~ ~~~~ ~~~~~~~~ ~ ~ ~ ~~ ~ ~ ~ ~ ~ ~~~~ ~ ~~~~~~~ ~~~~ ~~~ ~~~~
Heat o Can be easily scrapped off with a wire brush o Forms in comparatively colder portions of the boiler such as bends etc. etc. o Formed because of MgCO3, MgCl2, CaCl2, MgSO4 Mg(OH)2,(more soluble in hot water)

b) Scales:
x x x

o Dissolved salts deposit because of continuous evaporation of water concentration of salts increases o These are hard and stick strongly to the walls o Difficult to be removed even with a hammer and chisel. o Formed because of CaCO3, CaSO4, CaSiO3, MgSiO3

Heat

11

Examples of Sludge and Scale

12

Scales
A. Decomposition of calcium bicarbonate:
o Scales are the main source of boiler troubles. Scale composed chiefly of calcium carbonate is soft and is the main cause of scale formation in lowpressure boilers.

Scale

o But in high-pressure boilers, CaCO3 is soluble. highCaCO3+ H2O Ca(OH)2 (Soluble) + CO2

13

B. Hydrolysis of magnesium salts

o Dissolved magnesium salts undergo hydrolysis forming magnesium hydroxide precipitate which forms a soft type of scale

MgCl2 + 2H2O

Mg(OH)2 + 2HCl

C. Presence of Silica
o Presence of silica in small quantities deposits as calcium silicate (CaSiO3) or magnesium silicate (MgSiO3). These deposits stick very firmly on the inner side of the boiler surface and are very difficult to remove

14

Disadvantages of scale formation

o Low thermal conductivity
Thickness of scale in (mm) Wastage of fuel 0.325 10% 0.625 15% 1.25 50% 2.5 80% 12 150%

o Lowering boiler safety o Decrease in efficiency o Danger of explosion

15

Prevention of scale formation

o External Treatment o To remove hardness-producing constituents of water hardnesso Internal Treatment o Colloidal Conditioning o Phosphate conditioning o Carbonate conditioning o Calgon conditioning o Treatment with sodium aluminate

16

Disadvantages of hard water

2. Priming and Foaming:
a) Foaming:
o

Foaming is the production of persistent foam or bubbles in boilers which do not break easily. easily. This is because of presence of oils which reduce the surface tension of water. water. Can be avoided by adding anti-foaming agents like caster oil or antiremoving oil from the boiler feed water by adding sodium aluminate. aluminate.

b) Priming: Priming:
o

Along with steam, some particles of water are carried (wet steam) which is called priming. priming. This is because of large amounts of dissolved salts, high steam velocities, sudden boiling, improper boiler design, sudden increase in steam production rate. rate. Priming can be avoided by maintaining low water level in boilers, avoiding rapid steam generation, efficient softening, installing mechanical steam purifiers. purifiers.
17

Disadvantages of hard water

3. Caustic embrittlement:
o o

Caused by using highly alkaline water in boiler When water is softened by lime-soda process, free Na2CO3 is present limein softened water. water. In high pressure boilers, this Na2CO3 decomposes to NaOH and CO2 Na2CO3 + H2O 2 NaOH + CO2

o o

This NaOH makes the water caustic. caustic. This NaOH flows through minute cracks present in the boiler by capillary action. action. As water is boiling it evaporates and the conc. of NaOH increases. conc. increases. This caustic soda attacks the boiler and forms sodium ferroate. ferroate. This makes the boiler parts brittle (embrittlement). (embrittlement).

o o o

18

Concentration cell formed during caustic embrittlement

Caustic attack on boiler parts can be represented as:

+
Iron at rivettes, bends, Joints etc.
o

Conc. NaOH soln.

Dil. NaOH soln.

