UNIT- WATER TECHNOLOGY

Lecture session 1: Topics: Sources of water Characteristis of water- hardness and

alkalinity.
Water plays an important role in our daily life. 70% of the earth is covered by water,
out of which 97% is in oceans and hence saline (not usable) 2% is locked as polar ice
caps (not available for use) only 196 is available as surface and ground water (Usable)
Though the ground water is clear, it contains dissolved salts, hence not pure. Surface
water contains dissolved salts, dissolved gases and suspended impurities. Water is

an essential commodity for any engineering industry. The sources for water are of
stationary or of flowing type. Depending on the source, water may consist of impurities
in soluble or dispersed or suspended form. The impurities in water impart some
undesirable properties to water and hence render water ineffective for the particular

engineering application.

Main sources of water:

1. Surface water- River water lake water etc.

2. Sea water It is the most impure water
3. Underground water-shallow and deep springs and wells

Types of impurities:

1. Physical Impurities: Clay, sand oil globules, vegetable and animal matter.

2. Chemical Impurities:

Dissolved Inorganic salts: Ca, Mg, Cr, sO etc.

Dissolved Gases: CO2,02, N2, Oxides of nitrogen.

3. Biological impurities: microorganisms like bacteria,fungi etc.

DEPT.OF APPLIED CHEMISTRYISVCE

Lecture session 2: Topics: Characteristics of water- hardness and alkalinity.

Hardness the property of water which prevents it from lathering. Water which does not
produce lather with soap solution but produces white precipitate is called hard water
and which produces lather readily with soap solution are called soft water.

Temporary Hardness or Carbonate Hardness (CH) or Alkaline Hardness (AH): This is

due to the presence of bicarbonates of calcium and magnesium. It can be removed by
mere boiling. The bicarbonates are converted into insoluble carbonates and
hydroxides, which can be remOved by filtering.

Ca (HCO }2 CaCOI+ H20 +CO2

Mg (HCOs) Mg(OH)2 +2C0
Permanent Hardness or Non-carbonate Hardness (NCH) or Non- alkaline Hardness
(NAH): This is caused by the presence of chlorides and sulphates of calcium and
magnesium. It cannot be removed by boiling. can be removed only by Chemical or
special treatment.

Units of Hardness ppm: 1 part of Caco equivalent hardness in 10 parts of water

mg/ L:1 mg of CacO 3 equivalent hardness in 1 L of water Weight of 1 L of water = 1
Kg. = 1000 g= 1000000 mg = 10 ° mg Hence 1 ppm = 1mg/L

Expression of Hardness in terms of Caco Equivalents (Importance of calcium

carbonate equivalents). Hardness is expressed in terms of CaCOs equivalents
because ) it is most insoluble salt obtained in water treatment i)Molecular weight is
100(Eq.Wt50)

Alkalinity: The alkalinity of water is its acid neutarlising capacity .It is attributed to the
presence of the following species hydroxide (OH). Carbonates COand
bicarbonates(HCOs-) of alkali or alkaline earth metals.

DEPT.OF APPLIED CHEMISTRY/svCE

Lecture session 3 Topics: Requirements of boiler feed water. Disadvantages of hard
water in boilers and heat exchangers-Scales and sludges.

BOILER FEED WATER

Water is largely used in boilers (as feed) for the production of steam. The presence of
impurities in water sample renders it hard (and corrosive too in some cases) and any
water sample cannot be used as boiler feed as it may pose the problems of corrosion,
embrittlement of the boiler vessel etc. Water with some specifications, used in boilers
for steam generation is called boiler feed water.

Requisites of boiler feed water: () it should be free from suspended solids and
dissolved corrosive gases such as CO2, SOx, NO., halogens, hydrogen halide etc. (i)
hardness should be less than 0.1 ppm (i) alkalinity (soda and caustic alkalinity values)
should be in the range 0.1 - 1 ppm; less than 0.5 ppm alkalinity is preferable (ii) it
should be free from dissolved salts and oily / soapy matter that reduces the surface
tension of water. Boiler feed water should be free from hardness producing substances.
If hard water is fed directly into the boiler it leads to the following boiler troubles which
reduce the efficiency of the boiler.

