UNIT-III

HARD WATER AND BOILER TROUBLES

Objective:
 To understand the troubles with hardness of boiler feed water.
 To learn internal and external treatment of hard water for boiler
applications.
Syllabus:
Hardness of water – calculation of hardness- disadvantages of using hard water
in boilers – priming and foaming – sludge and scale formation – caustic
embrittlement– boiler corrosion. Treatment of boiler feed water – Zeolite
process, Ion exchange process – Internal treatment – Calgon conditioning –
Phosphate conditioning – Colloidal conditioning – Desalination of Brackish
water by RO method.

Outcomes:

After completion of the course the students will be able to

 explain how the hardness of water effects boiler.

 calculate hardness of water.
 explain internal treatment for softening of hard water.
 explain Zeolite process, Ion exchange process and RO methods of
treatment of water.

Introduction

Water is the most essential compound for all living matter on the earth.
It plays an important role in human living and industries. Besides domestic
purpose, clean water is required in large quantities for many industries like
thermal and nuclear power plants. In this chapter, we would learn about
different impurities in water and their removal methods.

Types of water

There are two types of water. They are (i) soft water and (ii) hard water.

(i) Soft water is the water which contains very few or no minerals such as
calcium and magnesium. Soft water readily gives lather with soap.

(ii) Hard water is the water with high mineral content. Hard water does not
give lather with soap.
Hardness of water

There are two types of hardness in water. They are:

(i) Temporary Hardness: (Carbonate hardness)

It is due to the presence of calcium bicarbonate [Ca(HCO 3)2] and

magnesium bicarbonate [Mg(HCO3)2]. Temporary Hardness can be
removed by boiling or by adding slaked lime (Clark’s process). In boiling and
Clark’s processes, bicarbonates will be precipitated as insoluble carbonates of
corresponding salts.

(ii) Permanent Hardness: (Non-Carbonate hardness)

It is due to the presence of chloride, nitrate and sulphate salts of calcium

and magnesium. (CaCl2, Ca(NO3)2 & CaSO4 and MgCl2, Mg(NO3)2 &MgSO4).It
cannot be removed by boiling. Hence it is known as permanent hardness.

Disadvantages of a hard water sample

 Hard water cannot be used for drinking purpose.

 It cannot be used for cooking purposes.
 It cannot be used for bathing and washing purposes as it does notgive
lather with soap.
 It cannot be used in laboratories as it gives unwantedchemical reactions.
 It cannot be used in steam raising boilers.
 It cannot be used in sugar and paper industries.

Degree of Hardness

Usually, the hardness of water is expressed in terms of calcium carbonate

equivalents, because the molecular weight of CaCO 3 is 100, which is easy for
calculation and CaCO3 is an insoluble salt. The formula used to convert the
mass of hardness producing salt to mass of CaCO3 equivalents is given below,
Wt . of Hardness causing salt × Molecular wt . of CaC O 3
Calcium carbonate equivalents =
Molecular wt . of Hardness causing salt

Units for measuring hardness

 Parts per million (ppm) is the parts of CaCO 3 equivalent hardness per 106
parts of water, i.e., 1 ppm = 1 part of CaCO 3 equivalent hardness in 106
parts of water.
  Milligrams per litre (mg/L) are the number of milligrams CaCO 3
equivalent hardness present per litre of water.

 Degree Clark (0Cl) is parts of CaCO3 equivalent hardness per 70,000 parts
of water.

 Degree French (0Fr) is the parts of CaCO3 equivalent hardness per 105
parts of water.

1 ppm = 1mg L-1 = 0.07 0Cl = 0.1

0
Fr
1 0Cl = 14.3 ppm = 14.3 mg L-1 =
1.43 0Fr
Boiler feed water:

Water is converted into steam in boilers. If water contains suspended

and dissolved mater, they get deposited on the walls of boiler. It is called scale
formation. This scale forms a layer on the inner walls of the boiler. Therefore
boiler feed water needs prior treatment before its use. Boiler feed water
treatment involves two stages. In the first stage, the suspended and dissolved
matter is removed by different chemical methods. In the second stage, called
internal treatment, some chemicals are added to take care of suspended or
dissolved mater which was not removed in first stage.

However, if raw water (hard water) is directly used in boiler, the following types
of problems occur.

1. Sludge and scale formation

2. Boiler corrosion
3. Caustic embrittlement
4. Priming and foaming

1. Sludge and scale formation:

In boiler, water continuously evaporates. So concentration of salts in

water increases. When the ionic product of salts increases solubility product,
they get precipitated. If the precipitate is slimy then it is called sludge or if the
precipitate is hard adhering material then it is called scale.

