Sources of water

Plenty of water is available in nature. Water is obtained in nature from different sources. Depending
on the source water may be classified as:
(a) Under –ground water, (b) Surface water, (c) Sea water, and (d) Rainwater.
(a) Under-ground water: Underground water or ground water is accumulated under ground through
seepage of surface water and rainwater forming different layers of water depending upon the
impervious strata of rock and soil. Sometimes this water exudes in the form of springs. Water of
some springs contains dissolved sulfur compounds. Such water may be used for curing some skin
disease and dandruff. Some time this water also contains soluble salts of calcium and magnesium
such as Ca(HCO3)2, CaCl2, CaSO4, Mg(HCO3)2, MgCl2, MgSO4.
(b) Surface water: Surface water may be classified as
(i) flowing water: The origin of this water is rain and snow of the mountain. In summer snow of the
mountain region melts and flows in the form of river. The rain of hilly area also comes down in the
form of river water. The original river water is pure, but it takes dissolved and suspended impurities
as it flows through plain lands. It also dissolves CO2 from the open atmosphere. This dissolved CO2
enables the water to dissolve carbonate salt as it comes in contact with it.
CaCO3 + H2O + CO2 ⟶ Ca(HCO3)2
(ii) Still water: Water of ponds, lakes and reservoirs is usually considered as still water. This water
varies widely in composition from locality to locality. It always contains fine mud as suspended
particles. The fine particles of mud can be settled down by using coagulants. Mud free still water
usually colourless and clear. The hardness of this water is also high but usually less than ground
water. The uses of this water causes scale formation in boilers, economizers, coolers etc. unless it is
treated properly.
(c) Sea water: Sea water may be considered as the vast reservoir of water. But this water is too saline
to be used as industrial water except as coolant. This water is also neither suitable for municipal use
nor for irrigation.
(d) Rainwater: The purest form of water is the rainwater. It may be considered as the water distilled
by the natural process. However, this water is not suitable for industrial application. This is because of
its irregular supply and its collection is relatively expensive.

Effect of rocks and minerals on under-ground water:

During their seepage, rain and surface water comes in contact with different types of minerals. The
effects of such contact of water are briefly discussed below:
I. Dissolution: Rocks always contain some minerals, which are soluble in water. For example,
Ca(HCO3)2, CaCl2, CaSO4, Mg(HCO3)2, MgCl2, MgSO4 etc. are readily soluble in water and ions of
these salts are found in under-ground water.
II. Hydration: Rocks always contain some minerals, which are easily hydrated. Minerals in hydrated
forms have larger volume than the dehydrated minerals. As a results, disintegration of rocks is
observed and in under-ground water these easily hydrated minerals are found to be present. For
example, in contact with water anhydrous calcium sulphate is hydrated to gypsum with 33%
volume expansion.
CaSO4 + 2H2O ⟶ CaSO4 . 2H2O (33% volume expansion).
Mg2SiO4 + nH2O ⟶ Mg2SiO4 . nH2O.
III. Dissolved oxygen: Oxygen is also to some extent soluble in water. Consequently, it is found in
almost all-natural water in dissolved condition. Dissolved oxygen in water leads to oxidation and
hydration of some constituent ores of rocks.
Oxidation hydration
Fe3O4 ⟶ Fe2O3 ⟶ 3Fe2O3. 2H2O
2FeS2 + 7O2+ 9H2O ⟶ 2FeSO4 . 7H2O + 2H2SO4