Disadvantages of using hard water in boiler: The main destructive effects of using
hard water in boilers are (i) formation of scales and sludges (i) boiler corrosion (ii)
caustic embrittlement and (iv)priming and foaming. Formation of scales and sludges is
the main disadvantage of using hard water in boiler.

BOILER TROUBLES

1. SCALES AND SLUDGES:

In boiler, water is converted to steam. During this process, when the volume of water
decreases, a saturation point is reached and all the dissolved salts precipitate out.
Depending on the physical and chemical nature of the impurity (salt) it may form a
loose, slimy, non- adhering precipitate (Sludge) or hard strongly adhering precipitate
(Scale)

DEPT.OF APPLIED CHEMISTRY/SVCE

 A

Loose Precipitate
Suspended in water
Adherent
coating inside
(sludge) ne poier
(6cale)

heat
Sludge : Loose, slimy and non adhering precipitate due to presence of salts like
MgClh, Mgso 4, CaClh, MgCO . It forms in colder portions of boilers and the portion
where water flow rate is low.

Disadvantages: Sludges are p0or conductor of heat. Excess of sludge formation

decreases the efficiency of boiler.

Prevention and removal: By using softened water and performing frequent blow down
operation.

Scale: Hard, adherent coating due to presence of salts like Mg(HC0s)a.Mg(OH)2

Ca(HCOs)2. CasO4
Disadvantages: The scale formation in boilers, poses a variety of problems, such as
wastage of fuel, overheating of the boiler leading to explosion etc.

1. Wastage of fuel: Scales are poor conductors (almost insulators) of heat and resut in
a low heat transfer rates. To maintain steady heat supply to water, greater heat energy
has to be supplied. This results in over-heating of the boiler and also increased fuel
consumption. The extent of fuel wastage depends on the thickness and nature of the
Scale, as evidenced from the following table:
Scale thickness 0.32 0.62 1. 2.
(mm)_ 5 5
Fuel wastage (%)
10 15 50 80
2. Decrease in efficiency: Scales, if deposited in the boiler components such as valves,
condensers etc., choke in fluid paths and hence lead to decreased efficiency of the
boiler.

3. Lowering ofboiler safety: Scale formation demands over-heating of the boiler for
maintaining a constant supply of steam. The over-heating of the boiler tubes renders
the boiler material softer and weaker and hence the boiler becomes unsafe at
high
steam pressures.

4. Danger of explosion: when scales undergo cracking, water comesin contact with
overheated boiler plates suddenly. This results in sudden formation of large amount

DEPT.OF APPLIED CHEMISTRY/SVCE

 of steam and hence the development of high pressure of steam, which may cause
the boiler explosion.

Prevention and removal i) By dissolving in acids like HCI, H:SO i) By applying

external and internal treatment. in) Removed by scrapping, wire brushes etc.
Lecture session 4: Topics: Boiler troubles- Priming and Foaming.
PRIMING & FOAMING

Priming: When steam is produced rapidly in boilers the steam velocity suddenily
increases and some droplets of liquid water are carried along with steam. Steam
water is called wet steam. The process of wet steam
containing droplets of liquid
formation is called Priming.

Priming is caused by

Presence of large amount of dissolved solids.

High steam velocity.
Sudden boiling.
Improper boiler design.
Priming can be prevented by

Using treated water.

Controlling the velocity of steam.
Fitting mechanical steam purifiers.
Maintaining low water level.
Good boiler design.

Foaming: Oil or any other polymeric substance present in boiler feed water, reduces
surface tension of water forming bubbles which do not break easily in boilers giving a
foam appearance. This process is called foaming.

Foaming is caused by

Presence of oil & grease.

Presence of finely divided sludge particles.

Foaming can be prevented by adding coagulants like sodium aluminate, ferrous

sulphate etc.

Caustic embrittlement:

DEPT.OF APPLIED CHEMISTRY/SVCE

Caustic embrittlement means intercrystalline cracking of boiler metal. Boiler water
usually contains a small proportion of Na c03. In high pressure boilers this undergoes
decomposition to give NaOH. This NaOH flows into the minute hair cracks and crevices,
usually present on the boiler material, by capillary action and dissolves the surrounding
area of iron as sodium ferroate. This causes brittlement of boiler parts, particularly
stressed parts like bends, joints, rivets, etc., causing even failure of the boiler.