Sludge: “Sludge is a soft, loose, non sticky and slimy precipitate formed within
the boiler.” It forms at comparatively colder portion of the boiler and deposits in
the bent area of boiler where the flow rate is slow. Sludge is formed by
substances which have greater solubility in hot water than in cold water. The
formation of sludge may be due to the presence of salts like MgCO 3, MgCl2,
CaCl2, MgSO4 etc., in water
Scale: “Scale is hard adhering deposit which sticks firmly to the inner surfaces
of the boiler.” Scale is difficult to remove. The formation of scale may be due to
the presence of salts like CaCO 3, Ca (OH)2, CaSO4, CaSiO3, Mg(OH)2, MgSiO3
etc., in water.
Disadvantages of sludge & scale formation:
1. Sludge and Scale are poor conductors of heat. So heat used to boil water
will be wasted.
2. It blocks openings like valves and tubes of boiler. So troubles the
operation of boiler.
3. It causes corrosion of boiler material.
4. If sludge is formed along with scale, sludge will be entrapped in scale. So
thick layer of scale will be formed.
5. Distortion of boiler tubes due to its uneven expansion.

Removal of sludge and scale:

1. By giving thermal shocks, i.e., strong heating and sudden cooling.

2. By blow down operation (replacing the water concentrated with
impurities of the boiler with fresh water).
3. By spraying chemicals in which the scale is soluble.
Ex: Calcium carbonate scale is soluble in 10% HCl. Calcium phosphate
scale can be removed by EDTA solution.
4. By scrapping with wire brush.

2. Boiler corrosion:

“Decay of boiler material due to chemical or electrochemical attack of its

environment is called Boiler corrosion.”

Causes for boiler corrosion: Boiler corrosion is mainly due to

1. The presence of alkalinity.

2. Presence of free mineral acids
3. Presence of dissolved gases like oxygen, carbon dioxide, hydrogen
sulphide etc. in water.
4. Formation of sludge and scale in the boiler.
5. Formation of series of galvanic cells.

Control of boiler corrosion:

 Boiler corrosion can be minimized by

 Removing dissolved gases from the boiler feed water

 Feeding the boiler with soft and salt free water.
 Preventing the formation of sludge and scale in the boiler.
 Neutralizing free acids and bases present in water before feeding it to
boiler.

3. Caustic embrittlement:

Caustic embrittlement is one type of boiler corrosion which is caused due

to the feeding highly alkaline water into the boiler. In soda-lime softening
technique, some amount of sodium carbonate left unreacted in water. This
Na2CO3 dissolves in water to give NaOH which makes the water alkaline.
Na2CO3 + H2O → 2NaOH + CO2 ; Fe + 2NaOH → Na2FeO2 + H2↑

When this NaOH entrapped in small cracks and pits of boiler, it reacts
with iron to form sodium ferrate. This type of corrosion is called Caustic
embrittlement. This type of corrosion occurs mainly at stressed areas in boiler.

(-) iron NaOH NaOH (+) iron

(stressed portion – (concentrated (dilute solution (at plane surface -
anode) solution trapped outside of cracks) cathode)
in cracks)
The iron at concentrated NaOH becomes anodic and gets corroded. The caustic
embrittlement can be prevented by adding sodium sulphate or lignin to boiler
water. Or by using sodium phosphate as softening agent in place of Na 2CO3.

4.Priming and foaming: Due to the presence of oily impurities (or due to rapid
heating), boiler feed water faces two problems, viz., priming and foaming. The
salts carried out due to priming and foaming will be deposited on turbine
blades and on other machine parts. As a result the efficiency and life of boiler
and machines decreases.
Priming: “The process of wet steam formation in the boiler due to excess of
dissolved solids and uneven or sudden heating of water” is called priming.
Foaming: “the production of foam or bubbles in the boiler due to presence of
impurities in water” is called foaming.
Causes of priming and foaming: Priming & Foaming occurs mainly due to
1. Presence of dissolved impurities
2. Presence of oily, soapy impurities for foaming in boiler feed water.
3. Formation of sludge and scale in the boiler.
4. Sudden and uneven heating of water.
 5. Defective boiler design and excess water feeding (more than its level) in
boiler.