Iron at Plane surfaces

The iron in contact with dil. NaOH becomes cathode and the iron in contact with conc. NaOH becomes anode. The anodic part slowly dissolves and corrodes. Caustic embrittlement can be avoided by adding: a) sodium phosphate (Softening agent) b) tannin or lignin (Blocks hair line cracks) c) sodium sulphate (Blocks hair line cracks)
19

o o

Boiler corrosion
o o

Decay of boiler material by chemical or electrochemical attack by surrounding environment. Reasons for boiler corrosion are: a) Dissolved oxygen b) Dissolved carbon dioxide c) Acids from dissolved salts

a)

Dissolved oxygen (DO): 2 Fe + H2O + O2 2 Fe(OH)2 + O2

2 Fe(OH)2

2 Fe2O3.2H2O Rust or corrosion DO can be removed by adding calculated qty. of sodium sulphite or hydrazine or sodium sulphide: 2 Na2SO3 + O2 2 Na2SO4 N2H4 + O2 N2 + 2H2O Na2S + 2O2 Na2SO4 DO can be removed by mechanical aeration also.
20

Boiler corrosion
b) Dissolved CO2:
o

Dissolved CO2 forms carbonic acid which corrodes the boiler slowly. CO2 + H2O H2CO3 CO2 is removed by adding calculated quantity of ammonia: 2 NH4OH + CO2 (NH4)2CO3 + H2O It is also removed by mechanical aeration along with oxygen.

c) Acids from dissolved salts: o Dissolved magnesium salts hydrolyse to form acids: MgCl2 + 2 H2O Mg(OH)2 + 2 HCl
o

This acid reacts with boiler and corrodes: Fe + 2 HCl FeCl2 + H2 FeCl2 + 2 H2O Fe(OH)2 + 2 HCl Small quantity of magnesium salts will large amount of boiler corrosion
21

Internal treatment methods for boiler feed water

o o o

Method is also called as Sequestration. Sequestration. Ions are complexed to give more soluble salts. salts. Internal treatment is carried out to: to: a) precipitate scale forming impurities into sludges which can be removed by blow-down (Partial removal of hard water from blowthe bottom of the boiler) b) convert scale forming impurities into compounds with higher solubility so that they remain in solution. solution.

The methods are: are: a) Colloidal conditioning b) Phosphate conditioning c) Carbonate conditioning d) Calgon conditioning e) Treatment with sodium aluminate (NaAlO2)
22

Internal treatment
a) Colloidal conditioning: o In low pressure boilers, scales are avoided by adding tannin, lignin, agaragaragar. agar.
o

These form a layer on the scale forming materials and loose precipitates are formed which can be easily removed by blow down. down.

b) Phosphate conditioning: conditioning:

o

In high pressure boilers, scales are avoided by adding sodium phosphate. phosphate. This converts the scale forming impurities to soft sludge of calcium and magnesium phosphate which can be removed by blow down. down. 3 CaCl2 + 2 Na3PO4 Ca3(PO4)2 + 6 NaCl

The phosphates used are: are: i) NaH2PO4 ii) Na2HPO4 iii) Na3PO4 (acidic) for highly alkaline water (weakly alkaline) for medium acidic/alkaline water (alkaline) for highly acidic water

Internal treatment
c) Carbonate conditioning:
o

In low pressure boilers, Na2CO3 is added to the water to convert CaSO4 into CaCO3 so that CaSO4 scale formation is avoided. avoided. CaSO4 + Na2CO3 CaCO3 + Na2SO4

CaCO3 forms sludge and is removed by blow down. down.

d) Calgon conditioning: conditioning:

o o

Sodium hexa meta phosphate (NaPO3)6 is Calgon. Calgon. When added to water, it prevents formation of scales and sludges by forming a soluble complex with CaSO4. Na[Na4(PO3)6] 2 CaSO4 + [Na4P6O18]22 Na+ + [Na4P6O18]2[Ca2P6O18]2- + 2 Na2SO4 Soluble complex ion
24

Internal treatment
e) Treatment with sodium aluminate(NaAlO2):
o

NaAlO2 hydrolyses with water to precipitate Al(OH)3 : NaAlO2 + 2 H2O NaOH + Al(OH)3

NaOH formed reacts with magnesium salts to yield Mg(OH)2 Gelatinous ppt. MgCl2 + 2 NaOH Mg(OH)2 + 2 NaCl
o

The Mg and Al hydroxides trap suspended impurities including oil drops and silica in the sludge. This sludge is removed easily by blow down operation.

f) Electrical conditioning (using sealed electric bulbs), Radioactive conditioning (using radioactive salt tablets) and complexometric method (form stable and soluble complexes) are other internal treatment methods. methods.

