WATER CHEMISTRY

Water Technology
MODULE 1

MODULE 1
 WATER CHEMISTRY

MODULE-I

Introduction, Hardness of water, Numerical problems, Water analysis- complexometric

titration, Potable water treatment, Desalination Techniques, Boiler feed water - Boiler
Troubles, Water softening methods-internal and external softening methods.

MODULE 1
 WATER CHEMISTRY

Lecture-1

Hardness of Water-Causes, Types of Hardness, Degree of Hardness, Units,

Numerical Problems

Types of Water:

Water can be classified into two types. Water which gives lather easily with soap solution is called
SOFT WATER and which does not produce lather with soap solution readily is called HARD WATER.

Hardness:-

Hardness is a characteristic property of impure water that does not produce lather/foam with soap
but forms a white precipitate (scum).

Causes:

Hardness of water is due to the presence of dissolved salts ofCa2+ and Mg2+ions with bicarbonates
(HCO3-), sulphates (SO42-) and chlorides (Cl-) and few other soluble salts of heavy metal present in
water.

Methods to Detect Hardness:

A sample of hard water when treated with soap (sodium or potassium salt of higher fatty acid like
oleic, palmitic or stearic) does not produce lather with soap, but on the other hand forms a white
scum or precipitate. This is formed due to insoluble precipitate of Ca2+ and Mg2+ ions.
2C17H35COONa + CaCl2 (C17H35COO)2Ca↓ + 2NaCl
SodiumStearate (soap) Calcium stearate
(Scum, Insoluble precipitate)

2C17H35COONa + MgSO4 (C17H35COO)2Mg↓ + Na2SO4

Magnesium Stearate
(Scum, Insoluble precipitate)

Types of hardness:

1. Temporary Hardness:-

• It is caused due to the presence of dissolved bicarbonates of Ca, Mg and other heavy metals
and carbonate of Iron.
• It is also called carbonate or alkaline hardness.
• Temporary hardness can be removed by boiling of water. When bicarbonates are
decomposed, they yield insoluble carbonates or hydroxides, which are deposited as ‘crust’
at the bottom of the vessel, while carbondioxide is liberated.
Ca(HCO3)2 ∆ CaCO3↓ + H2O + CO2↑
(Soluble) (Insoluble)

HARDNESS MODULE 1 L1
 WATER CHEMISTRY

Mg(HCO3)2 ∆ Mg(OH)2↓ + 2CO2↑

(Soluble) (Insoluble)

2. Permanent Hardness:-

• It is due to presence of chlorides and sulphates of Ca, Mg, Fe and other heavy metals.
• It is also called non-carbonate or non-alkaline hardness.
• It cannot be removed by boiling.
• It can be removed by techniques like, Lime Soda process, Ion exchange process, Zeolite
process, etc.
Na2Ze + MgCl2 MgZe + 2NaCl
Sodium Zeolite
CaSO4 + Na2CO3 Na2 SO4 + CaCO3 ¯
MgSO4 +Ca(OH)2 Mg(OH)2 ↓ + CaSO4

Total Hardness = Temporary Hardness + Permanent Hardness

Degree of Hardness or Expression of water

𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑖𝑛 𝑡𝑒𝑟𝑚𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡

𝑀𝑎𝑠𝑠 𝑜𝑓 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑖𝑛𝑔 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 × 𝐶ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑜𝑓𝐶𝑎𝑂
3
=
𝐶ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑜𝑓 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑖𝑛𝑔 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒

𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑖𝑛 𝑡𝑒𝑟𝑚𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡

𝑀𝑎𝑠𝑠 𝑜𝑓 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑖𝑛𝑔 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 × 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝑂
3
=
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑖𝑛𝑔 𝑠𝑎𝑙𝑡

Why CaCO3 is used for estimation of hardness?

The concentrations of hardness as well as non-hardness constituting ions are usually expressed in
terms of equivalent amount of CaCO3. The choice of CaCO3 in particular is due to its molecular
weight 100 (equivalent weight = 50), makes the calculation easier and it is the most insoluble salt
that can be precipitated in water treatment.