Minimization of priming and foaming: Priming & foaming can be minimized by,

1. Feeding soft water and feeding the water free from oily, soapy impurities
for foaming.
2. Using properly designed boilers which maintain uniform heating.
3. Maintaining uniform heat supply.
4. By removing scale and sludge from time to time.
5. Adding the anti-foaming agents like castor oil, cottonseed oil and bees
wax, etc.
6. Connecting steam purifiers to the boiler.

Internal treatment methods:

a. Colloidal conditioning: In low pressure boilers, organic compounds such

as agar-agar, glue, kerosene etc., are added. These will be coated on
scale forming precipitate. So scale becomes non-sticky which can be
easily removed by blowdown operation.
b. Phosphate conditioning: In high pressure boilers, sodium phosphate is
added as conditioner. So, phosphate ion concentration increases in
water. This ion captures Ca+2 and Mg+2 ions and forms non-adherent,
easily removable calcium and magnesium phosphates.
3Ca 2+ + 2Na3PO4 → Ca3(PO4)2 + 6Na+
c. Calgon conditioning: Calgon (sodium hexametaphosphate) is added to
water which changes scale forming salts to highly soluble complexes. So
the salts will not be precipitated in the boiler. Therefore, there will not be
any scale formation.
Ca2+ + Na2[Na4(PO3)6] → Na2[Ca2(PO3)6] + 4Na+

SOFTENING METHODS:
Water required for industrial purposes (such as for steam generation)
should be very soft. The process of removing hardness – producing salts from
water, is known as softening of water. In industry, mainly three methods are
employed for softening of water. They are,
1)Zeolite or Permutit process:
Hydrated sodium aluminosilicate is called ‘zeolite’. When hard water
passed through zeolite (Na2O.Al2O3.x SiO2. YH2O; where x = 2 to 10 and Y= 2 to
6), sodium ions will be exchanged by Ca+2, Mg+2 ions present in water.
Zeolite isof two types,
 (i) Natural Zeolite is non – porous. For example, Na 2O.Al3O3.4SiO2.2H2O.
(ii) Synthetic Zeolite is porous and possesses gel structure.
Synthetic zeolite is prepared by heating together china clay, feldspar and
soda ash. Such Zeolite possesses higher exchange capacity per unit weight
than natural Zeolite.

Process: For softening of water by Zeolite process,

hard water is percolated at a specified rate
through a bed of Zeolite, kept in a cylinder. The
hardness causing ions are retained by the Zeolite
as CaZe and MgZe, while the outgoing water
contains sodium salts. Reactions taking place
during the softening process are,
Na2Ze + Ca(HCO3)2⟶ CaZe + 2NaHCO3
Na2Ze + Mg(HCO3)2⟶ MgZe + 2NaHCO3
Na2Ze + CaCl2 (or CaSO4)⟶ CaZe + 2NaCl (or
Na2SO4)
Na2Ze + MgCl2 (or MgSO4) ⟶ MgZe + 2NaCl (or
Na2SO4)
Advantages: 1) It can produce the water of 10 ppm residual harness. 2) Water
treated from zeolite method, if used in boiler, does not cause any sludge formation. 3)
It requires less space, less skill and less time for softening of water.
Disadvantages:
1) This method replaces only Ca +2 and Mg+2 ions with Na+ ions, but all the acidic ions
like Cl-, SO42-, HCO3- etc. are left behind. When this water is used in the boiler, it
causes boiler corrosion and caustic embrittlement.
2) Highly turbid water cannot be treated efficiently by this method.
3) Hot water cannot be treated as zeolite tends to dissolve in it.
Regeneration of zeolite:
By continuous utilization, zeolite becomes calcium and magnesium rich after
some time and its capacity will be reduced. At this stage, hard water flow is stopped
and the zeolite is regenerated by passing 10% NaCl solution(Brine solution).
CaZe + 2NaCl → Na2Ze + CaCl2

2) Reverse Osmosis Method( Super filtration or Hyper filtration):

[The process of solvent flowing into the solution when the solvent and the solution are
separated by a semipermeable membrane is called osmosis. Semipermeable membrane allows
solvent molecule only to pass through it but not solute molecule. Copper ferrocyanide precipitate
film deposited in the pores of a porous container, some animal membranes, parchment paper,
cellophane paper etc., act as semipermeable membranes.]
 Osmosis describes the flow of solvent from dilute to concentrated solution
through a semipermeable membrane. Whereas reverse osmosis describes the
flow of solvent in opposite direction i.e., from concentrated solution to dilute
solution across a semipermeable membrane by applying hydrostatic pressure
(on concentrated solution side) higher than osmotic pressure.