25

Water Softening methods

1. Lime soda a) Batch process b) continuous process - Cold lime-soda lime- Hot lime-soda lime2. Zeolite (permutit process) 3. Ion-exchange Ion4. Mixed bed ion-exchange ion26

Reactions of lime and soda

a. Reaction of permanent calcium:
Ca2+ + Na2CO3 Mg2+ + Ca(OH)2 Ca2+ + Na2CO3 CaCO3 + 2Na+ Ca2+ + Mg(OH)2 CaCO3 + 2Na+

b. Reactions of permanent magnesium:

(exc. Reaction of HCO3- (ex-Na2CO3):

2 HCO3+ Ca(OH)2 CaCO3 + H2O + CO32-

d. Reaction of Ca(HCO3)2 : Ca(HCO3)2 + Ca(OH)2 e. Reaction of Mg(HCO3)2 : Mg(HCO3)2 + 2 Ca(OH)2 Mg(OH)2 2 CaCO3 + 2 H2O +
27

2 CaCO3 + 2 H2O

Reactions of lime and soda

f. Reaction of CO2:
CO2 + Ca(OH)2 g. Reaction of H+: 2 H+ + Ca(OH)2 Ca2+ + Na2CO3 h. Reactions of coagulants: i) Reaction of FeSO4: Fe2+ + Ca(OH)2 Fe(OH)2 + Ca2+ 2 Fe(OH)3 CaCO3 + 2 Na Fe(OH)2 + H2O + O2 Ca2+ + Na2CO3 Ca2+ + 2 H2O CaCO3 + 2 Na+ CaCO3 + H2O

ii) Reactions of Aluminium sulphate (Al2(SO4)3 : 2 Al3+ + 3 Ca(OH)2 3 Ca2+ + 3 Na2CO3 2 Al(OH)3 + 3 Ca2+ 3 CaCO3 + 6 Na+

iii) Reactions of sodium aluminate (NaAlO2): NaAlO2 + H2O Al(OH)3 + NaOH

A. Lime [Ca(OH)2]requirement : 74
100

{ Temp. Ca2+ + 2 temp. Mg2+ + Perm(Mg2+ + Al3+ + Fe2+)

+ CO2 + H+ + HCO3- - NaAlO2

B. Soda[Na2CO3] requirement :
106 + Al3+) + H+ - HCO3-

{
29

{ Perm. (Ca2+ + Mg2+ Fe2+ 100

30

o Hot lime-soda process consists of three parts:

a) Reaction tank to mix all ingredients b) Conical sedimentation vessel where the sludge settles down

c) Sand filter where sludge is completely removed

31

Advantages of hot lime-soda process limeo The precipitation reaction is almost complete o Reaction takes place faster o Sludge settles down rapidly; No coagulant is needed o Dissolved gases (which may cause corrosion) are removed o Viscosity of soft water is lower, hence filtered easily o Residual hardness is low compared to cold lime-soda process

32

o Advantages of Lime soda process:

1. 2. 3. 4. Economical Process improves the corrosion resistance of water Mineral content of water is reduced pH of water raises thus reducing content of pathogenic bacteria 5. No skilled labour is required

o Disadvantages of Lime soda process:

1. Huge amount of sludge is formed and its disposal is difficult 2. Due to residual hardness, water is not suitable for high pressure boilers