NaCOa + HO 2 NaOH+CO

Fe+ 2 NaOH -

Na FeO + Ha

Caustic embrittlement can be prevented by i) using sodium phosphate as softening

agent instead of sodium carbonate. li)by adding tannin, lignin to the boiler water, which
blocks the cracks.

Lecture session 5: Topics: Boiler troubles- Boilercorrosion.

BOILER CORROSION!

Boiler corrosion is decay of boiler material by chemical or electrochemical attack of its

environment. Boiler corrosion is due to presence of

Dissolved oxygen
Dissolved carbon dioxide
Dissolved salts like magnesium chloride

1. Dissolved oxygen : When water containing dissolved oxygen is fed into boilers the
following reaction occurs corroding the boiler material (rust formation)

2Fe +2H0+O2 2Fe(OH)

4Fe(OH)2 + O 2 [Fe203 2H20]

D. O. oxygen can be reduced

i) By adding hydrazine/ sodium sulphite

N2H + O2 N2 + 2H:0
2NasOa + O2 2 N a soD

DEPT.OF APPLIED CHEMISTRY/svCE

ii) By mechanical deaeration method.

2. Dissolved carbon dioxide When water containing bicarbonates is heated, carbon

dioxide is evolved which makes the water acidic. This is detrimental to the metal. It
leads to corrosion called of boiler material.
Ca(HCOs) CaCO+ HO+CO2: CO2 H20 H2CO3

Prevention methods for removing dissolved carbon dioxide:

By treatment with ammonium hydroxide:

2NHOH +CO2 - (NH)CO3 + H20

Can be removed by mechanical deaeration method along with oxygen.

3. Dissolved MgCl: Acids produced from salts that are dissolved in water are mainly
responsible for the corrosion of boilers. Salts like magnesium and calcium chloride
undergo hydrolysis at high temperature to give HCl, which corrodes the boiler. Presence
of HCl is more damaging due to chain reaction.

MgCla + 2H.0 -Mg(OH)2 I + 2HCI

Fe+2HCl F e C l ; + H2t

FeCl 22H20 Fe(OH)2 + 2HCl

MgClh can be removed by i) internal conditioning and ii) external conditioning

Lecture session 6: Topics: Softening of hard water or external conditioning : Zeolites

process and ion exchange process:

EXTERNAL CONDITIONING:

Three types of external conditioning methods in use are (i) Lime-soda process )
Permutit or zeolite process and (ii) Demineralization process. The first process is based
the precipitation of hardness causing ions by the addition of soda (Na,cos) and lime
(Ca(OH):) whereas the second and third process is based ion exchange mechanism
(ion exchange process).
An ion exchange process may be defined as a reversible exchange of ions between a
liquid phase and a solid phase. Materials capable of exchanging cations are called
cation exchangers and those which are capable of exchanging anions are called anion
exchangers. Both anion and cation exchangers are used in water treatment.

NATURAL AND SYNTHETIC ZEOLITE PROCESS.

DEPT.OF APPLIED CHEMISTRYISVCE

 Zeolites are of two types natural zeolites and Synthetic zeolites.

Natural Zeolites are non porous materials Ex. Natrolite Na:0.AlkO3sioa.3H:O.

Synthetic Zeolites also called permutits are porous and poses a gel structure. Ex
Sodium Zeolite. Synthetic Zeolites have higher exchange capacity per unit
weight.
Sodium Zeolites are used for water softening and they have general chemical
structure as Na;0.AlO3.XSiO2y2H:0 wher x= 2-10: y=2-6

They are considered as hydrated sodium aluminosilicates which are capable of

exchanging their sodium ions for divalent ions of metals present in water

Zeolites are represented as Na:z .where Z is insoluble zeolite frame work.