iv. Dissolved CO2: CO2 is the most highly soluble gas in water. CO2 present in water converts the
insoluble carbonates of Ca, Mg and Fe into their relatively more soluble bicarbonates.
CaCO3 + CO2 + H2O ⟶ Ca(HCO3)2
Rocks containing minerals like silicates and aluminosilicates of Na, K, Ca and Fe are attacked by CO 2
producing soluble carbonates, bicarbonates and silica.
K2O Al2O3 6SiO2 + H2O + CO2 ⟶ K2CO3 + Al2O3 2SiO22H2O + 4SiO2
 Hardness of Water
Hardness of water may be defined as its incapability to produce lather /foam when treated with soap
or Water hardness is the amount of dissolved calcium and magnesium in the water. The hardness of
water is caused mainly by the presence of Ca2+ and Mg2+ in dissolved condition in water. The
incapability of forming lather/foam by soap is due to the fact that when hard water is treated with
soap, the Ca2+ and Mg2+ ions react with soap and form insoluble scum of calcium and magnesium salts
of higher fatty acids. Ca and Mg salts of higher fatty acids are not soluble in water, thus do not have
any soap/detergent effect.
CaCl2/MgCl2 + 2C17H35COONa ⟶ (C17H35COO)2Ca/Mg + 2NaCl

Types of hardness
Temporary Hardness: Calcium and Magnesium salts when present in the form of bicarbonate, their
hardness are considered as temporary hardness. This is due to the fact that on simply boiling, calcium
and magnesium bicarbonates are precipitated out as calcium/magnesium carbonate.
Ca/Mg(HCO3)2 + heat ⟶ CaCO3/MgCO3 (ppt) + H2O +CO2
Permanent hardness: The hardness caused by the presence of dissolved chloride, sulphates and
nitrates of Ca2+, Mg2+ , Fe2+ and other heavy metal ions are refereed to as permanent hardness. These
can’t be removed by simple boiling. The summation of temporary and permanent hardness is refferd
to as total hardness.

Moreover, there are also alkaline and non alkaline hardness, alkaline hardness is due to the presence
of Mg, Ca, Fe, Al salts which imparts alkalinity to the water. Non alkaline hardness are due to the
presence of chlorides and sulphates of Mg and Ca salts which do not impart any alkalinity to the
water.
 Determination of temporary hardness (Hehner’s Method)

Temporary hard is due to the presence of bicarbonates of Ca and Mg. Temporary hardness can easily
be removed by simply boiling. On boiling CO2 evaporates out with the precipitation of carbonates.
Ca(HCO3)2 ⟶ CaCO3 + H2O + CO2
Mg(HCO3)2 ⟶ MgCO3 + H2O + CO2
Since bicarbonates imparts alkalinity to water, therefore, the temporary hardness can be
conveniently determined by titration with a standard solution of HCl before and after boiling. On
boiling removal of Ca and Mg-bicarbonates takes place as they are converted into insoluble
carbonates, hence the depletion of in alkalinity of sample water due to boiling can be taken as a
measure of temporary hardness.

Determination of permanent hardness of water by alkali mixture method:

Permanent hardness is due to the presence of sulphates, chlorides, and nitrates of Ca, Mg, Fe and
other heavy metals. These are soluble in water and are not precipitated on boiling, so these cannot
be removed by boiling. The principle involved in the determination of permanent hardness is the
complete conversion of the Ca2+ and Mg2+ into insoluble carbonates and hydroxides respectively by
adding excess amount of alkali mixture (NaOH and Na2CO3) into boiled sample water. After complete
precipitation of CaCO3 and Mg(OH)2, excess of alkali remaining unreacted is titrated with a standard
solution of HCl using methyl orange as indicator.
CaSO4 + Na2CO3 ⟶ CaCO3 + Na2SO4
MgCl2 + 2NaOH⟶ Mg(OH)2 + NaCl
 Determination of total hardness of water by soap solution
method:
Soluble soaps are Na and K-salts of higher fatty acids. When the soaps are used in hard water, they
react with the substances causing hardness of water and form insoluble precipitate. They do not form
lather and foam until all the hardness are precipitated out.
Ca/Mg(HCO3)2 + 2C17H35COONa ⟶(C17H35COO)2Ca/Mg+ NaHCO3