Unitsofhardness:-

1. Parts Per Million (ppm):-Number of parts of CaCO3 equivalent hardness per 106 parts of water

2. Milligrams Per Litre (mg/L):- Number of milligrams of CaCO3 equivalent hardness present per
liter of water.

3. Degree Clarke(oCl):-Number of parts of CaCO3 equivalent hardness per 70,000 parts of water.

4. Degree French (oFr):-Number of parts of CaCO3 equivalent hardness per 105 parts of water.

Relationship between various units of hardness:

1ppm = 1mg/L = 0.1oFr = 0.07oCl

HARDNESS MODULE 1 L1
 WATER CHEMISTRY

Problems:
1. Calculate total, temporary and permanent hardness of water sample containing
Mg(HCO3)2=7.3 mg/L, Ca(HCO3)2= 16.2 mg/L, MgCl2 = 9.5 mg/L, CaSO4 =13.6mg/L.
Solution: Conversion into CaCO3equivalents:

Constituent Multiplication factor CaCO3 equivalent

Mg(HCO3)2=7.3mg/L 100/146 7.3 x 100/146=5mg/L

Ca(HCO3)2=16.2mg/L 100/162 16.2 x 100/162=10mg/L

MgCl2=9.5mg/L 100/95 9.5 x 100/95=10mg/L

CaSO4=13.6mg/L 100/136 13.6 x 100/136=10mg/L

Temporary hardness of water due to Mg(HCO3)2and Ca(HCO3)2 = 5+10=15mg/L

Permanent hardness due to MgCl2 and CaSO4 = 10+10=20mg/L or 20ppm.
Total hardness = Temporary hardness + Permanent hardness= 15+20=35 mg/L.

2. Calculate the temporary, permanent and total hardness of a water sample containing
Mg(HCO3)2= 73mg/L, Ca(HCO3)2=162mg/L, MgCl2= 95mg/L, CaSO4 = 136mg/L.
Solution: Calculation of CaCO3 equivalents:

Constituent Multiplication factor CaCO3 equivalent

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

Ca(HCO3)2=162mg/L 100/162 162 x 100/162=100mg/L

MgCl2=95mg/L 100/95 95 x 100/95=100mg/L

CaSO4=136mg/L 100/136 136 x 100/136=100mg/L

Temporary hardness of water due to Mg(HCO3)2and Ca(HCO3)2=100 + 50 = 150 mg/L

Permanent hardness due to MgCl2 and CaSO4 = 100+100=200 mg/L.
Total hardness ofwater=Temporary hardness + Permanent Hardness=150 + 200 = 3 0mg/L.

HARDNESS MODULE 1 L1
 WATER CHEMISTRY

Lecture-2
Estimation of Temporary and Permanent Hardness using EDTA (Ethylene
Diamine Tetraacetic Acid) Method or Complexometric Method

Since EDTA is insoluble in water sodium salt of EDTA is used which yields the anion and this forms
complex with Ca+2 and Mg+2 ions.(Molecular Wt. =372.24, Equivalent Wt. = 186.14i.e.,M =2N)

Principle:

In order to determine the equivalence point (i.e., metal-EDTA complex formation) indicator
EriochromeBlack-T (EBT) is used which forms an unstable wine red complex with Ca+2 and Mg+2 ions.
The indicator is effective at about pH 10. When EBT and buffer solution (NH4OH/NH4Cl buffer solution)
are added to hard water, and the pH is maintained at 9-10, a wine red unstable complex is formed.
Thus,
pH=10
+2 +2
Ca /Mg + EBT [Ca+2/Mg+2–EBT] complex
(unstable wine red)

HOOCC H2

HOOCCH2

During the course of titration against EDTA solution, EDTA combines with Ca+2 / Mg+2 ions and forms a
stable complex Ca+2/Mg+2–EDTA. When nearly all M+2 (Ca+2orMg+2) ions have formed [M+2-EDTA]
complex wine red color changes to blue color (due to free EBT). Thus at equivalence point,
pH=10
[Ca+2/Mg+2–EBT]+EDTA [Ca+2/Mg+2–EDTA] + EBT
Wine red color (stable, Colorless) (bluecolor)
Thus, change of wine red to blue color marks the end point of titration.

Stepsinvolved/Procedure:
1. Preparation of standard hard water: Dissolve 1 gm of pure dry CaCO3 in minimum quantity of dil.
HCl and then evaporate the solution to dryness on water bath. Dissolve the residue in distilled water
to make 1L solution. Each 1ml of this solution contains 1mg of CaCO 3 hardness.
2. Standardization of EDTA solution: Rinse and fill the burette with EDTA solution. Pipette out 20
mlof standard hard water in a conical flask. Add 2-3ml of buffer solution and 2-3 drops of EBT