Process: Hardwater is allowed to percolate through a bed of Zeolite kept in a

cylinder. The hardness causing ions are taken up by the zeolite and
simultaneously releasing the equivalent sodium ions in exchange for them.
Na-Z+Ca- Caz+ 2Na
Regeneration: When the zeolite bed is exhausted (i.e saturated with Ca and Mg
*) it cannot soften water further. Exhausted Zeolites is reclaimed by treating
the bed with a concentrated NaCl solution(10% brine)
Caz + 2Na - Ca + Na:z

Had wotei Unet

--
be

obaton

Lecture session 7 Topics: Softening of hard water or external conditioning lon

exchange process:

DIMINERALISATION USNG ION EXCHANGE RESINS

DEPT.OF APPLIED CHEMISTRYIsVCE

 Dimineralisation or Deionisation can be carried out using in exchange resins
(ER). IE resins are insoluble, cross-linked long chain organic polymers with
micro-porous structure. The functional groups attached to the polymeric chain
have the tendency to exchange the (hardness causing) ions. Acidic functional
groups such as carboxyl (-coOH), sulphonic acid ((SO3H) have the capacity to
exchange cations whereas basic functional groups such as amines (-NH:),
hydroxyl (-OH) have the capacity to exchange anions. lon exchange resins are
generally synthesized such as styrene-divinyl benzene copolymers

The copolymer has the structure of alternate styrene and divinyl benzene units
with the aromatic rings bearing the substituents of acidic / basic functional groups
such as sulphonic acid, carboxylic acid, (substituted) amines etc.

GH CH A

to;*

Process: it is the process of removal of any mineral (cation or anion) from the
water sample. Water sample is first passed through a column called cation
exchanger, which is packed with cation exchange resins. This causes the
removal of cations by ion exchange process, but renders the water sample
acidic.The cation exchange resins are synthesized by the carboxylation or
sulphonation of styrene-divinyl benzene copolymers. The structure of these
resins is given below

Cation exchange resin is generally represented as R*; the ion exchange

process is represented as 2 RH + Ca* - RCa +2 H" 2 RH+ Mg*
RaMg+ 2 H
The exchange of any metallic cation (M") can be written as

n RH+M - R,M+nH'

The acidic water water coming out of the cation exchanger is then fed to a
column called anion exchanger, which is packed with anion exchange resins.
This causes the removal of anions by ion exchange process and also neutralizes
the acidity of the water sample, explained as follows. The anion exchange resins

DEPT.OF APPLIED CHEMISTRYISVCE

 10

are synthesized by the hydroxylation or amination of styrene-divinyl benzene

copolymers. Anion exchange resin is generally represented as ROH; the ion
exchange process is represented as

2 ROH+SO - R:SO4 +2 OH: 2ROH+CO - R.co +2 OH

ROH+X RX+OH
The ultimate reaction taking place on passing the water sample through the
cation and anion exchanger systems is H" +OH HO

Aal

Lecture session .8: Topics: internal conditioning methods:

INTERNAL CONDITIONING OR SEQUESTRATION:

Internal conditioning is treating the water after feeding into the boiler. An internal
treatment is accompanied by adding a proper chemical to the boiler water either a) to
precipitate the scale forming impurities in the form of sludges removed by blow down
operation. or b jto convert them into compounds which will stay in dissolved form
Without causing harm to boiler.

Carbonate conditioning:
Scale forming salts like CasO4 present in the water adheres more strongly This can be
prevented by precipitating Ca as CaCOj which gives rise to a loosely adhering scale
by adding Na,cO3
CaSOs+Na:cO CaCOal+ Na:so
Disadvantage/ Limitation: 1. Applicable only for low pressure boiler 2.Causes caustic
embrittlement and corrosion in high pressure boilers as the unreacted Na,cos will be
converted to NaOH and CO2.

DEPT.OF APPLIED CHEMISTRYISVCE

 11

Phosphate Conditioning:
In high-pressure boilers, scale formation can be avoided by the addition of sodium
phosphate to the water sample. Here, calcium (and also magnesium) ions (responsible
for hardness) are precipitated as their phosphates (sludges) and can be removed easily
by filtration. Three types of phosphates mono, di and trisodium phosphates are
employed in phosphate conditioning. The advantages of phosphate conditioning over
carbonate conditioning are () it can be applied to high-pressure boilers and () it can be
used for softening /conditioning acidic, neutral or alkaline water sample.
Ca +2 NaPO4 - Ca(PO,)2

If acidic water is to be conditioned, trisodium phosphate can be used. For neutral and
alkaline water samples disodium phosphate and monosodium phosphate can be used
used respectively.

Calgon conditioning:
It is the process of addition of calgon or sodium hexametaphosphate to boiler feed
water. The calcium ions (responsible for scale / sludge formation) are complexed by
calgon to form a soluble complex and hence prevented from their scale forming action.