Ca/MgSO4 + 2C17H35COONa ⟶ C17H35COO)2Ca/Mg+ Na2SO4

Ca/MgCl2 + 2C17H35COONa ⟶ C17H35COO)2Ca/Mg+ 2NaCl

Therefore, after precipitating out all the Ca2+ and Mg2+ ions, the addition of a drop soap solution gives
lather/foam on shaking.
Thus, the total hardness of sample water can be determined by the titration of a given amount of
sample water with a standard soap solution in alcohol. The end point is detected by the formation of
stable lather/foam persisting even after shaking for about 2 minutes.
Temporary hardness is determined by the same titration taking same amount of boiled water. The
difference in volume of soap solution required for the titration of sample water and boiled sample
water can be used to calculate the value of temporary hardness of the water.
 Determination of total hardness of water by EDTA (complexometric) method:
Ethylenediaminetetraacetic acid (EDTA) is a reagent that forms EDTA-metal complexes with many
metal ions (but not with alkali metal ions such as Na+ and K+). In alkaline conditions (pH›9) it forms
stable complexes with the alkaline earth metal ions Ca2+ and Mg2+. The EDTA reagent can be used
to measure the total quantity of dissolved Ca2+ and Mg2+ ions in a water sample. Thus the total
hardness of a water sample can be estimated by titration with a standard solution of EDTA.

EDT Di-sodium salt of EDTA

Suitable conditionsA for the titration are achieved by the addition of a buffer solution of pH 10. The
buffer solution stabilizes the pH at 10. There are H+ ions produced as the reaction proceeds, and
without the buffer solution the pH would decrease.
The disodium salt of EDTA is more commonly used as the reagent rather than EDTA itself. If Na 2H2Y
represents this salt, it ionizes in aqueous solution to H2Y2-, which complexes in a 1:1 ratio with
either Ca2+ or Mg2+ ions (which are represented as M2+). The reaction can be represented as follows:
H2Y2- + M2+ → MY2- + 2H+
The indicator Eriochrome Black T is used to detect the end point. This indicator has a different
colour when complexed to metal ions than when it is a free indicator. The reaction between the
red indicator-metal complex and the EDTA reagent at the end point can be represented as follows:
MIn- + H2Y2- → HIn2- + MY2- + H+
Wine Red blue
 Determination of chloride ion in water by Mohr’s
method:present in water are usually NaCl, MgCl , CaCl etc. Chloride ion readily reacts with
The salts of chloride 2 2
the silver ion of AgNO3 and forms AgCl ppt. AgNO3 reacts with potassium chromate in the absence of
Cl- ion of sample water, the additional drop of AgNO3 reacts with potassium chromate and forms red
silver chromate. K2CrO4 is yellow in color but Ag2CrO4 ppt is red in color. Thus changes of color from
yellow to red indicates the end point. Therefore, the concentration of chloride ion can be determined
by the titration with standard silver nitrate solution using K2CrO4 as indicator.
Cl- + AgNO3 ⟶ AgCl (white ppt)+ NO3-
K2CrO4(Yellow)+ AgNO3 ⟶ Ag2CrO4 (Reddish Brown) + KNO3

Determination of dissolved oxygen in water:

Oxygen is present in water in dissolved condition. The principle involved in the determination of
dissolved oxygen is to oxidize an equivalent amount of KI to iodine molecules by the dissolved oxygen
with the help of MnSO4 and NaOH as intermediate reagents. The basic manganic oxide formed from
MnSO4 and NaOH acts as oxygen carrier and brings the dissolved oxygen into nascent form to take
part in the reaction (oxidation of KI to I2).
MnSO4 + NaOH ⟶ Mn(OH)2 + Na2SO4
Mn(OH)2 + O2 ⟶ 2MnO(OH)2 (Basic manganic oxide)
MnO(OH)2 + H2SO4 ⟶ MnSO4 + 2H2O + [O]
2KI + H2SO4 +[O] ⟶ K2SO4 + 2H2O + I2
The liberated iodine (equivalent to dissolved oxygen) is then titration with a standard solution of
sodium thiosulphate using starch as an indicator. The reaction involved in this titration is
I2 + Na2S2O3 ⟶ Na2S4O6 + 2NaI
 Treatment of water:
Water treatment is any process that makes water more acceptable for a specific end-use. The end
use may be drinking, industrial water supply, irrigation, river flow maintenance, water recreation
or many other uses, including being safely returned to the environment.
Different impurities present in water are removed by different methods and purification of water
is usually done by the following operations;
1. Removal of volatile and oxidisable impurities
2. Removal of suspended impurities
3. Removal of soluble impurities
4. Removal of bacteria and micro-organisms
5. Removal of oil

Removal of suspended impurities

Suspended impurities in water may have both organic and inorganic origin and can be removed by
the following methods
(a) Sedimentation:
The sedimentation process removes many particles including clay and silt based turbidity, natural
organic matter, and other associated impurities. The principle involves in this process water is
allowed to keep at rest in a big tank or reservoirs for few days or even weeks. as a result floating
particles in water fall down to the bottom by gravitational force. The floc that falls to the bottom of
the basins is collected into a hopper by large rotating scrapers where it is removed several times daily
by the plant operators. The particles which are relatively bigger among the suspended particles, will
sediment easily.
 Coagulation:
To separate the dissolved and suspended particles from the water coagulation process is used. Most
solids suspended particles in water possess a negative charge; they consequently repel each other.
This repulsion prevents the particles from agglomerating, causing them to remain in suspension.
Coagulation destabilizes the particles’ charges. Coagulants with charges opposite to those of the
suspended solids are added to the water to neutralise the negative charges on dispersed non-settable
solids such as clay and organic substances. Once the charge is neutralised, the small-suspended
particles are capable of sticking together. Some times they do not settle down at all, in order to settle
down these finer particles quickly some chemical agents(coagulant) are used. The coagulants are
normally salts of iron and aluminium. Theses salts react with carbonate radicals present in water and
produce precipitates of these metals. These precipitates adsorb suspended impurities and cause them
settle down. Some example of coagulant are Al2(SO4)3, NaAlO2, FeSO4.7H2O, FeCl3 or FeCl3.6H2O and
Fe2(SO4)3
A12(SO4)3 + 3 Ca(HCO3)2 ------------> 2 Al(OH)3 + 3CaSO4 + 6 CO2
Fe2(SO4)3 + 3 Ca(HCO3)2 ------------> 2 Fe(OH)3 + 3CaSO4 + 6 CO2