33

Permutit or Zeolite Process

o

Zeolite is hydrated sodium aluminium silicate having a general formula, Na2OAl2O3.xSiO2.yH2O. It exchanges Na+ ions for Ca2+ and Mg2+ ions. ions. Common Zeolite is Na2OAl2O3.3SiO2.2H2O known as natrolith. natrolith. Other gluconites, green sand (iron potassium phyllosilicate with characteristic green colour, a mineral containing Glauconite)etc. Glauconite)etc. are used for water softening. softening. Artificial zeolite used for water softening is Permutit. Permutit. These are porous, glassy particles having higher softening capacity compared to green sand. sand. They are prepared by heating china clay (hydrated aluminium silicate), feldspar (KAlSi3O8-NaAlSi3O8 CaAl2Si2O8) are a group of rock-forming tectosilicate minerals which make up as much as rock60% 60% of the earths crust) and soda ash (Na2CO3)
34

o o

o o

Zeolite process
o

Method of softening: Na2Ze + Ca(HCO3)2 Na2Ze + Mg(HCO3)2 Na2Ze + CaSO4 Na2Ze + CaCl2 2 NaHCO3 + CaZe 2 NaHCO3 + MgZe 2 Na2SO4 + CaZe 2 NaCl + CaZe

Regeneration of Zeolite: CaZe (or) MgZe + 2 NaCl Brine solution Na2Ze + CaCl2 or MgCl2

35

Zeolite Process
o

Advantages:
o o o o o o

Residual hardness of water is about 10 ppm only Equipment is small and easy to handle Time required for softening of water is small No sludge formation and the process is clean Zeolite can be regenerated easily using brine solution Any type of hardness can modifications to the process be removed without any

Disadvantages:
o

Coloured water or water containing suspended impurities cannot be used without filtration Water containing acidic pH cannot be used for softening since acid will destroy zeolite.
36

IonIon-Exchange Process
Iono Ion-exchange resins are cross linked long chain polymers with microporous structure. structure. o Cation exchange resins will exchange cations with H+. o Anion exchange resins will exchange anions with OH-. o Functional groups present are responsible for ion-exchange ionproperties. properties. o Acidic functional groups (-COOH, -SO3H etc.) exchange H+ for etc. cations & o Basic functional groups (-NH2, =NH etc.) exchange OH- for etc. anions. anions.
37

IonIon-Exchange Process
A. Cation-exchange Resins(RH+): - Styrene divinyl benzene copolymers - When sulphonated, capable of exchange H+

38

IonIon-Exchange Process
B. Anion-exchange resins (R OH):
- Styrene divinyl benzene copolymers or amine formaldehyde copolymers with NH2, QN+, QP+, QS+, groups. - On alkali treatment, capable of exchange of OH-

Anion Exchange resin

39

IonIon-Exchange Process
The Process of Ion-exchange is:
2 RH+ + Ca2+/Mg2+ ROH+ ClR2Ca2+/R2Mg2+ + 2 H+ (Cation exchange) R+ Cl+ OH(anion exchange) (anion exchange) (anion exchange)

2 R OH- + SO422 R OH- + CO32Finally, H+ + OH-

R 2 SO42- + 2 OHR 2 CO32- + 2 OHH2O

Regeneration of exhausted resins: Saturated resins are regenerated: R2Ca2+/R2Mg2+ + 2H+ 2 RH+ + Ca2+/Mg2+ (cation) (Stong acid) (washings) 2 R OH- + SO42(Strong base) (washings)
40

R 2 SO42- + 2 OH-

IonIon-exchange process

Note: Hard water should be first passed through the cation exchanger and then Anion exchanger to avoid hydroxides of Ca2+ and Mg2+ getting formed
41

42

Mixed bed ion-exchanger iono Contains intimate mixture of cation and anion exchangers o Water is in contact for a no. of times with the two exchangers alternatively Anion exchanger (low density) NaOH

Mixed Mixed ionizer ionizer bed bed

Exhausted mixed ionizer bed

Cation exchanger (higher density) Backwash water

H2SO4

Raw water inlet

Comp. air

Deminaralised water

Washings to sink
43

Advantages & Disadvantages of ionion-exchange process

o

Advantages:
- Can be used for highly acid and highly alkaline water - Residual hardness of water is as low as 2 ppm. - Very good for treating water for high pressure boilers