Cellulose acetate, polymethacrylate, polyamide membranes etc., are used

for reverse osmosis systems. Reverse osmosis is largely used for purification of
sea water for domestic use.

Reverse osmosis phenomenon to produce pure water (or) Desalination of

Brackish water:
The water containing dissolved salts and having very salty taste is called
brackish water, like the sea water and it is not suitable for drinking. The
process of removal of common salt from this brackish water is called
desalination. Commonly used method for the desalination of brackish water is
reverse osmosis.

Purification of brackish water by reverse osmosis

In this process, pressure of order 15 to 40 kg cm -2 is applied to sea water

or impure water to force the pure water to come out through the semi
permeable membrane. Only pure water crosses the semi permeable membrane
leaving behind the dissolved solids.

The membrane consists of very thin films of cellulose acetate affixed to

either side of perforated tube. Now-a-days, polymethacrylate and polyamide
polymers are used to prepare semi permeable membranes.

Advantages of reverse osmosis purification of water:

1. Removal of ionic, non-ionic, colloidal and high molecular weight solutes

from water.
 2. Regeneration of the process involves the easy replacement of the
semipermeable membrane.
3. Easy maintenance and economical, as the membrane lifespan is high.
4. Uninterrupted supply of large volume of water for industrial or domestic
purpose can be obtained.

3) Ion exchange method (Demineralization process or Deionization

process): Ion exchange resins are cross-linked long-chain organic polymers.
They have micro-porous structure. They are insoluble in water. The functional
groups attached to the chains are responsible for the ion exchange properties.
Ion exchange resins may be classified into two groups. 1) Cation exchange
resins (R-H) (Ex: styrene divinylbenzene copolymer compounds) and 2) Anion
exchange resins (R-OH) (Ex divinyl benzene or amine formaldehyde copolymer
compounds).

Process:The apparatus used for deionization of water is shown in the following

figure. It consists of two types of cylinders. Cation exchange cylinder and anion
exchange cylinder. The hard water is passed first through cation exchange
cylinder, where all the cations like Ca 2+, Mg2+, Na+, K+etc., are removed off by
exchanging with H+ ions of resin and equivalent number of H + ions are released
to the water.

Water coming from cation exchange resin, is passed through anion

exchange resin. The anions like HCO3-, Cl-, SO42- etc. present in the water are
removed off by exchanging with OH- ions of resin and equivalent amount of
OH- ions are released to water.

2RH + Ca2+ → R2Ca + 2H+

2RH + Mg2+ → R2Mg + 2H+

R'OH + Cl- → R'Cl + OH-

2R'OH + SO42- → R'2SO4 +2OH-

 H+ and OH- ions released from cationand anion exchange column,
respectively combine to produce water molecule.
H+ + OH- → H2O
Thus, the water obtained in this process is free from ions. This water is
called deionized or demineralized water.
Regeneration: When the resins are completely filled with hard-water ions, then
they can be regenerated. Cation exchange resin is regenerated by dilute HCl
and anion exchange resin can be regenerated by NaOH solution.

R2Ca + 2HCl → 2RH + CaCl2

R'Cl + NaOH → R'OH + NaCl

Advantages:
1. This process is capable of softening highly acidic or alkaline water also.
2. It can produce very low residual hardness (nearly 2ppm).

Disadvantages:
1. The equipment and resins are costly.
2. Turbid water cannot be easily purified. If turbid water is used, the pores
of resin are blocked by turbidity-particles.
3. If water contains ions of Mn, Fe and Pd, they will react with resin and
block it.
Assignment-Cum-Tutorial Questions
Section A. Objective Questions
1. Temporary hardness in water is removed by [ ]
(a) Filtration (b) Sedimentation (c) Boiling (d) Coagulation.
2. Hard water is unfit for use in boilers for generating steam because [ ]
(a) Its boiling point is higher.
(b) Hard water does not produce lather inside the boiler.
(c) Water decomposes in to O2 and H2.
(d) It produces scales inside the boiler.
3. Hardness in water is caused due to the presence of [ ]
(a) Un-dissolved salts of calcium and magnesium.
(b) Dissolved sulphates of potassium.
(c) Dissolved salts of calcium and magnesium.
(d) Un-dissolved calcium carbonate.
4. The purest form of the naturally occurring water is [ ]
(a) Rain water (b) Lake water (c) Pond water (d) Well water.
5. One part of CaCO3 equivalent hardness per 105 parts of water is called
[ ]
(a) Degree Clark (b) PPM (c) Degree French (d) mg/L
6. Hard water can be softened by passing it through [ ]
(a) Lime stone.
(b) Sodium aluminate.
(c) Ion exchange resin.
 (d) Sodium silicate.
7. The compound used in recharging of permutit is [ ]
(a) NaCl (b) HCl (c) NaOH (d) CaCl2
8. Rain water picks up gases like CO2, O2 etc. from ______________.
9. Anion exchange resin is regenerated by using_______________.
10. The chemical formula of Zeolite is _______________________________.
11. The solvent molecules move from low concentration region to high
concentration region through the semi permeable membrane is
called____________.
12. Which of the following statement is correct? [ ]
(I) Temporary hardness in water cannot be removed by boiling.