Ca +Naa[Nau(POs)»] -Na:[Ca.(PO))+2Na
This phenomenon of complexing of the ions is called sequestration. Calgon is the
sequestering agent used. The other internal conditioning agents used are
ethylenediamine tetracetic acid (EDTA) and sodium aluminate (NaAlO,). EDTA
functions by sequestration phenomenon whereas sodium aluminate functions by
precipitation phenomenon.
Colloidal conditioning:
In low pressure boilers scale formation can be avoided by adding organic substances
like kerosene, tannin, agar-agar etc. They get coated over the Scale forming
precipitates, converting into loose deposits which can be easily removed

Lecture session 9:Topics: Reverse Osmosis:

Desalination: Water sample is of three types namely fresh water, brackish

water and sea waterdepending upon the total dissolved salt (TDS) content.
Water type TDS content
A water sample is said to be saline if it has much
(g1) of dissolved salt content. Desalination is the process
Fresh water 1-10 of removal of salinity- dissolved content from a

Brackish 10-35
WateF APPLIED CHEMISTRY/SVCE

Sea water 235

 12

water sample. Four methods of desalination are distllation, freezing. reverse osmosis
and electrodialysis.

Reverse Osomosis (RO):

Principle: Osmosis can be defined as the phenomenon of spontaneous flow of

solvent molecules from dilute solution side to concentrated solution side, when
they are separated by a semi-permeable membrane. The driving force for this
phenomenon is called osmotic pressure. If a hydrostatic pressure in excess of
osmotic pressure is applied on the concentrated solution side, the direction of
solvent flow can be reversed i.e higer concentration to lower concentration and
the process is called reverse osmosis.

The dilute solution can be re replaced by fresh water to get fresh water effectively
from impure or sea water. Thus in Reverse Osmosis (RO), the solvent / wateris
separated from the contaminants (solution).

semipermeable
pressure membrane

salt fresh
woter water

The membranes used are cellulose acetate, Polymetha acrylate,polyamide, poly

Sulphone etc.
Pressure of 15- 40 Kg/cm2 is usually applied.

Advantages
1. The life time of the membrane is high.
2. Membrane can be replaced within short time.
3. It removes all types of impurities
4. Water obtained by this process is used for high pressure boilers
5. Process is used for converting sea water into drinking water.

DEPT.OF APPLIED CHEMISTRY/SVCE

 13

UNITI:WATER TECHNOLOGY
PART A

1. Name the chief sources of water.

2. What is the cause for alkalinity of natural waters?
3. What is hard water? What are the disadvantages of using hard water in boilers?
4. What is hardness of water?
5. What is temporary hardness? How it can be removed?
6. How are scales and sludges formed in boilers?
7. Differentiate between scale and sludge.
Write the names of three sludge forming and three scale forming substances
9. What is brackish water?
10. What is meant by reverse osmosis?
11. What is calgon conditioning?
12. Why is calgon conditioning better than phosphate conditioning?
13. Why is carbonate conditioning not used for high pressure boilers?
14. All demineralised water is soft water but all soft water is not demineralised water.
Explain.
15. How is the exhausted resin regenerated in ion-exchange method of water
softening?
16. Differentiate between desalination and deionization.
17. What is desalination?
18. Define ppm.
19. The presence of cO2 in boiler feed water should be avoided, why?
20. Why is demineralization process preferred over zeolite process?
21. What is the main advantage of reverse osmosis process over ion-exchange
process?
22. In the deionization process, water is usually first passed through the cation
exchanger and then through the anion exchanger. Give reason.
23. What is meant by softening of water?
24. Why does hard water consume lot of soap?
25. Name the gases dissolved in water that cause corrosion.
26. What is caustic embrittlement?
PART B

DEPT.OF APPLIED CHEMISTRY/SVCE

1. What are scales and sludges? How do they affect the boiler ? How can it be
prevented?
2. Write a note on i) Caustic embrittlement. ii) Priming and foaming.
3. Write an explanatory note on Boiler corrosion
4. Explain the various internal treatment methods of water softening.
5. Explain the Permutit (zeolite) process of water softening.
6. How demineralization is carried out using ion exchange process.
7. Define the term desalination. With a neat diagram describe desalination by
reverse osmosis method and what are its advantages?

DEPT.OF APPLIED CHEMISTRYsVCE