WATER ANALYSIS MODULE-1 L-2

 WATER CHEMISTRY

indicator. Titrate with EDTA solution till wine red color changes to blue color. Let the volume used be x
ml.
3. Estimation of total hardness of water sample: Titrate 20ml of water sample just as in step 2. Let
the volume used be yml.
4. Estimation of permanent hardness of water sample: Take 100 ml of water sample in a large
beaker and boil till the volume is reduced to 20 ml (all the bicarbonates are decomposed into insoluble
CaCO3and Mg(OH)2). Filter, wash the precipitate with distilled water and collect the filtrate and
washings in a 100ml standard flask. Finally make up the volume to 100 ml with distilled water. Then
pipette out 20 ml of this water sample in a conical flask and titrate just as in step 2. Let the volume
used be z ml.
Calculations:
Molarity of prepared hard water = M

Molarity of EDTA solution,M2: M1V1/n1=M2V2/n2

where,n1 and n2 are the no. of moles of Ca+2 and Mg2+,

M1= Molarity of standard hard water = 0.01 M; V1= Volume of Standard hard water,
M2=Molarityof EDTAsolution; V2=Volume of EDTA solution=x mL

∴Molarityof EDTAsolution, M2=M1V1/V2=0.01 xV1/xM

Molarity of hardwater sample, M3: M2V2=M3V3

M2=Molarity of EDTA solution; V2=Volume of EDTA solution= y mL

M3=Molarity of hard water sample; V3=Volume of hard water sample

∴Molarity of hard water sample, M3=M2V2/V3 M

Total Hardness of water sample = M3x 100x1000mg/L = M3x100x1000ppm

Permanent hardness of water sample is calculated by,M2V2=M4V4

M2=Molarity of EDTA solution; V2=Volume of EDTA solution = z mL
M4=Molarity of boiled hard water sample; V4=Volume of boiled hard water sample
∴Molarity of boiled hard water sample, M4=M2V2/V4
Permanent hardness of water sample = M4 x 100x1000mg/L = M4x100x1000ppm

Temporary hardness of water sample =Total hardness –permanent hardness

=[M3x100x1000]–[M4x100x1000]ppm.

Advantages of EDTA method:This EDTA method is preferable because of a) greater accuracy,

b)convenience, c)More rapid procedure.

WATER ANALYSIS MODULE-1 L-2

 WATER CHEMISTRY

Lecture-3
Complexometric Method - Numerical Problems, Estimation of Alkalinity
1. 50ml of a sample water consumed 15ml of 0.01 EDTA before boiling and 5ml of the same
EDTA after boiling. Calculate the degree of hardness, permanent hardness and
temporaryhardness.

Solution:50ml of water sample=15ml of 0.01M EDTA

Molarity of water= 15x100ml = 0.003M
50
Total hardness of water sample =0.003x1000 x100mg/L=300mg/L
50mlof boiled water sample =5ml of 0.01M EDTA
Molarity of boiled water = 5x100 ml = 0.001M
50
Permanent hardness of water sample=0.001 x1000 x100 mg/L=100 mg/L
∴Temporary hardness=Total hardness–permanent hardness=300-100=200ppm.

2. 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 total, temporary and permanent hardness.
Solution:
Molarity of water=0.5x1000=0.01M
100 x500

50ml of prepared water required = 48ml of EDTA

Molarity of EDTA= 0.01x50ml = 0.01M
48
50ml of water sample= 15 ml of 0.01 EDTA
Molarity of water= 0.01x15ml = 0.003M
50
Total hardness of water sample = 0.003x1000 x100mg/L=300mg/L
50ml of boiled water sample=5ml of 0.01M EDTA
Molarity of boiled water=0.01x10 ml = 0.002M
50
Permanent hardness of water sample=0.002 x1000 x100 mg/L=200 mg/L

∴Temporary hardness=Total hardness–permanent hardness=300 – 200=100ppm.

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 WATER CHEMISTRY

Lecture-4
Potable Water: Specifications and Steps Involved in the Treatment
Standards required for Potable water/Municipal water/Drinking water:

Potable water is generally obtained from rivers and lakes. Water obtained from these sources are
never pure and as such it is unfit for drinking.
Definition: Water which can be used for drinking is known as potable water.
Characteristics:
1. It should be clear, colourless, odourless and pleasant to taste.
2. Its turbidity should not exceed 10 ppm.
3. Its total dissolved solids should be less than 500ppm.
4. Its alkalinity should not be high. pH should be neutral.
5. Hardness should be less than 200 (WHO standards) or 250(BIS standards) ppm.
6. Its chloride content should be less than 250 ppm.
7. Its fluoride content should be less than 1.5 ppm.
8. It should be free from disease producing microorganisms or harmful bacteria.
9. It should be free from elements such as lead, arsenic, chromium, manganese salts.
10. It should be free from objectionable dissolved gases like H2S, CO2.

