Unit - 1

Water (H2O)
Impurities in natured water
The natural water contains the following impurities

1) Suspended Impurities
i) The insoluble impurities floating on the surface of water and present
inside the water are known as suspended impurities.
ii) Natural water contains solid particles having specific gravity greater
than 1 and size greater than 10-4 an called as suspended impurities.
iii) for example, leaves, branches of trees, pieces of wood blades of grasses,
sand, clay, fine silica, soil and organic matter.
iv) These impurities cause the change in colour, odour, taste and turbidity
to the water.
v) These, impurities can be removed by sedimentation filtration,
coagulation

2) Colloidal impurities
i) Natural water contains solid particles having specific gravity less than
1 and size between 10-5 to 10-7 are called as colloidal impurities.
ii) Example, fine clay particles soil and organic particles
iii) These impurities cause the turbidity, change in colour odour and taste
of water.
iv) These impurities are removed by coagulation.

3) Dissolved impurities
i) Natural water contains dissolved impurities like salts and gases.
ii) For e.g. salts of Ca, Mg, Na, K, Al, Fe etc in the form of their chlorides,
sulphates, carbonates & bicarbonates. It also contains gases like. O 2,
Co2, H2S and NH3 etc.
iii) These impurities cause acidity, alkalinity & hardness to H2o
1....
iv) They can be removed by chemical methods, like soda-ashprocess,
Zeolite process, ion exchange process and reverse osmosis (R.O)
process.

4) Biological impurities
i) Natural water contains suspended biological impurities.
ii) For e.g. bacteria and micro- organisms, vegetables and small animals
etc. as well as algae, fungi, protozoa etc.
iii) These impurities can cause, change in colour, taste, acidity, various
water borne disease and pollution to the water.
Water borne diseases are cholera, Dysentery, Typhoid fever,
Gastroenteritis, Hepatitis A and polio.
iv) These impurities are removed by sterilization (chlorination)

Acidity of water
i) The acidity of water is the capacity to neutralize the given standard
alkali or base. It is measure of acids present in water
ii) Natural water becomes acidic due to addition of (i) acidic salts, (ii)
acidic gases, (iii) acidic industrial waste water
iii) The acidity of water mainly increase due to dissolved Co 2 in the water
which forms carbonic acid.
H2O+Co2  H2 Co3 (carbonic acid)
H2 Co3  H+ + HCo-3
HCo-3  H++Co3--
iv) Also dissolved H2S gas forms H2So4 acid and some organic matter on
decomposition forms organic acids making water acidic
v) Acidic water is unsuitable for domestic and industrial applications. It
increases the corrosion of metals so, it is necessary to find out the
acidity of water.
vi) If water is acidic it can be neutralized by adding alkalis.

2....
vii) The acidity of water is determined by using acid base titration. Water is
titrated with standard. Alkali in presence of indicators phenolphthalein
(pH-8.3) and methyl orange (4.4)
viii) Phenolphthalein indicator determines total acidity and methyl orange
determines mineral acidity of water
ix) The acidity of water can be expressed in terms of CaCo 3 equivalent in
ppm.
Normality of std. alkali x volume of alkali x 50x1000
Acidity = --------------------------------------------------------------------------
Volume of water sample taken
Total Acidity :
Take 100 ml of water sample in a tall cylinder to decree the surface and
minimize the loss of dissolved carbonic acid during titration. Now add few
drops of phenolphthalein as indicator and titrate the sample very rapidly
against 0.02 N NaOH with constant stirring until a faint pink colour is
obtained.

Alkalinity of water
1) The alkalinity of water is the capacity to neutralize the given standard
acid or it is the measure of alkalis present in water
2) Water becomes alkaline due to the addition of (i) Alkaline salts (ii)
Alkaline gases (iii) Alkaline waste water
3) Highly alkaline water causes the scale and sludge formation in the
boiler. Alkaline water is unsuitable for domestic and indusrial use.
4) Depending on the type of ion alkalinity is classified.
a) Hydroxide alkalinity - due to O-H ion
b) Carbonate alkalinity - due to Co3-- ion
5) Alkalinity can also be classified as
i) Caustic alkalinity - NaoH or KOH, Na2Co3 or K2Co3, MaHCo3 or KHCo3
ii) Temporary alkalinity - due to Ca(HCo3)3 and Mg(HCo3)2