2 FeCl3 + 3 Ca(HCO3)2 ------------> 2 Fe(OH)3 + 3CaCl2 + 6CO2
Filtration
The sludge formed by sedimentation and coagulation is removed by filtration. Filtration is carried
out by passing water through a filtering bed. The filters bed are made of layers of sand and gravel,
and in some cases, crushed anthracite. Filtering bed consist of 3 feet fine sands below which
one-foot thick coarser sand which in turn is supported by 18 inches thick bed of different graded
gravels. Below the gravels there are drains for taking out water . After long use when a lot of
precipitates deposit in sands, the filtration process become slow. At this stage the sand bed is taken
out, washed and is then replaced again.
Filtration
 Removal of soluble impurities or hardness
Boiling method
By simple boiling method, bicarbonates of calcium and magnesium can be removed. The soluble
bicarbonates of calcium and magnesium decompose on boiling and are precipitated as insoluble
carbonates and hydroxide respectively which are settled down and then filtered off.
Ca(HCO3)2 ⟶ CaCO3↓ +CO2 + 2H2O
Mg(HCO3)2 ⟶ MgCO3 + CO2 + 2H2O
Mg(HCO3)2 + 2H2O ⟶ Mg(OH)2↓ + 2H2O + CO2
 Clark Process of softening of water
In this process a calculate amount of lime is added. Lime converts bicarbonates of Ca and Mg into
insoluble CaCO3 and Mg(OH)2 respectively, which are then easily removed by filtration.
H2O + CaO ⟶ Ca(OH)2
Ca(HCO3)2 + Ca(OH)2 ⟶ CaCO3↓ + 2H2O
Mg(HCO3)2 + Ca(OH)2 ⟶ MgCO3 + CaCO3↓ + 2H2O
MgCO3 + Ca(OH)2 ⟶ Mg(OH)2↓ + CaCO3↓
Ca(HCO3)2 + CaO ⟶ 2CaCO3↓ + H2O
Mg(HCO3)2 + 2CaO ⟶ Mg(OH)2↓ + 2CaCO3↓
In the Clark process the bicarbonate hardness of water is reduced to 0.7-1.00 ppm. Hardness due to
Mg is removed if there is excess of OH-. The dissolved CO2 is also remove by the addition of lime
CO2 + CaO ⟶ CaCO3↓
The hardness caused by the presence of sulphates and chlorides of Ca and Mg cannot be removed
by this process. Thus the following two special methods are used for such cases.
Lime-Soda Process of softening of water
In this process soda ash is added after the addition of lime in the water. The lime removes
bicarbonates of Ca and Mg by converting them into insoluble CaCO3 and Mg(OH)2 respectively. The
sulphate and chloride salts are removed by soda and lime by converting them into insoluble CaCO 3
and Mg(OH)2 respectively, as shown below.
MgCl2 + Ca(OH)2 ⟶ Mg(OH)2↓+ CaCl2
CaCl2 + Na2CO3 ⟶ CaCO3↓ + 2NaCl
CaSO4 + Na2CO3 ⟶ CaCO3↓ + Na2SO4
MgSO4 + Na2CO3 + Ca(OH)2⟶ CaCO3↓ + Mg(OH)2↓+ Na2SO4
 Permutit or Zeolite Process of softening of water
Zeolite is a relatively open, three-dimensional crystalline structure and porous aluminosilicate, which
trapped water molecules in the gaps between them. There are two types of zeolite such as natural
or nonporous zeolite and synthetic or porous zeolites.
Natural Zeolite:
Thomsonite: (Na2O,CaO) Al2O3 2SiO2, 2.5 H2O
Natrolite: (Na2O), Al2O3 3 SiO2, 2 H2O
Stilbite: (Na2O,CaO) Al2O3 6 SiO2, 6 H2O
Synthetic Zeolite:
Permutit : Na2O, Al2O3 n SiO2, x H2O ( where, n = 5-13 and x – 3-4)
Permutit is more generally used than natural zeolite due to possessing porous and gel like structure.
Permutit is insoluble in water but can act as base exchanger when brought in contact with water
containing cations. The permutit or zeolite is placed in a suitable column in the filter. Hard water
containing Ca2+ and Mg2+ is allowed to percolate through it. During the percolation Ca 2+ and Mg2+ ions
are taken up by zeolite. At the same time zeolite release equivalent amount of Na +.