Municipal Water Treatment:

In general water treatment for municipal supply or domestic use consists of following stages:
1. Removal of Suspended Impurities:
a) Screening: The raw water is passed through screens having large number of holes where floating
materials are retained.
b) Sedimentation: The water is allowed to stand undisturbed for 2-6 hrs in big tanks about 5
meters deep when most of suspended particles settle down at the bottom due to force of gravity.
The clear water is taken out by using pumps.
c) Coagulation and Flocculation: Coagulation is the process of removing fine suspended and
colloidal impurities by theaddition of coagulants (chemicals) to water. Coagulant when added to
water, form insoluble gelatinous, flocculent precipitate which adsorbs and entangles very fine
suspended impurities forming bigger flocs,whichsettle down easily.
[Link][K2SO4.Al2(SO4)3.24H2O], NaAlO2, FeSO4.7H2O.

Al2(SO4)3 + 6H2O 2Al(OH)3+ 3H2SO4

Al2(SO4)3+ 3Ca(HCO3)2 2Al(OH)3+ 3CaSO4+ 6CO2
NaAlO2+2H2O Al(OH)3 + NaOH
(Gelatinous ppt)
The aluminium hydroxide floc causes sedimentation. The sodium hydroxide thus produced,
precipitates magnesium salts such as Mg(OH)2.
MgSO4+2NaOH Mg(OH)2+Na2SO4
d) Filtration: A sand filter consists of a thick top layer of fine sand placed over coarse sand layer
followed by fine gravel and coarse gravel. It is provided with an inlet for water and an under drain
channel at the bottom for exit of filtered water. The sand filter is uniformly distributed over the
entire fine sand bed. During filtration, the sand pores get clogged, due to retention of impurities in
the pores. When the rate of filtration becomes low the working of filter is stopped and about 2-3cm

POTABLE WATER TREATMENT MODULE-1 L-4

 WATER CHEMISTRY

of the top fine sand layer is scrappe off and replaced with clean sand and the filter is put back into
use again. The scrapped sand is washed with water, dried and stored for reuse at the time of next
scrapping operation.

2. Removal of Microorganisms:
Even after removal of suspended impurities, water may possess some microorganism which are
harmful to health. The process of killing/removing harmful bacteria/fungi/algae from water and
making it safe for use is called disinfection or sterilization of water.
The chemicals or substances which are added to water for killing the bacteria are known as
disinfectants.
a) Boiling: By boiling water for 10-15 minutes, all the disease producing bacteria are killed and
water be comes safe for use.
b) Adding bleaching powder: 1 kg of bleaching powder per 1000 kilo litres of water is mixed and
water is allowed to stand undisturbed for several hours. The chemical action produces hypochlorous
acid (HOCl), a powerful germicide.
CaOCl2 + H2O Ca(OH)2 + Cl2
Cl2 + H2O HCl + HOCl
Germs +HOCl germs are killed.
The disinfecting action of bleaching powder is due to the chlorine made available by it.
Drawbacks:
i) Bleaching powder introduces calcium in water which makes it harder.
ii) Bleaching powder deteriorates due to its continuous decomposition during storage.
iii) Excess of bleaching powder gives bad taste and smell to treated water.
c) By chlorination: Chlorine (either in gas or in concentrated solution form) produces
hypochlorousacidwhichis a powerfulgermicide.
Cl2 + H2O HCl+ HOCl
Germs +HOCl germs are killed.
d) By using Ozone: Ozone is produced by passing silent electric discharge through cold and dry
[Link] is highly unstable and breaks down, liberating nascent oxygen. The nascent oxygen is
verypowerful oxidizing agent and kills all bacteria and oxidises organic matter in water and make
water safefordrinking.
O3 O2 + [O]
Nascent Oxygen
Germs + [O] germs are killed.

Flow diagram of municipal water treatment:

Sterilization/ Coagulation/

POTABLE WATER TREATMENT MODULE-1 L-4

 WATER CHEMISTRY

Lecture-5
Water Treatment Method - Disinfection Methods
By Chlorine Method or Chlorination
Cl2 is the most widely used disinfectant throughout the world. Liquid Cl2is most effective when applied
to filtered water at such a point where adequate mixing is done.
Mechanism of action: The death of microorganisms, bacteria etc., result from chemical action of
hypochlorous acid with the enzymes in the cells of the microorganisms, which are essential for the
metabolic processes of the microorganisms. The death of microorganisms results due to inactivation of
enzyme by hypochlorous acid.
HOCl H++OCl–
This explains the fact that chlorine is found to be more effective is infectant at lower pH values (below 6.5).
This is due to the fact that HOCl is about 80 times more destructive to bacteria than OCl –. The apparatus
used for this purpose is known as chlorinator. It is a high tower having a number of baffle plates. Chlorine
treated water is taken out from the bottom. To carryout the disinfection process of water about 0.3-
0.5ppm of Cl2 is sufficient.