3....
6) Alkalinity of water is determined by using acid base titration water
sample is titrated against standard acid by using phenolphthalein and
methyl orange indica
7) The reactions taking place are as below
H+ + O-H  H2O
H++ Co3--  HCo3-
H++ HCo3-- H2 Co3
H2Co3  H2O + Co2
8) Phenolphthalein indicator determine caustic alkalinity and methyl
orange indictor determines total alkalinity
9) To find out the alkalinity standard acid is taken in burette and water
sample is in titration flask by pipette.
10) To the water sample phenolphthalein is added and end point V 1ml is
obtained to the same flask then methyl orange is added and addition of
ctd. Acid is continued and second end point V1+V2 ml is obtained.
11) Phenolphthalein alkalinity (p) in terms of CaCo3 equivalent
(end point - pink to colourless)
Normality of acid x V1 x 50 x 1000
P= --------------------------------------------------- in ppm
Volume of water taken
12) Methyl orange alkalinity (M) in terms of CaCo3 equivalent
(end point - Yelow to orange colour)
Normality of acid x (V1 + V2) x 50 x 1000
M= --------------------------------------------------------- in ppm
Volume of water sample taken

Chlorides in water
1) The amount of chloride ions present in natural water is called as
chloride content of water.
2) The various rocks and soil contain a large amount of solid minerals and
salts as chloride. As the rain water comes in contact with these rocks
then various chloride salts dissolved in it.

4....
3) The chloride ions present in natural water is in the form of CaCl 2,
MgCl2, MgCl2, NaCl, KCl, AlCl3, FeCl3
4) If amount of free chlorine is present beyond the certain limit, water
becomes unfit for drinking purposes. Similarly if chloride ions are more
in water it increases corrosion of metals. So it is necessary to estimate
the chlorine content in water.
5) The chlorides of water is determined by using precipitation titration.
6) The drinking water is disinfected by chlorine to remove the bacteria,
fungi and other micro- organisms.
7) In precipitation titration water sample is titrated against a standard
solution of silver nitrate in presence of potassium chromate as an
indicator.
8) The reactions in this titration are as follows
NaCl + AgNo3  AgCl + NaNo3
When all of the chloride ions are removed completely the excess of
AgNo3 reacts with K2CrO4 to form brick red precipitate of silver
chromate (Ag2CrO4) indicating the end point of titration.
2AgNo3+ K2CrO4  Ag2CrO4+ 2KNO3
brick red
ppt
9) Suppose Vml of standard AgNo3 required
Vx Normality of AgNo3 x 35.5 x 1000
Chloride content = ----------------------------------------------------
Volume of water sample taken

Ill effect of high chloride content

If chloride content of water exceeds 200 ppm then it causes various ill
effects as mentioned below
1) High amount of NaCl or KCl makes the water saline. Such water is not
suitable for domestic, industrial and agricultural use.

5....
2) High amount of CaCl2 and MgCl2 salts makes the water hard. The hard
water is not suitable for steam generating boilers because it causes
scale and sludge formation in boilers.

Dissolved Oxygen (DO)

1) The amount of free oxygen present in natural water in dissolved state
is called as dissolved oxygen.
2) Dissolved oxygen is very corrosive to the metals like iron, steel, brass
etc. If it is less in water it becomes harmful to the living organism.
3) Dissolved oxygen is usually determined by Winkler's method i.e. by
audiometric titration.
4) In this titration water sample is treated with 10% KI solution which
librates the equivalent amount of iodine.
5) The liberated Iodine is then titrated against std Na 2S2O3 solution using
starch as an Indicator. End point of titration is blue to colourless.
6) Molecular oxygen is not capable to react with KI solution, so water
sample is treated with MnSO4 presence of alcoholic NaOH solution and
then with H2SO4. This convert molecular oxygen to nascent oxygen.
7) The chemical reactions in this titrations are
MnSO4 + 2NaOH  Mn(OH)2 + Na2SO4
2Mn(OH)2+ O2  2MnO(OH)2 (Manganese oxide)
MnO(OH)2 + H2SO4  MnSO4 + 2H2O+(O) nascent oxygen
2KI+ H2SO4 + (O)  K2SO4 + H2O + I2
2Na2S2O3 + I2  2NaI + Na2S4O6
Starch + I2  Starch iodide (blue)
8) Some times water contains nitrites, sulfites etc. which gives wrong
results in the determination of oxygen content. To avoid this sodium
oxide is added to the water. It decomposes the nitrites and sulfites.
9) If vml of sodium thiosulpahte used by water sample to give end point,
then D.O. is calculated as
6....
 Normality of Na2S2O3 x Vml of Na2S2O3 x 8 x 100
Dissolved oxygen (D.O.) =--------------------------------------------------------------
Volume of water sample taken
10) D.O. is required for aquatic plants and animals but causes corrosion
Hence, we have to analyses the water for D.O.
Total salts, total dissolved salts and total suspended salts
TS = Total Salts
TDS = Total Dissolved Salts
TSS = Total Suspended Salts
TS = TDS + TSS
TDS = TS - TSS, TSS= TS - TDS