Mg/Ca(HCO3)2 + Na2Z(Zeolite) ⟶ Mg/CaZ+ 2NaHCO3

Mg/CaCl2 + Na2Z⟶ Mg/CaZ + 2NaCl
Mg/CaSO4 + Na2Z ⟶ Mg/CaZ ↓ + Na2SO4

When zeolite bed is saturated with Ca2+ and Mg2+ ions then
its water softening capacity is lost. It is then flashed with
saturated brine solution to regenerated zeolite bed.
MgZ/CaZ + NaCl ⟶ Na2Z + MgCl2/CaCl2
 Advantages of Zeolite process
a) It removes hardness up to 10 ppm
b) It does not form any precipitate/sludge.
c) The maintenance and operation is easy and does not require special skills.
d) Requires less time for softening.
e) Equipment are compact and requires less space.

Disdvantages of Zeolite process

a) It removes only hardness contributing cations but leaves sodium salts in it. Hence,
it cannot be used in high pressure boilers (NaHCO3 and Na2CO3 leads to caustic
embrittlement)
b) It is not suitable if the water is turbid. The colloidal particles present in the water
will clog the process of the zeolite.

The major troubles arise in the boiler due to use of impure

water are as follows
a) Scale or sludge formation
b) Corrosion
c) Priming and Foaming (Carry over)
d) Caustic embrittlement etc.
 Scale or sludge in boiler
Water is used as a raw materials in the boiler for the generation of steam in the industries. In the boiler
a part of water always evaporates out. As a result, the concentration of impurities present in small
amount gradually increases. Sometimes it goes beyond the saturation limit and is deposited. The
deposited stick to the metal surface are known as scales. The soft and muddy deposits, which do not
stick to the metal surface but remain in the form of suspensions and can be flushed out easily, are
called sludge. Scale and sludge are usually found in the form of oxide, carbonate and sulphates
Fe2+ + 3H2O ⟶ Fe2O3+ 3H2
Mg2+ + H2O ⟶ MgO + H2
Ca2+ + CO2 + H2O ⟶ CaCO3 + H2
Ca2+ + SO4- ⟶ CaSO4
Ca2+ + 2HCO3- ⟶ CaCO3 + CO2 +H2O
Reasons of scale formation in the boiler
1. When water is heated in the boiler the soluble bicarbonates are converted into insoluble
carbonate, which are usually precipitated out.
Ca(HCO3)2 ⟶ CaCO3 + CO2 +H2O