Factors affecting efficiency of chlorine:

1. Time of contact: It has been experimentally shown that no. of microorganisms destroyed by Cl2 per unit
time is proportional to the no. of microorganisms remaining alive. Consequently, the death rate is
maximum to start with and it goes on decreasing with thetime.
2. Temperature of water: The rate of reaction with enzymes increase with temperature. Consequently,
death rate of microorganism by Cl2 increases with rise in water temperature.
3. pH: At lower pH values (5-6.5) a small contact period is required to kill same percentage
oforganisms. Disadvantages: Excess of chlorine if added produces a characteristic unpleasant taste and
odour. It causes irritation on mucus membrane.
The quantity of free chlorine in treated water should not exceed 0.1-0.2 ppm. It is more effective below
6.5pH and less effective at higher pH values.
Break-Point Chlorination:
The process of applying calculated amounts of chlorine to water in order to kill the pathogenic bacteria is
called chlorination. Chlorine also reacts with water and gives hypochlorous acid, which kills bacteria.
Cl2 + H2O HOCl + HCl

DISINFECTION METHOD MODULE-1 L-5

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 WATER CHEMISTRY

Chlorine is a powerful disinfectant than chloramine and bleaching powder. Calculated amount of chlorine
must be added to water because chlorine after reaction with bacteria and organic impurities or ammonia,
remains in water as residual chlorine which gives bad taste, odour and toxic to human beings. The amount
of chlorine required to kill bacteria and to remove organic matter is called Break-Point Chlorination.
The water sample is treated with chlorine and estimated for the residual chlorine in water and plotted as a
graph as shown below which gives the break point chlorination.

From the graph it is clear that the area under represents,

Upto1:chlorine added oxidizes reducing impurities of water.
From1to2:chlorine added forms chloramine and chloro compounds.
From2to3:chlorine added causes breakdown of chloroorganic compounds and inturn destruction of
bacteria.
Point3:It is break-point. At this point free residual chlorine begins to appear. At breakpoint, water is free
from bad taste and odour.
Advantages of chlorination:
1. It removes taste, colour, oxidise completely organic compounds, ammonia and other reducing impurities.
2. It destroys completely (100%)all disease producing bacteria.
3. It prevents growth of any weeds in water.
4. It is effective and economical, requires little space for storage, stable.
Dechlorination:
The excess chlorination is removed by passing the water through a bed of granular carbon and also by
addition of SO2 and sodium thiosulphate.
SO2 +Cl2+2H2O H2SO4 +2HCl

Na2S2O3+Cl2+H2O Na2SO4+2HCl

DISINFECTION METHOD MODULE-1 L-5

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 WATER CHEMISTRY

Lecture-6
Boiler Feed Water - Boiler Troubles

A boiler is a closed vessel in which water under pressure is transformed into steam by the
application of heat. Water is mainlyused in boilers for the generation of steam (for industries and
power houses).
A boiler feed water should have the following specifications:
1. Its hardness should be below 0.2ppm.
2. Its caustic alkalinity (due toOH-) should lie in between 0.15ppm to0.45ppm.
3. Its soda alkalinity(due to Na2CO3)should lie in between 0.45–1ppm.

Essential requirements of boiler feed water: The following should be removed from boiler feed
water.
1. Hardness causing and scale forming constituents like salts of calciumand magnesium. This is
because scale formation would result in wastage of fuel, lowering of boiler safety, decrease in
efficiency and danger of explosion.
2. Caustic alkali to avoid caustic embrittlement.
3. Dissolved gases like oxygen, carbondioxide etc. In order to prevent boiler corrosion.
4. Turbidity, oil etc. to reduce the tendency for priming and foaming. Hence water must be
softened before use in boilers.
BOILERTROUBLES:
The troubles caused in boiler during to steam generation due to impurities are called boiler
troubles. These are of four types scales and sludges, aaustic embrittllement, priming and foaming
and boiler corrosion.
A) Scale and Sludge:
In boilers, water evaporates continuously and the concentration of the dissolved salts increases
progressively. When the dissolved salts concentration increases and reaches saturation point, they
are thrown out of water in the form of precipitates on the inner wall of the boiler.
• If the precipitation takes place in the form of loose and slimy precipitate it is called sludge.
• If the precipitated matter forms a hard adhering crust or coating on the inner walls of the boiler, it
is called scale.