1) Pure water is colorless, odourless and tasteless. It is a universal

solvent, therefore water has tendency to pick up and dissolve solid
impartialities.
2) The dissolved salts can be solid salts, metals, minerals cations and
anions etc.
3) The term total dissolved salts refer to carbonates, bicarbonates,
chlorides, sulphates and nitrates of Ca, Mg, Na, K, Amla and Fe and
small amount of dissolved organic matter in water.
4) TDS in water is due to many factors such as
a) Natural sources of water
b) Industrial waste water
c) Chemical used in water treatment
d) Nature of pipelines.
e) Agricultural run off
5) TS, TDS and TSS are determined by gravimetric methods.
6) In this method known volume of water sample is taken in known
weight of evaporating dish and water is evaporated and final weight is
taken. It is TS for this water sample should be taken without filtration.
7) for TDS procedure is same as above only filtered water sample is taken.

7....
8) (W2-W1) x 106
TS/TDS = -------------------------------------- in ppm
V ml of water sample taken
W1 = initial wt.of evaporating dish.
W2 = final wt. of evaporating dish
V = volume of water sample taken.
9) TDS limit is less than 500 mg/l for drinking water.
TDS is not health hazards, Higher TDS interfere in washing clothes.
High TDS corrode pipelines.
COD (Chemical oxygen Demand)

i) COD is defined as amount of oxygen required by the chemical

substance to decompose organic and inorganic oxidisable matter into
Co2 & H2O in waste water.

C6H2O6 + 6O2 microbes 6 CO2 + 6H2O + new microbes.

ii) Industrial or domestic waste water gets oxidized completely by std.

K2Cr2O7 in presence of H2So4, Ag2SO4, HgSo4 to produce Co2 & H2O

iii) The excess K2Cr2O7 remaining after 2hrs refluxion is titrated with
ferrous ammonium sulphate (FAS) using ferrion indicator end point is
blue to wine red.

iv) COD values determines the pollution of water if COD is high pollution
of water is high.

v) COD values are used for treatment of waste water which are greater
than BOD.

vi) Formula for COD.

(A-B) x N x8 x 1000
COD in ppm = ----------------------------------------
Volume of water sample taken

8....
 A= Ml of FAS used for distilled water
B= Ml of FAS used for waste water sample
C= Normality of FAS solution
D= Milliequivalent weight of oxygen

BOD (Biological Oxygen Demand)

1) BOD is defined as the amount of oxygen required by bacteria in

decomposing / oxidizing organic matter in waste water sample under
aerobic condition at 200C over a period of 5 days.

C6H12O6 + 6O2 microbes 6CO2 + 6H2O + new microbes.

2) This test mainly involve measurement of O 2 consumed by micro -

organism while sterlising organic matter under aerobic condition.

3) It is necessary to provide standard conditions of nutrient supply, pH,

and absence of microbial growth.

4) In waste water there are two major biodegradable compounds.

i) Decomposition of Carbonaceous compound.
ii) Decomposition of Nitrogenous compound.

5) BOD concentration of different sample.

Type of sample BOD in mg/L Remarks
Pure water 1-3 reasonable
River 5 - 20 tolerable
Sewage 50 - 100 very bad
Industrial waste 100 - 10000 extremely poor

Requirement for BOD

i) pH of water sample should be between 65 to 85

9....
ii) seeding some sample may be sterile add - seeds the purpose of seeding
is to introduce a biological population capable to oxidizing organic
waste.
iii) Lock of nutrient - add nutrient
iv) Presence of residential chlorine
v) High D-O up to gmg/L needed
vi) Presence of heavy metals Cu, Cr, pb partially inhibit O2 consumption.

Calculation

(D1 - D2) - (B1 - B2 ) x F

BoD5 mg/L = ---------------------------------------------
P

D1 = D.O. of sample bottle on 0th day

D2 = D.O. of sample bottle on 5th day
B1 = D.O. of blank bottle on Oth day
B2 = D.O. of blank bottle after 5th day
F = ratio of seed in diluted sample
P = decimal fraction of diluted water used.