2. The concentration of soluble impurities rise up to the extend of saturation and get deposited by the
evaporation of water (i.e, steam generation).
3. The solubility product constant (Ksp) for some salts are very law particularly in hot or boiling water.
As a results they become insoluble and get deposited in the form of scales e.g. CaSO 4, CaSiO3,
MgSiO3.
4. Suspended and colloidal matters settle down at high temperature (because of law viscosity) and
 Disadvantage of scale formation in boiler:
The scale deposited on the surface of the boiler imparts the following difficulties:
1. Scale deposits firmly stick to the metal surface, and are very difficult to remove particularly if it is
silica scale.
2. Scale is poor conductor of heat, thus it decreases the evaporation capacity of the boiler. Hence
larger quantity of fuel is to be used for getting equal amount of steam.
3. Scale does not allow water to come in contact with the heating plates or tubes of the boiler. This
causes overheating and sometimes burning out of the heating plates and tubes.
4. Due to deposition of scale and sludge, the water feed and steam outlet tubes may get blocked
and the efficiency of the boiler is decreased.
5. There are some salts e.g. MgCl2 if deposited as scale, corrode away the tubes, plates. Corrosion in
localized area at boiler may lead to sudden failure of the boiler tubes. These may cause a serious
accident.
Prevention of scale and sludge formation:
The following to methods are usually used to prevent scale formation in the boiler
1. Softening of water by various methods (discussed previously such as Clark, lime-soda and zeolite
process)
2. Internal prevention: (i) Scale and sludge formation in the boiler can be avoided by introducing
colloid forming substances such as kerosene, tannin or other organic substances. These
substances get coated over the scale forming particles and thus prevent the coalescence or
joining together and also to stick on the metal surface. So the insoluble materials remain loose or
suspended in water and can be easily removed by blowing off.
(ii) In the boiler feed water, phosphate concentration is maintained slightly higher than the
required amount, so that calcium ion present in the feed water precipitated as loose sludge.
10CaCl2 + 6Na3PO4 + 2NaOH⟶ Ca10(PO4)6(OH)2 + 20NaCl
 Silica scales and their removal :
Silica is one of the harmful scale forming constituent of the boiled feed water. It forms many insoluble,
sticky compounds like CaSiO3, Na2AlSiO3 and thus deposited and blocked the steam passage.
The silica from the boiled feed water can be removed by
(a) Using magnesium compound: Magnesium compounds like MgCl2, Mg(OH)2 absorbs silica on their
surface. Thus silica may be removed by these substances. But since Mg is undesirable in boiler feed
water because of its corrosive nature, this method is not used widely.
(b) Using ferric sulphate as coagulant: Fe2(SO4)3 may be used as coagulant along with Ca(OH)2 at an
optimum pH of about 9. At this pH value Fe2(SO4)3 is converted to Fe(OH)2, which causes
coagulation of fine silica particle and filtered off.
Fe2(SO4)3 + 3Ca(OH)2 ⟶ 2Fe(OH)2 + 3CaSO4
(c) By fluorosilicate process: Silica in water is converted to fluorosilicic acid by adding NaF into water.
Fluorosilicic acid is highly ionized and is removed by passing over a weakly basic anion exhanger.
SiO2+ H2O + 6NaF⟶ H2SiF6 + NaOH
H2SiF6 + Na2Re⟶ Na2SiF6 + H2Re
 Corrosion of boiler
If untreated water is used in the boiler, corrosion may take place on boiler tubes or plates due to the
following reasons:
(i) Presence of free acid in water.
(ii) Acids formed by hydrolysis of salts in water.
(iii) Acids formed by the hydrolysis of fatty lubricating oils
(iv) Presence of dissolved gases such as O2, CO2, H2S in water. H2S gets oxidized into H2SO4.
(v) Some salts in water may also be the cause of corrosion, e.g. MgCl2 corrodes the boiler tubes as
follows:
MgCl2 + Fe + 2H2O ⟶ Mg(OH)2 + FeCl2 +H2
Manganese sulfide (MnS2) in water may be oxidized and hydrolyzed to form sulphuric acid, which
corrodes the boiler tubes and plates
Prevention of corrosion
Introducing a calculated quantity of alkali into water to neutralize acidity can prevent corrosion of
boiler. Antioxidants may also be used to remove dissolved oxygen. Therefore, to prevent corrosion in
boiler tubes and plates the above mention point can be done by
(i) The concentration of free NaOH in boiler water must be kept in a favorable ratio that is by
keeping pH of water in between 8-9. In addition to this certain amount of excess phosphate ion is
also kept in the boiler feed water.
(ii) Dissolved oxygen must be eliminated as far as possible
 Carryover, priming and foaming

Priming:
When a boiler is steaming (i.e., producing steam) rapidly, some particles of the liquid water are
carried along-with the steam. This process of 'wet steam' formation is called priming. Priming is
mainly attributed to the presence of suspended impurities and to some extend dissolved impurities in
the water.. The other cause of priming are;
(i) high steam velocity
(ii) very high water level in the boiler
(iii) presence of foam on the surface of water
(iv) sudden increase in demand of steam and
(v) faulty boiler design

Priming can be minimized by-

(i) Good boiler design, which maintains the uniform heat distribution, consequently proper
evaporation of water
(ii) maintaining low water level
(iii) avoiding rapid changes in steam requirement
(iV) efficient softening and filtration of the boiler-feed water.
 Foaming: The formation of small but persistent water bubble at the surface of water in boiler is called
foaming. During evaporation, the steam causing excessive priming carries these bubbles. Foam is
usually formed when there is a difference in concentration of solute and suspended matter between
surface film and the bulk water. Clay, organic matter, oil, grease, finely divided particles of sludge may
be the cause of water foaming. The detrimental effect of foaming is:
(i) If the steam bubbles is persistent enough, then they may be moved to the pre-heater. The
accompanying liquid may carry dissolved salts, suspend solid, and other stabilizing materials, which will
be deposited on the cylinder walls, turbine blades, or in steam lines.
(ii) If the stability of the the bubble is such that it breaks near the steam outlet, tiny droplets of the
liquid from the collapsing bubble may introduce into the steam lines giving wet steam.