1) SLUDGE: It is a soft, loose and slimy precipitate formed within the boiler.
Reasons:
It is formed at comparatively colder portions of the boiler and collects where the flow of water rate

BOILER TROUBLES MODULE-1 L-6

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isslow or at bends. Sludges are formed by substances which have greater solubility in hot water
than in cold water.
Eg: MgCO3,MgCl2,CaCl2,MgSO4,etc.
Disadvantages:
i. Sludge is poor conductor of heat which tends to waste a portion of heat generated and efficiency
of boiler is decreased.
ii. If sludge is formed along with scales, then sludge gets entrapped in the latter and both get
deposited as scales.
[Link] formation disturbs the working of the boiler as it settles in the region of poor
watercirculation such as pipe connection; plug opening, guage-glass connection thereby causing
even choking of the pipes.
Prevention:
i. By using wellsoftened water, scales and sludge formation can be avoided.
ii. By frequent “BlowDown” operation i.e.,drawing off a portion of the concentrated water.

2) SCALES: Scales are hard deposits which stick strongly to the inner surfaces of the boiler. These are
difficult to be removed.
Formation of Scales:
1. Decomposition of Ca(HCO3)2: At high temperature, bicarbonates undergo decomposition
to form precipitate as scale.
Ca(HCO3)2 CaCO3↓+H2O+CO2
The formation of CaCO3scale is soft and is the main cause of scale formation in low pressure boiler.
In high pressure boilers, CaCO3is soluble.
CaCO3+H2O Ca(OH)2+CO2↑

2. Deposition of CaSO4: The solubility of CaSO4in water decreases with rise in temperature i.e.,
CaSO4is soluble in cold water but completely insoluble in super-heated water. CaSO4 gets
precipitated as hard scale on the heated portions of the boiler. This is the main cause of scales in
high pressure boilers.
3. Hydrolysis of Magnesium Salts: The Mg salts dissolved undergo hydrolysis at high temperature
forming Mg(OH)2 precipitate which forms scale.
MgCl2 + 2H2O Mg(OH)2↓ + 2HCl↑
(scale)
Disadvantages:
i. Wastage of fuel: Scales have a low thermal conductivity so rate of heattransfers from boiler
toinside water is greatly decreased due to which excessive or over heating is done and this causes
increase in fuel consumption and in turn efficiency of boiler is decreased.
ii. Lowering of boiler safety: Over heating of boiler tube makes boiler softer and weaker and this
causes distortion of boiler tube and makes the boiler unsafe especially in high pressure boilers.
iii. Decrease in Efficiency:Scales may deposit in the valves and condensers of the boilers
andchokethempartially. This results in decrease in efficiency of the boiler.
iv. Danger of explosion: The thick scales formed if cracked due to uneven expansion, the water
comessuddenly in contact with red hot boiler metal. This causes the formation of a large amount
of steam suddenly, so sudden high pressure is developed which causes explosion of boiler.
Removalof Scales:-
i. If scales are loosely adhering they can be removed with the help of scrapper or wire brush

BOILER TROUBLES MODULE-1 L-6

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orpieceofwood.
ii. Bygivingthermal shocks (i.e., heatingtheboilerand then suddenlycoolingwith cold water) if
theyarebrittle.
iii. Scales can be removed by chemical treatment. They can be removed by treating with 5-10% HCl
solution with which they form soluble complexes.
iv. Scales during initial formation, can be removed by frequent blow down operation.

Distinguishbetweenscalesandsludges.

Sludges Scales
1. They are soft, loose and slimy precipitate. Theyformharddeposits.
[Link] form non-adherent deposits and can be They stick firmly to the inner surface of the boiler
easily removed. and are very difficult to remove.
3. They are formed by substances like CaCl2, They are formed by substances like CaSO4,
MgCl2, MgSO4, MgCO3,etc. Mg(OH)2,etc.
4. They are formed at comparatively colder They are formed at hot portions of theboiler.
portions of the boiler.
[Link] decrease efficiency of boiler but are less They decrease efficiency of boiler and chances of
dangerous. explosion are also there.
6. They can be removed by blow down They can be removed by 5-10% HCl solution.
operation.