Applications
1) To determine the strength of domestic and industrial waste in terms of
oxygen required for stabilization of waste.
2) To measure amount of biologically oxidisable organic matter present in
waste.
3) BOD is a major criteria in pollution control
4) BOD data are used to assess the self purification capacity of receiving
water bodies
5) Used for designing of waste water treatment plant like STP (sewage
treatment plant) and ETP (Effluent treatment plant)

10....
Hardness –Hardness is the tendency of water to resist foam formation

when soap solution is added.

1) When soap is dissolved in water then lather foam does not form
instead curd like insoluble substance is formed which is called as hard
water. Hard water contain soluble impurities of Ca & Mg

2) We use water for domestic purpose like cooking, cleaning, washing,

cloths, drinking and gardening etc. It is our observation that water
from certain wells do not produce foam with soap while some produce
foam with soap.

3) When soap is dissolved in water then foam is formed which is called

soft water e.g. water, distilled water.

Type of Hardness

There are two types of hard water.

1) Temporary/Carbonate/Alkaline Hardness
2) Permanent/non-carbonate/non-alkaline Hardness

1) Temporary Hardness
i) It is also called as carbonate and alkaline Hardness

ii) If the hardness of water is due to presence of carbonates (Co 32), and
bicarbonates (HCO3-) salts such as MgCo3, CaCo3, Mg(HCO3)2 and
Ca(HCO3)2 etc is called temporary hardness.

iii) CaCo3 and MgCo3 are slightly soluble.

iv) This type of hardness can be removed simply by boiling of water.

During boiling carbonates and bicarbonates are converted into
insoluble salt form such as (O-H)

11....
v) Insoluble salts can be removed by filtration process since hardness can
be removed by simple method it is called temporary hardness

heat
Mg(HCO3)2  Mg(OH)2  + 2Co2 
1000 C

heat
Ca(HCO3)2  Ca(OH)2  + 2Co2 
1000 C

heat
MgCo3 + H2O  Mg(OH)2  + 2Co2 
1000 C

heat
CaCo3 + H2O  Ca(OH)2  + 2Co2 
1000 C

2) Permanent Hardness

1) Permanent hardness is also called as non- carbonate or non - alkaline

hardness

2) Permanent hardness is due to dissolved salts of metals other than

carbonates and bicarbonates.

3) The salts which are present in water are generally nitrates, sulphates
and chlorides.

4) Permanent hardness causing salts are CaSO4, CaCl2, MgCl2, MgSO4, etc.

5) This hardness of water cannot removed just by boiling. It requires

special chemical treatment

6) Total hardness is sum of temporary and permanent hardness.

7) Units of hardness ppm or Mg/L

8) Quality of water Hardness in ppm CaCo3 equivalent

Soft Below 100 ppm
Moderately hard 100 - 250 ppm
Hard 250 - 350 ppm
Very hard Above 350 ppm

12....
 Sr Salts Molecular weight
No
1 Ca(HCO3)2 162
2 Mg(HCO3)2 146
3 CaSO4 136
4 MgSO4 120
5 CaCl2 111
6 MgCl2 95

Calculation
Amount of hardness causing substance x 100
Hardness in ppm = --------------------------------------------------------
Mol wt of hardness causing substance

Units of hardness

1) parts per million (ppm)

It is the parts of CaCo3 equivalent hardness per 106 parts of water

i.e. 1ppm = 1 part of CaCo3 equivalent hardness in 106 parts of water

2) Milligrams per liter (mg/L)

Mg/L is the number of milligrams of CaCo 3 equivalent hardness present

per liter of water.

1 mg/L = 1mg of CaCo3 equivalent hardness of 1 liter H2O

3) Clarkes degree (0Cl)

10 Cl= 1 part of CaCo3 equivalent hardness per 70000 parts of water

13....
4) Degree farenheight (0Fr)

It is part of CaCo3 equivalent hardness per 105 parts of water

10Fr = 1 part of CaCo3 hardness per 105 parts of water

1 ppm = 1 mg/Lit = 0.10 Fr = 0.070 Cl

Examples: -
1) Calculate temporary and total hardness of a sample of water containing
following salts.
Mg (HCO3)2 = 7.3 mg/lit., MgCl2 = 9.5 mg/lit.
Ca (HCO3)2 = 16.2 mg/lit., CaSO4 = 13.6 mg/lit.
Solution: Calculation of equivalent of CaCO3