Disadvantages:
- Expensive equipment and chemicals - Turbidity of water should be < 10 ppm. Otherwise output will reduce; turbidity needs to be coagulated before treatment. - Needs skilled labour

44

Treatment of water for municipal supply

o

Drinking or potable water should be safe to drink and should satisfy the following requirements:
Sparklingly clean and odourless Pleasant in taste Perfectly cool Turbidity should not exceed 10 ppm. Free from objectionable minerals like Pb, As, Cr and Mn Free from dissolved gases like H2S Alkalinity should not be too high (pH should be around 8.0) Should be reasonably soft TDS should be less than 500 ppm Free from pathogenic microorganisms

a) b) c) d) e) f) g) h) i) j)

45

Purification of water for domestic supply

The following are the steps of purification:
A. Removal of suspended impurities: a) Screening: Floating matter is filter through large screens having large no. Screening: no.
of holes. holes.

b) Sedimentation: To remove suspended particles, water is allowed to Sedimentation:

stand in big tanks where suspended matter settles down in the bottom. bottom. Supernatant water is pumped off. off. If water contains colloidial and fine clay particles, a coagulant is added during sedimentation and the process is called Sedimentation with coagulation . Coagulant such as alum or ferrous sulphate will form insoluble gelatinous ppts. ppts. and settle them down in the bottom. bottom. Alum (K2SO4.Al2(SO4)3.24H2O, Sodium Aluminate (NaAlO2) and Ferrous 24H sulphate (FeSO4.7H2O) are normally used coagulants. coagulants.
46

Purification of water for domestic supply

e) Filtration: Filtration is a process of removing colloidal matter, most of the microorganisms etc. Filtration is carried out using Sand Filter bed containing coarse and fine sand layers through which water is passed. The irregular pores in the sand filter hold the sedimented materials etc., allowing water without these impurities to pass through. f) Removal of microorganisms: The process of destroying pathogenic microorganisms etc., from water is called Disinfection. Disinfection can be carried out by:
1.

By boiling: Boiling for 15 minutes to kill all microorganisms. This cannot prevent growth of microrganisms again. By adding bleaching powder:1 kg. of bleaching powder is added per powder:1 1000L of water and allowed to stand for several hours. CaOCl2 + H2O Cl2 + H 2O Ca(OH)2 + Cl2 HCl + HOCl (Hyporhlorous acid) microorganisms are killed
47

2.

Microorganisms + HOCl

Drawbacks: Bleaching powder introduced calcium to water increasing the hardness. Bleaching powder deteriorates on storage for a long time Excess beaching powder will gives bad taste and smell to the water. 3. By Chlorination: Chlorine (gas or concentrated liquid) produces hypochlorous acid which destroys the microorganisms Cl2 + H2O HOCl HOCl + HCl

H+ + OCl- (Hypochlorite ion)

This HOCl inactivates the enzymes of microorganisms. By Liquid chlorine: Liquid chlorine is found to be most effective and most widely used disinfectant throughout the world. A Chlorinator is used for adding adequate quantity of chlorine so that the residual chlorine is 0.1 to 0.2 ppm. in treated water. While chlorination, time of contact (depends on no. of microorganisms) temperature of water (higher temperature will kill microrganisms faster) pH of water (lower pH of water, say 5-6.5, needs lower contact time) 548

Diagram of chlorinator
Raw water inlet Concentrated chlorine solution

Baffle plates

High tower

Sterilized water outlet

49

Chlorination of water
Advantages of chlorine:
o o o o o

Effective and economical Needs very little storage space Chlorine is stable and does not deteriorate Can be used at low and high temperatures Does not introduce any salt impurities to water

Disadvantages of chlorine:
o o o o

Excess of chlorine produces characteristic smell and taste It also causes irritation to mucus membrane Residual chlorine should not exceed 0.1-0.2 ppm. 0.1It is most effective below pH 6.5 and not very effective at higher pH.