B) Caustic Embrittlement:
It is a type of boiler corrosion caused by using highly alkaline water in the boiler. During
softening process by Lime-Soda process, free Na2CO3 is usually present in small proportion. In high
pressure boilers,Na2CO3decomposes to give NaOHand CO2and thismakestheboilerwater‘caustic’.

Na2CO3 + H2O 2NaOH +CO2

The NaOH containing water flows into minute hair cracks always present in inner side of boiler by
capillary action. Here water evaporates and the dissolved caustic soda concentration increases
progressively. This caustic soda attacks the surrounding area, there by dissolving iron of the boiler
as sodium ferroate.
2Fe+2NaOH 2Na2FeO2 +H2↑
Sodium ferroate
This causes embrittlement of boiler parts(like bends, joints, etc.,) causing even failure of the boiler.
Concentrated NaOH becomes anodic part; which is consequently dissolved or corroded.
Preventionofcausticembrittlement:Causticembrittlementcanbeavoided:
i) By using Na3PO4as softening reagent instead of Na2CO3.
ii) By adding tannin or lignin to boiler water since these block the hair cracks there by preventing
infiltration of caustic soda solution in these.
iii) By adding Na2SO4depending on the pressure in the boiler.

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Lecture-7
Water Softening Methods – External Treatment – Ion Exchange Method

Water Softening Methods

Water used for industrial purposes should be sufficiently pure. It should therefore be free from
hardnessproducing salts before use. The process of removing hardness producing salts from water is
known as‘Softening’of water.
It is carried out by two ways.
1) Internal Treatment 2) External Treatment
External treatment:1)Ion-exchange Process/deionization/demineralization:
Ion exchange resins are insoluble, cross linked,long chain organic polymers with a microporous
structure and the functional groups attached to the chains are responsible for ion exchanging
properties. Resins containing acidic functional groups(-COOH,-SO3H) are capable of exchanging their
cations; those containing basic functional groups (-NH2,NH-) as HCl are capable of exchanging their
anions with other anions, which comes in their contact.

The ion exchange resins may be classified as:

i) Cation Exchange Resins (RH+):-These are mainly styrene-divinylbenzene co-polymers which on
sulphonation or carboxylation become capable to exchange their H+ions with cations in the water.
ii) Anion Exchange Resins (R’OH-):- These are styrene-divinyl benzene and amine formaldehyde
copolymers which contain amino or quaternary ammonium or quaternary phosphonium or tertiary
sulphonium groups as an integral part of resin matrix. These, after treatment with dil NaOH solution,
become capable to exchange their OH- anions with anions in water.

Process:-
Raw water is first passed through cation exchanger andthe removal of cations Ca +2,Mg+2 etc takes
place and equivalent amount of H+ ions are released from this column to water. Thus,

2RH + Ca(HCO3)2 R2Ca + 2H2CO3

2RH + Mg(HCO3)2 R2Mg + 2H2CO3

WATER SOFTENING METHODS MODULE-1 L-7

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 WATER CHEMISTRY

2RH + CaCl2 R2Ca + 2HCl

2RH + MgCl2 R2Mg + 2HCl
2RH + CaSO4 R2Ca + H2SO4
2RH + MgSO4 R2Mg + H2SO4
2RH + Ca(NO3)2 R2Ca + HNO3
2RH + Mg(NO3)2 R2Mg + HNO3

After cation exchange column, the hard water is passed through anion exchange column, which
2- 2-
- -
removes all the anions like SO4 , Cl , CO3 etc present in the water and equivalent amount of OH
ions are released from this column to water.
R’OH + HCl R’Cl + H2O
2R’OH + H2SO4 R’SO4+2 H2O
2R’OH + H2CO3 R’CO3+2 H2O
R’OH + HNO3 R’NO3 + H2O
Thus, water coming out from the exchanger is free from cations as well as anions. Ion-free
water is known as deionized or demineralized water.
Regeneration of ion exchangers:
After the deionization of certain amount of raw water the cation and anion exchangers will be
[Link] of cation exchanger is carried out by passing dil. HCl or H2SO4 solution into
the bed. The column is washed with deionized water and the washings(Ca+2, Mg+2etc) are passed to
sink or drain.
R2Ca+2HCl 2RH+CaCl2
R2Mg+2HCl 2RH+MgCl2

The exhausted anion exchange column is regenerated by passing a solution of dil. NaOH solution.
The column is washed with deionized water and washings containing Na + and SO42- or Cl- ions are
passed to sink or drain.
R2SO4+2NaOH 2ROH+Na2SO4
R2Cl2+2NaOH 2ROH+2NaCl

The regenerated ion exchange resins are then used again.