1. Mg (HCO3)2  7.3 mg/lit., MgCl2 = CaCO3

7.3 x 100
= = 5 mg/lit.
146

2. Ca(HCO3)2  16.2 mg/lit. = CaCO3

16.2 x 100
= = 10 mg/lit.
162

3. MgCl2  9.5mg/lit = CaCO3

9.5 x 100
= = 10 mg/lit.
95

4. CaSO4  13.6 mg/lit. = CaCO3

13.6 x 100
= = 10 mg/lit.
136

Temporary Hardness = Ca(HCO3)2+Mg(HCO3)2

= 10 + 5
= 15mg/lit.
Permanent Hardness = MgCl2 + CaSO4

14....
 = 10 + 10
= 20mg/lit.
Total Hardness = Temporary Hardness + Permanent Hardness
= 15 + 20 = 35 mg/lit. or 35 ppm
_________________________________________________________________________________________

2) A sample of water on analysis was found to contain the following

impurities expressed in mig/lit
Ca (HCO3)2 = 10.0 mg/lit.,
Mg (HCO3)2 = 8.5 mg/lit.,
CaSO4 = 12.3 mg/lit.
MgSO4 = 14.0 mg/lit.
Calculate the temporary, permanent and total hardness of water in
mg/lit.
Solution : Calculation of equivalent of CaCO3
1. Ca (HCO3)2  10 mg/lit.,
10 x 100
= = 6.17 mg/lit.
162

2. Mg(HCO3)2  8.5 mg/lit.

8.5 x 100
= = 5.82 mg/lit.
146

3. CaSO4  12.0mg/lit
12.0 x 100
= = 8.82 mg/lit.
120

4. MgSO4  14.0 mg/lit.

14.0 x 100
= = 11.67 mg/lit.
120

Temporary Hardness = Ca(HCO3)2+Mg(HCO3)2

= 6.17 + 5.82 = 11.99mg/lit.

15....
 Permanent Hardness = CaSO4 + MgSO4
= 8.82 + 11.67 = 20.46 mg/lit.
Total Hardness = 11.99 + 20.46 = 32.48 mg/lit.
_________________________________________________________________________________________

_________________________________________________________________________________________
4) On analysis the water sample was found to contain the following
impurities expressed in mg/lit.
Ca(HCO3)2 = 12.0 mg/lit.
Mg (HCO3)2 = 10.0 mg/lit.
CaSO4 = 20.0 mg/lit.
MgSO4 = 9.0 mg/lit.
Calculate the temporary, permanent and total hardness of water
in degree French.
_________________________________________________________________________________________
5) A sample of water on analysis was found to contain the following
impurities.
Ca(HCO3)2 = 8.0 mg/lit.
Mg (HCO3)2 = 10.0 mg/lit.
CaSO4 = 6.0 mg/lit.
MgSO4 = 5.0 mg/lit.
Calculate the temporary, permanent and total hardness of water
in degree clerk,
_________________________________________________________________________________________
6) A sample of water on analysis was found to contain the following
impurities expressed in mg/lit.
Ca(HCO3)2 = 6.0 mg/lit.
Mg (HCO3)2 = 8.0 mg/lit.
16....
 CaCl2 = 7.0 mg/lit.
MgCl2 = 5.0 mg/lit.
CaSO4 = 4.0 mg/lit.
KCl=5.0 mg/lit
Calculate the temporary, permanent and total hardness of water
in mg/lit
_________________________________________________________________________________________
7) A sample of water on analysis was found to contain the following
impurities expressed in mg/lit.
Hardness Amount Mol.wt.
Ca(HCO3)2 9.00 162
Mg (HCG3)2 10.50 146
CaCl2 8.00 111
MgCl2 12.50 95

Calculate the temporary, permanent and total hardness of water in

mg/lit.
Hardness Amount Mol.wt.
Ca(HCO3)2 9.00 162
Mg (HCG3)2 10.50 146
CaCl2 8.00 111
MgCl2 12.50 95

Ill effecs of hard water in steam generation in boilers

When hard water is used in boilers in industry it may produce

following froubles.
a) Scale and Sludge formation
b) Priming and foaming
c) Boiler corrosion

17....
 d) Caustic embrittlement

a) Scales and Sludges

water
loose precipitate Boiler wall Hard adhering coating
suspended in on inner walls of boiler
water (sludge) (scale)

Heat Heat
MgSO4, MgCl2, CaCl2, MgCo3 CaCo3, Mg(OH)2, CaSo4

In a boiler water is continuously evaporated to form stem. This

increases the concentration of dissolved salts and gives scales and
sludges.