(II) Temporary hardness in water can be removed by boiling.

(III) Hard water gives lather easily with soap solution.
(IV) Temporary hardness is also called as bi carbonate hardness.
(a) only II (b) both II & IV (c) only IV (d) both I & III
13. Which of the following statement is correct for ion exchange bed? [ ]
(I) Cross linked polymers with micro porous structure.
(II) Branched polymers with porous structure.
(III) Cross linked polymers with non-porous structure.
(IV) Branched polymers with non-porous structure.
(a) only I (b) both I & III (c) only II (d) both II & IV

14. Match the list-I and list-II of the following. [ ]

List-I List-II
(1) Natrolite (A) Sodium Chloride
(2) Calgon (B) Natural Zeolite
(3) Sea Water (C) Styrene divinyl benzene
(4) Ion exchange resin (D) sodium hexametaphosphate
(a) 1-B,2-D,3-A,4-C (b) 1-A,2-C,3-D,4-B
(c)1-C,2-A,3-D,4-B (d)1-A,2-B,3-C,4-D

Section B: Subjective Questions:

1. Define carbonate and non carbonate hardness of water; list out the
various disadvantages of hard water.
2. What is hard water? Give the action of hard water on soap.
3. How many types of hardness are there in hard water? Define each one.
4. What happens when temporary hard water is boiled? (Give equations)
5. Why hardness of water is expressed in terms of CaCO3 equivalents?
6. Explain the softening of hard water by Zeolite process.
7. How can you apply the Ion –exchange process for the softening of hard
water? Explain in detail.
8. What are the chemicals used for regeneration of ion exchange resins?
9. What is principle of reverse osmosis? How it is used for the conversion of
sea water to pure water.
10. Distinguish between zeolite and Ion – Exchange processes.
11. Enumerate advantages of Reverse osmosis over Ion exchange process.
12. Explain internal treatment of water.
13. Discuss boiler troubles with hard water.
14. Why a soft water need not be demineralised water but demineralized
water is always soft water?
15. Explain the following;
a) priming and foaming b) Caustic embrittlement C) Calgon conditioning
Problems:
1. Determine the hardness of water in terms of ppm, oFr, if the hardness of
water sample is14°Clark.
2. A sample of water contains 100ppm of total hardness and 25ppm of
temporary hardness. Calculate the permanent hardness of water in
degree Clark and degree French.
3. Calculate the CaCO3 equivalents of the following dissolved salts present
in 1000 liters of a sample of water containing in ppm,
Ca(HCO3)2=16.2,CaCl2=11.1,MgSO4=60, MgCl2=19.
4. Calculate the temporary hardness of a water sample having the following
analysis.
Ca(HCO3)2=162mgs/L, Mg(HCO3)2=7.3mgs/L, CaCl2=22.2mgs/L and
MgCl2=95mgs/L.
5. A sample of hard water contains the following dissolved salts per litre.
CaCl2=111mg, CaSO4=1.36mg, Ca(HCO3)2=16.2mg, Mg(HCO3)2=14.6mg,
Silica=40mgs, Turbidity=10mgs. Calculate the temporary, permanent
and total hardness of water in ppm, degree Clark and degree French.
6. Water sample on analysis gave the following results; Mg(HCO3)2=70mg/L,
CaCl2=220mg/L, MgSO4=120 mg/L, Ca(NO3)2 =164 mg/L. Calculate the
carbonate and non-carbonate hardness of the water sample.
7. A sample of water on analysis has been found to contain following in
ppm.
Ca(HCO3)2=4.86; Mg(HCO3)2=5.84; CaSO4=6.80; MgSO4=8.40; Calculate
the temporary and permanent hardness of water.
(Atomic weights: Ca=40; Mg=24; C=12; S=32; O=16, H=1).

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