BreakBreak-point chlorination
Oxidn. Of reducing compounds by chlorine

Formation of chlorochloro-organic compounds and chloramines

Destruction of chlorochloroorganic compounds and chloramines

Free residual chlorine

Residual chlorine

a Applied dosage of chlorine

51

Advantages of break point chlorination

1.

Oxidises the organic compounds, ammonia and other reducing compounds completely Removes colour from water Destroys 100% of the microorganisms 100% Removes bad smell and taste of water

2. 3. 4.

Dechlorination: Dechlorination: Excess chlorine beyond the break-point produces bad taste and smell. breaksmell. Excess chlorine can be removed by: by:
a) b) c)

Passing the excess chlorinated water through a bed of carbon Adding activated carbon and allowing a short reaction time Adding small quantities of sulphur dioxide or sodium sulphite or sodium thiosulphate: thiosulphate: SO2 + Cl2 + 2H2O Na2SO3 + Cl2 + 2H2O Na2S2O3 + Cl2 + H2O H2SO4 + 2 HCl Na2SO4 + 2 HCl Na2SO4 + 2 HCl + S
52

Disinfection of water
4. By using chloramine (ClNH2):
o

When chlorine are added in the ratio of 2:1, chloramine is formed. formed. Cl2 + NH2 ClNH2 + HCl

Chloramine is more reactive than chlorine alone and is a better bactericidal agent than chlorine. chlorine. ClNH2 + H2O HOCl + NH3

Chloramine does not produce any bad smell and also adds good taste to water. water.

5. Disinfection by Ozone: Ozone:

o o

Ozone gas is a very good disinfecting agent. agent. Zone is unstable and breaks down to give nascent oxygen. oxygen. O3 O2 + [O]

o o o

This nascent oxygen is a powerful disinfecting agent and kills all the microorganisms. microorganisms. The disadvantage is that the method is very expensive. expensive. Advantage is that it removes colour, smell and taste without giving any residue. residue.

53

Diagram of Ozone sterilizer

Raw water inlet Ozone inlet

Disinfected water outlet

Contact tank

54

Flow diagram of municipal water treatment

Raw water Alum

Sand filter Mixing tank Fine sand Coarse sand gravel Liquid chlorine To Supply

55

Desalination of brackish water

o Water containing dissolved salts with a peculiar salty (brackish) taste is brackish water o The process of removing common salt from water is desalination The methods of desalination are: 1. Electrodialysis 2. Reverse osmosis
1. o

Electrodialysis: Electrodialysis consists of a large container with two membrane separators, one permeable to positive ions and the other permeable to negative ions. ions. In the outer compartments anode and cathode are arranged to pass DC Voltage. Voltage. When DC voltage/current is passed through the cell, Na+ will move towards cathode and Cl- will move towards anode through the membrane. membrane. Hence, the concentration of salt decreases in the compartment and increases in the side compartments. compartments. middle

Water from the middle compartment is collected and this water is desalinated water. water.
56

Electrodialysis diagram

For efficient separation, ion-selective membranes are used which ionselectively allow cations or anions to pass through them.
57

Electrodialysis cell
o Electrodialysis cell consists of Large number of pairs of rigid Plastic membranes. membranes. Saline water at a pressure of 5-6 kg/cm2 is passed through the membrane pairs. pairs. DC current is applied perpendicular to direction of water flow. flow.

the

Advantages are: are: 1. Unit is compact and installation is economical 2. Best suited if electricity is available. available.
58

Reverse osmosis
oWhen two solutions of unequal concentrations are separated by a Semipermeable membrane, solvent will flow from lower conc. to higher conc. oThis phenomenon can be reversed (solvent flow reversed) by applying hydrostatic pressure on the concentrated side oIn reverse osmosis, pressure of 15-40 kg/cm2 is applied to sea water. oThe water gets forced through the semipermeable membrane leaving behind the dissolved solids.
59