Scales

Hard deposits which stick very firmly to the inner surfaces of boiler are
called as scales.

Causes of scale formation

1) Decomposition of Ca(HCo3)2

Ca(HCO3)2  CaCO3 + H2O + Co2

Scale

2) Deposition of CaSO4

Solubility of CaSO4 in water decreases with increase in temp. so CaSO 4

gets precipitated as hard scale on inner part of boiler.

3) Hydrolysis of dissolved magnesium salts.

Dissolved magnesium salts get hydrolysed as

MgCl2 + 2H2O  Mg(OH)2 + 2HCl

Scale

4) Presence of Silica

18....
 If a small amount of SiO2 is present, it may deposite as calcium silicate
(CaSiO3) and MgSiO3. These stick firmly to inner wall of boiler.

Disadvantages of Scale formation

1) Wastage of fuel.

2) Lowering of boiler sefty

3) Decrease in efficiency

4) Danger of explosion

Prevention of scale formation

1) By using softened water for boilers

2) By adding organic substances

3) By adding sodium phosphate

4) By adding sodium Carbonate

Removal of scales

1) Mechanical Methods

2) Chemical Methods

Sludges

Sludge is soft, loose and slimy precipitates formed in the boiler. Sludge
is formed in colder portion of boiler and where flow rate is slow.

Causes of sludge formation

Sludges are formed by substances which have greater solubility in hot

water than in cold water e.g. MgSO4, MgCl2, CaCl2, MgCO3

19....
Disadvantages of sludge formation

1) Sludges are poor conductor of heat, so heat is wasted.

2) Excessive sludge formation disturbs working of boiler.

3) It settles in area of poor circulation such as pipe connection, thereby

blocking of pipe.

4) Sludges are trapped into scales and increase scaling.

Prevention of sludge formation

1) Using well softened water

2) Frequently blow down operation

Removal of sludge

Sludge can be easily scrapped out with wire brush.

Distinguish between scales and sludges

Scales
1) Scales are hard deposits
2) They stick very firmly to 2)
the inner surface of boiler
and are very difficult to
remove.
3) Formed by substance like 3)
Sludges
1) Sludges are soft, loose and
slimy precipitate.
They are non-adherent
deposits and can be easily
removed.
Formed by substances like
20....
 CaSo4, Mg(OH)2 etc CaCl2, MgCl2, MgSo4, MgCO3
etc.
4) Formed generally at 4) Formed at comparatively
heated portions of the colder portions of the
boiler boiler
5) Decrease the efficiency of 5) They decrease the
boiler and chances of efficiency of boiler but are
explosions are also there less dangerous
6) Cannot be removed by 6) Can be removed by blow
blow down operations down operation

b) Priming and Foaming

1) Priming

When steam is produced rapidly in the boilers, some droplets of

the liquid water are carried along with the steam. This process of 'wet
steam' formation is called preming.

Priming is caused by
1) presence of dissolved solids
2) High steam velocities
3) Sudden boiling
4) faulty design of boiler

Priming can be avoided by

1) Controlling repaid change in steaming velocities

2) Proper design of boilers
3) ensuring efficient softening
4) Filtration of the boiler water carried over to boiler

Disadvantages of priming

21....
1) More heat is required to adjust the steam pressure in boiler then
efficiency of steam production is lowered.
2) TDS and water may enter the machine part and lowers the life of it.
3) The level of water may not be judged in boiler.

2) Foaming
1) Production of persistent foam or bubbles in boiler which do not break
easily is called foaming.
2) Foaming is caused by presence of substance like oils.
3) Foaming is due to higher quantity of TDS matter in water which reduce
surface tension of water.

Foaming can be avoided by

1) Adding anti-foaming agent (Aluminum sulphate sodium aluminates)
2) Carrying blow-down operations.
3) removing oil from boiler water.

c) Boiler corrosion
Boiler corrosion is decay or disintegration of boiler body material
either due to chemical or electrochemical reaction with its
environment

Boiler corrosion occurs due to

i) Dissolved oxygen (O2)
ii) Dissolved carbon dioxide (CO2)
iii) Dissolved acidic substances.
iv) Dissolved alkaline substances.