Foaming can be prevented by-

(a) Removing the foam forming and stabilizing agent from water
(b) By removing clay and other suspended matter as well as droplets of oil and grease by the treatment
of the boiler-feed water
(c) Preventing the water droplet from entering the steam line by adjusting spiral or cyclone baffles
near the steam outlets
(d) Controlling the concentration of salts and sludge in the boiler by intermittent and continuous
blow-down
(e) Using anti-foaming agent, e.g. castor oil, polyamide, anti-foamed mixture of aerosol and ethyl
cetab, can also prevent foaming
 Caustic embrittlement
Caustic embrittlement 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 the softened water. In high pressure boilers, Na2CO3 decomposes to give sodium
hydroxide and carbon dioxide,
Na2CO3 + H2O → 2NaOH + CO2
and this makes the boiler water basic ["caustic"]. The NaOH containing water flows into the
minute hair-cracks, present in the 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, thereby dissolving iron of boiler as sodium ferroate this
causes embrittlement of boiler parts, particularly stressed parts (like bends, joints, rivets, etc.),
causing even failure of the boiler.
Caustic embrittlement can be avoided :
1.by using sodium phosphate as softening agent, instead of sodium carbonate ;
2.by adding tannin or lignin to boiler water, since these blocks the hair-cracks, thereby preventing
infiltration of caustic soda solution in these;
3.by adding sodium sulphate to boiler water. Na2SO4 also blocks hair-cracks, thereby preventing
infiltration of caustic soda solutions. It has been observed that caustic cracking can be prevented,
if Na2SO4 is added to boiler water so that the ratio Na2SO4 /NaOH is kept as 1:1:2:1 and 3:1 in
boilers working respectively at pressures up to 10, 20 and above 20 atmospheres
A student has been given 1 L of water and asked to determine the concentration
of dissolved calcium and magnesium ions in the water.
Using a 0.010 mol L-1 standard solution of EDTA, the student titrated 100.0 mL
samples of the water using Eriochromshwartz-T as the indicator.
The student's titration results are shown below:
Titration No Volume of EDTA (mL)
1 10.14
2 10.10
3 10.12

Determine the total concentration of calcium and magnesium ions in the water sample.
1. Calculate the moles of EDTA required to complex with the Ca2+ and Mg2+ ions in the water.
concentration of EDTA = 0.010 mol L-1 volume of EDTA solution = average titrate = (10.14 + 10.10 +
10.12) ÷ 3 = 10.12 mL = 10.12 x 10-3 L moles EDTA = concentration (mol L-1) x volume (L) = 0.010 x
10.12 x 10-3 = 1.012 x 10-4 mol
2. Write the equation for the reaction between EDTA and Ca2+ and Mg2+:
Ca2+ + H2EDTA2- → CaEDTA2- + 2H+
Mg2+ + H2EDTA2- → MgEDTA2- + 2H+
Let M2+ = Ca2+ + Mg2+, then
M2+ + H2EDTA2- → MEDTA2- + 2H+
3. Calculate moles of M2+ (= Ca2+ + Mg2+) present in the 100.0 mL water sample From the balanced
chemical equation: 1 mole M2+ reacts with 1 mole EDTA
So 1.012 x 10-4 moles of EDTA react with 1.012 x 10-4 moles of M2+
4. Calculate the concentration of M2+ (= Ca2+ + Mg2+) in the water, concentration (M2+) = moles M2+ ÷
volume (L) moles M2+ = 1.012 x 10-4 mol volume = 100.0 mL = 100.0 x 10-3 L concentration (M2+) =
1.012 x 10-4 ÷ 100.0 x 10-3 = 1.012 x 10-3 mol L-1
5. The total concentration of dissolved calcium ions and magnesium ions in the water is 1.012 x
10-3 mol L-1