Advantages:
1) Highly acidic or alkaline/basic water can be purified by this process.
2) The hardness possessed by the deionized waterisverylow,~2 ppm.
3) The deionized water is most suitable for high pressure boilers.
Disadvantages:
1) The ion exchanging resins are expensive hence the cost of purification is high.
2) If water turbidity is above 10 ppm, then pores in the resin will be blocked and output of the
processis reduced and efficiency of the purification system decreases very early. Therefore,
pretreatment such as coagulation and filtration must be done before passing into the ion-
exchange chambers.

WATER SOFTENING METHODS MODULE-1 L-7

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Lecture-8
Internal-Carbonate, Calgon, Phosphate and Colloidal Conditioning

Internaltreatment:-
The internal treatment consists of adding chemicals directly to the water in the boilers for removing
scales and sludges.
1. Colloidal conditioning:- Organic substances like kerosene and agar-agar are added to water which
prevent the scales.
2. Phosphate conditioning: - Phosphates react with water and a loose sludge is formed
which can be easily removed by blow-down operation.
3CaSO 4 + 2 Na 3 PO 4 Ca 3 (PO 4 ) 2 + 3Na 2 SO 4

3. Carbonate conditioning:-In low pressure boilers, scale formation can be avoided by adding sodium
carbonatetotheboilerwater.
CaSO 4 + 2Na 2 CO 3 CaCO 3 + Na 2 SO 4

4. Calgon conditioning:- Sodium hexa meta phosphate (calgon) is added to boiler

water to prevent scale formation by formation of soluble complex.
2CaSO 4 + Na 2 [Na 4 (PO 3 ) 6 ] Na 2 [Ca 2 (PO 3 ) 6 ] + 2Na 2 SO 4
Calgon Soluble Complex

5. Sodium aluminate conditioning:- Sodium aluminate gets hydrolysed yielding NaOH

and aluminium hydroxide precipitate. The sodium hydroxide reacts with magnesium salts to
magnesium hydroxide. These hydroxides entrap finely divided particles and neutralize the charge
on colloidal particles, and the loose precipitate can be removed by the blow-down operation.

WATER SOFTENING METHODS MODULE-1 L-8

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Lecture-9
Desalination of Brackish Water-Reverse osmosis

The process of removing common salt (sodium chloride) from the water is known as
“Desalination”. The water containing dissolved salts with a peculiar salty or brackish taste is
called “Brackish water”.[Link] (contains an average of about 3.5%salts) is an example of
brackish water. It is totally unfit for drinking purpose. Commonly used methods for desalination
of brackish water are:-
1) Electrodialysis
2) Reverse Osmosis
Reverse Osmosis:
When two solutions of unequal concentrations are separated by a semipermeable membrane
(which doesnot permit selectively the passage of dissolved solute particles i.e., molecules, ions
etc) flow of solvent takes place from dilute to concentrated sides, due to Osmosis.
If a a hydrostatic pressure in excess of osmotic pressure is applied on the concentrated side,
the solvent flow reverses i.e.,solvent is forced to move from concentrated side to dilute across the
membrane. This is the principle of reverse osmosis. Thus, in reverse osmosis, pure solvent (water)
is separated from its contaminants, rather than removing contaminants from water. This
membrane filtration is also called“Super/ Hyper filtration”.

Method:
In this process, pressure (15-40 kg/cm2) is applied to salt water (to be treated) to force its pure
water through the semi-permeable; leaving behind the dissolved solids (both ionic and non-
ionic).The principle of reverse osmosis as applied for treating saline/sea water is as follows: given
in figure above.
The membrane consists of very thin film of cellulose acetate, affixed to either side of a perforated
tube. Superior membranes recently developed are made of polymethacrylate and polyamide
polymers have come in to use.
Advantages:
1) Reverse osmosis process has distinct advantage of removing ionic as well as non-ionic,
colloidal and high molecular weight organic matter.
2) It removes colloidal silica, which is not removed by demineralization.

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3) The lifetime of membrane isquitehigh,about 2years.

4) The membrane can be replaced within a few minutes there by providing nearly
uninterrupted water supply.
5) Low capital cost, simplicity, low operating cost and high reliability.
6) The reverse osmosis is gaining ground at present for converting sea water into drinking water
and for obtaining water for very high pressure boilers.

DESALINATION PROCESS MODULE-1 L-9