Disadvantages of corrosion are

i) Shorting of boiler life.
ii) Leakages of the joints

22....
iii) increased costs of repairs and maintances.

d) Caustic embrittlement
i) It is type of boiler corrosion caused by using highly alkaline water in
boiler.
ii) In high pressure boiler Na2Co3 decomposes to give sodium hydroxide
(NaOH) and Co2. This NaOH corrode the boiler.
Na2Co3 + H2O  2NaOH + Co2

iii) NoOH attack surrounding part of boiler crack and dissolve iron metal
of boiler thus causes embrittlement of boiler parts particularly at
joints, bends etc.

Caustic embrittlement can be avoided by

i) using sodium phosphate as softening agent
ii) adding sodium sulphate to boiler water which blocks hair cracks.
iii) The alkalinity is adjusted to pH 7 to 9

Methods of treatment of hard water

1) Zeolite or permutit process
2) Ion exchange process
3) Reverse Osmosis process
Zeolite process

1) Zeolites are naturally occurring hydrated sodium alumino silicate

minerals (like Na2O, Al2O3, 6SiO2, 2H2O) cabaple of exchanging
reversibly its sodium ions for hardness producing ions in water.

2) Zeolits are of 2 types

23....
 a) Natrual Zeolites
b) Synthetic Zeolites

Process

1) Zeolite process is the modern method used for softening of hard water.

2) Zeolite holds Na+ ions loosely and can be simply represented as Na 2Ze
where Ze represented insoluble radical frame work.

3) Na2Ze are capable to exchange sodium ions with cations of Ca ++ and Mg+
+
ions.

4) Zeolite process consists of a cylindrical tank filed with sodium zeolite.

5) Tank has two inlets one for hard water and other for 10% brine (NaCl)
solution.

6) When hard water is passed through inlet of tank, it goes through

zeolite bed. This bed, removes all calcium and magnesium cations. In
zeoite bed reactions takes place as below.

Na2Ze + CaCH(O3)2  CaZe + 2NaHCO3

Na2Ze + MgCH(O3)2  MgZe + 2NaHCO3
Na2Ze + CaCl2/CaCo3  CaZe + 2NaCl/Na2CO3
Na2Ze + CaSO4/MgSO4  CaZe, MgZe + Na2SO4

All Ca++ & Mg++ reacted with Ze and remain in bed and soft water free
from Ca++, Mg++ comes and through bottom outlet

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Regeneration of Zeolite bed

i) After passing hard water through zeolity bed few hours later bed gets
deactivated. So to regenerate Ze brine solution (NaCl) is passed
through bed & again we get Na2Ze.

Reactions takes place as below

CaZe/MgZe+ 2NaCl  Na2Ze + CaCl2, MgCl2

Brine regenerated

Washing containing CaCl2 and MgCl2 are led to drain and regenerated
zeolite bed thus obtained is used again for softening purpose.

Advantages of Zeolite Process.

1) The hardness is completely removed and water of about 10ppm

hardness is produced.

2) The equipment used is compact and occupies less space.

3) It is quite clean and repaid process which requires less time for
softening
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4) for maintenance and operations less skilled person is needed.

5) Impurities are not precipitated, so there is no danger of sludge

formation.

6) The process automatically adjust itself to water of different hardness.

Disadvantages of zeolite process

1) The treated water contains more sodium salts

2) The method only replaces Ca & Mg ions by Na ions but leaves acidic
ions (like HCO3 & Co3 etc ) as such in softened water.

Limitations of Zeolite process

1) If the supply of water is turbid, suspended particles must be removed

by co-agulation filtration etc. before the water is passed to the zeolite
bed otherwise turbidity will clog the pores of zeolite bed making it
inactive.

2) If water contains large amount of coloured ions such as Mn 2+ & Fe2+.

They must be removed first because ions produce Mn & Fe zeolite
which cannot be easily regenerated.

3) Mineral acids if present in water regenerated bed so it must be

neutralized with soda before passing the water to softening plant.

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Ion exchange process
1) In ion exchange process ion exchange resins are used for softening of
hard water. Ion exchange process is also known as demineralization.
Resins are the insoluble, synthetic or natural polymers having
ionizable functioned groups and called as ion exchanges.

Ion exchanges are of two types

a) Cation exchange resins : These resins are capable to exchange

cations (Ca++ and Mg++) from hard water with H ions (R-H+)

b) Anion exchange resins : These resins are capable to exchange

anions (Cl-, So-4, HCo-- 3 ) from hard water with hydroxyl ions
(R+OH-)

2) The ion exchange resin can be represented as R+A- or R-A+

In this method cations present in water are removed using cation

exchange resin either in Na+ form or H+ form

2R-H+ + Ca2+  R2Ca + 2H+

2R-H+ + Mg2+  R2Mg + 2H+

Construction and working

It is possible to remove completely TDS from water using cation and anion
exchange resins and pure water is obtained.