Advantages of Reverse Osmosis

o Advantage is in removing ionic, non-ionic, colloidal and high molecular wt. organic matter. o It removes colloidal demineralisation) silica (which is not removed during

o Cost is only the replacement cost of membranes (life is 2 years) o Membrane replacement is fast and hence uninterrupted water supply can be ensured o Because of the above reasons this process is being adopted for converting sea water into potable water and for high pressure boilers.
60

Estimation of water hardness

1. EDTA method 2. Alkali titration method 1. EDTA method:
o

Ethylene diamine tetraacetic acid disodium salt (EDTA disodium salt) is used as a strong complexing agent with Ca2+ and Mg2+ in hard water. water. The structure of EDTA disodium salt is: is: NaOOCH2C N HOOCH2C CH2 CH2 N CH2COONa CH2COOH

Initially, Ca2+ and Mg2+ are treated with Eriochrome black T (EBT) indicator using ammonia buffer (to maintain pH between 9-10) to get an 10) unstable complex of Ca2+ and Mg2+ formed with EBT. EBT. Ca2+/Mg2+ + EBT
pH 9-10

Ca2+/Mg2+ EBT (unstable complex wine red)

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EDTA method of water hardness estimation

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After titration with EDTA, EBT gets replaced with EDTA since EDTA forms a stronger complex with the metal ions. This is indicated by the formation of a steel blue coloured complex. Ca2+/Mg2+ EBT + EDTA
pH 9-10

Ca2+/Mg2+

EDTA

+ EBT

(Stable complex - Steel blue) Procedure:

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First EDTA Solution is standardized using standard hard water (1 mg/ml of CaCO3 equivalents is prepared as standard hard water). water). For this, first known aliquot of Standard hard water is taken and 10-15 mL of 10ammonia buffer is added to bring the pH between 9-10. 10. Then a few drops of EBT solution is added to form the unstable complex giving wine red colour. colour. This solution is titrated with the EDTA solution till the solution turns to steel blue indicating the formation of stable EDTA-Metal ion complex. EDTAcomplex. This volume of EDTA is noted as V1. The above procedure is repeated with sample hard water of unknown hardness. hardness. Volume of EDTA is noted as V2.
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EDTA method of water hardness estimation

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Then sample hard water of 250 mL is taken and evaporated to a volume of 50mL 50mL when the temporary hard salts settle down. down. The solution is filtered and washed thoroughly and made up again to 250mL. 250mL. From this solution, 50 mL is pipetted out and titrated in similar manner as done with standard hard water. water. Volume of EDTA is noted as V3.

Calculations: Calculations: a) Total hardness: hardness:

V1mL of EDTA is consumed by 50 mL of std. hard water std. V1mL of EDTA 1 mL of EDTA = = 50 mg of CaCO3 50/V1 mg of CaCO3 50/V

EDTA consumed by sample hard water = V2 mL So, V2 mL of EDTA = 50/V1 x V2 mg of CaCO3 50/V Hence, 50 mL of sample hard water contains 50/V1 x V2 mg of CaCO3 50/V Therefore, 1000mL of sample hard water 1000mL = 50/V1 x V2 x 1000 mg/L 50/V i.e. Total hardness of sample hard water = V2/V1 x 1000 mg of CaCO3 (ppm.63 (ppm.)

EDTA method of water hardness estimation

Permanent hardness: 50 mL of sample hard water after removing temporary hardness consumed V3 mL of EDTA. 1 mL of EDTA Therefore, = 50/V1 mg of CaCO3

V3 mL of EDTA = 50/V1 x V3 mg of CaCO3

50 mL of sample hardwater after boiling contained 50/V1 x V3 mg of CaCO3

50 Therefore, 1000 mL of sample hard water contains V3 V1 V1

V3 50

X 1000mg/L

Permanent hardness

X 1000 mg/L of CaCO3 (ppm.)

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EDTA method of water hardness estimation

Temporary hardness:
Temporary hardness = Total hardness permanent hardness

V1

X 1000

V1

X 1000

= 1000 X

[[[[

[[[[

V1

V1

= 1000 X

V1

{ {

V2 V3

{ {

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V2

V2

ppm.

{ {
ppm.
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{ {

V2

V3

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