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1) This method consists of two vessel connected to each other one
containing cation exchange bed and other containing anion exchange bed.

2) The first vessel has two stop cocks one for hard water inlet and other
for acid required for regeneration of cation exchanger.

3) Hard water is allowed to pass through cation exchange bed, then all
cations are removed then reaction takes place as below.

2R-H+ + Ca2+  R2Ca + 2H+

2R-H+ + Mg2+  R2Mg + 2H+

4) After removed of cations, water comes to the bottom of first vessel

from where it comes to top of second vessel. Which contains anion
exchange bed.

5) In anion exchanger bed all anions are removed, then reaction takes
place as below

R-OH + Cl-  RCl + O-H

2ROH + Co3--  R2Co3 + 2O-H

28....
 2ROH + So4--  R2So4 + 2O-H

6) Treated water comes to the bottom of second vessel and then comes to
top of third vessel. This vessel is fitted with degasifier unit to remove
Co2 to obtain deionised water. This water is pure water free from TDS.

Regeneration ion exchange bed

After long use resins lose the capacity of exchanging cation and anions.

a) To regenerate cation exchange bed, it is washed with HCl. When the

following reactions takes place.

R2Ca + 2HCl  2RH + CaCl2

R2Mg + 2HCl  2RH + MgCl2

After treatment of HCl cation exchange is repeatedly washed with

deionised water.

b) To regenerate anion exchanger bed, it is washed with dil NaOH

solution, then following reactions takes place.

RCl + NaOH  R-OH + NaCl

R2Co3 + 2NaOH  2ROH + Na2Co3

R2So4 + 2NaOH  2ROH + Na2So4

After treatment with NaOH anion exchanger bed is repeatedly washed

with deionised water.

After regeneration both beds can be used again

29....
Advantages

1) Height purity of water is obtained of hardness 2ppm only.

2) Process is useful for both acidic and alkaline water.

3) It is clean process because impurities like sludges do not form.

Disadvantages

1) Equipments are costly

2) The resin required for this method have high cost.

3) The turbid solution reduce output of process the turbidity should not
exceed 10ppm

4) If turbidity is higher should be removed by co-adulation first and then

used for ion exchange treatment.

Reverse osmosis method

1) Osmosis - The unidirectional flow of solvent through the semi
permeable membrane is called osmosis. Semi permeable membrane
allows solvent to flow through it but does not allow solute to pass
through membrane.

2) Reverse osmosis is the process of forcing solvent from a region of high

solute conc. Through a semipermeable membrane to a region of low
solute concentration by applying external pressure.

30....
 Diagram

a) RO consists of a tank with two compartments separated by special

semi permeable membrane.

b) The semi permeable membrane in RO is thin film of cellulose acetate or

polymethacrylate or polyamide polymer.

c) The membrane size is 50nm to 2 x 10-4nm. It allows to solvent to pass

but prevent the passage of solute. The membrane should be strong to
with stand the applied pressure.

d) In one Compartment Sea water or impure water is taken. In this

compartment solute concentration is high. This compartment high
pressure is applied with the help of piston.

31....
d) The pure water is forced through semi permeable membrane in other
compartment.

f) The ionic and non - ionic salts remain in first compartment.

g) The pure/desalined water coming out from RO system is corrosive. It is

stabilized adding lime or caustic (NaOH) to adjust pH 6.8 to 8.1 to
achieve potable water.

h) The water coming after pH adjustment is free from pathogenic

organism. But not bactaria, protozoa and viruses.

Disinfection is done by DV radiation from Dv lamp or chlorination process.

Advantages of RO process.

1) This method removes ionic, non - ionic matter as well as colloidal and
high molecular weight organic substances.

2) The maintenance cost is replacement of semi permeable membrane

which has life of two years.

3) The replacement time of membrane is small.

4) RO plants are used to convert sea water to drinking water.

5) The method uses no electricity and chemicals therefore, environmental

friendly.

Disadvantages of R.O. process

1) Method require pretreatment of feed water to remove species tht

adhere or precipitate, on membrane and foul its surface.

2) R.O. is not effective for removing dissolved gases.

3) Flow rate are usually limited.

4) pesticides, solvents, hydrogen sulphide (H2S) & chloramines can’t be

removed.
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