Water technology

Introduction :

Water is a ubiquitous chemical substance that is composed of hydrogen and oxygen and is vital
for all known forms of life. In typical usage, water refers only to its liquid form or state, but the
substance also has a solid state, ice, and a gaseous state, water vapor or steam . Water covers
71% of the Earth’s surface. On Earth, it is found mostly in oceans and other large water bodies,
with 1.6% of water below ground in aquifers and 0.001% in the air as vapor, clouds (formed of
solid and liquid water particles suspended in air), and precipitation. Oceans hold 97% of surface
water, glaciers and polar ice caps 2.4%, and other land surface water such as rivers, lakes and
ponds 0.6%. A very small amount of the Earth's water is contained within biological bodies and
manufactured products.

Clean, fresh drinking water is essential to human and other life forms. Access to safe drinking
water has improved steadily and substantially over the last decades in almost every part of the
world. There is a clear correlation between access to safe water and GDP per capital. However,
some observers have estimated that by 2025 more than half of the world population will be
facing water-based vulnerability. A recent report (November 2009) suggests that by 2030, in
some developing regions of the world, water demand will exceed supply by 50%. Water plays an
important role in the world economy as it functions as a solvent for a wide variety of chemical
substances and facilitates industrial cooling and transportation. Approximately 70% of
freshwater is consumed by agriculture.

Water is not only essential for the lives of animals and plants, but also occupies a unique position
in industries. Probably its most important use as an engineering material is in the steam
generation. Water is also used as coolant in power and chemical plants. In addition to it water is
widely used in other fields such as production of steel, rayon, paper, atomic energy, textiles etc.

CHARACTERISTICS IMPARTED BY IMPURITIES IN WATER

The natural water is usually contaminated by different types of impurities. The characteristic and
consequent effects of impurities on the quality of water are disclosed under the following three
heads:

Physical impurities: (a) Color in water is caused by metallic substance like salts of iron
,manganese, human materials, tannins, industrial effluents etc. Actually color in water is due
tom dissolved substances and substances present in fine colloids. The change in color of water is
not harmful, unless it is associated with toxic nature. Usually yellowish tinge indicates the
presence of chromium and appreciable amount of organic matter.Yellowish red color indicates
the presence of iron; while red brown indicates the presnce of peaty matter.

(b) Turbidity:
Turbidity is due to the colloidal, extremely fine suspension such as clay, slit, finely divided
matters (organic and inorganic) micro organisms like plankton, etc. Turbidity expresses the
optical properties of water containing insoluble substances, which scatter light rather than to
transmit I straight lie. The turbidity depends not only on the quantity of the insoluble substances,
but also on the size shape, and refractive index. Turbidity in water can be eliminated by
sedimentation, followed b coagulation, filtration etc.

(c) Taste:

Taste is usually interlinked directly with odour. However in some waste water, taste is not
accompanied by odour. Thus the presence of dissolved mineral I water produces taste, but not
odour. For example

i) Bitter taste can be due to the presence of iron, aluminum, manganese, sulphur or
excess lime.
ii) Soppy taste can be due to the presence of large amount of sodium bicarbonate.
iii) Brackish taste is due to the presence of unusual amount of salts.
iv) Palatable taste is due to the presence of dissolves gases and minerals in water.

(d) Odour:

Odour in water is undesirable for the domestic as well as industrial purposes. Disagreeable odour
in water may be caused by the presence of living organisms, decaying vegetation including
algae, fungi and weeds. The receiving water may be offensive where heavy pollution is caused
by sewage/industrial effluents. The most common disagreeable odour in water is due to the
presence of small quantity of sulphides. The cause of odour in polluted water are :

i) Presence of inorganic and organic compounds of N, S and P and the putrefaction

of proteins and other organic mistrials present in sewage.
ii) Industrial effluents containing organic substances such as alcohol, aldehyde,
phenols, ethers, ketones, etc. flowing into the water bodies.

Besides these (i) presence of alga in water bodies impart a strong grassy odour, due to the
liberation of traces of essential oils from their bodies, (ii) growth of iron and sulphur bacteria
may produce offensive odour, (iii) presence of colloidal vegetable matter in surface water
evolves a faint flavour called peaty odour (iv) clay and sand in finely divided state impart a faint
earthy odour,(v) improper bituminous coating on cast iron main pipes may give off a tarry odour
to water which passes through it, (vi) a faint odour is imparted to water. This ordour is due to the
impure hydrogen.

Chemical impurities in water

i) Inorganic and organic chemicals released from dyes, paints, drugs, pesticides, textiles,
tanneries etc .All these pollute water bodies .
ii) Acid discharge in water by DDT, high explosives, battery, industries etc. The use of this
water causes harmful effect on health of human beings.
 a) Acidity is not any specific pollutant and it simply determines the power to neutralize
hydroxyl ions and is usually expressed in terms of ppm of calcium carbonate equivalent.
Surface water and ground waters attain acidity from industrial wastage like acid, mine,
drainage, etc. Usually acidity is caused by the presence of free CO2, mineral acid and
weakly dissociated acids. Mineral acid are released when iron and aluminum salts
hydrolyzed.
b) Gases: All the natural water contains dissolved atmosphere CO2. Its solubility depends
upon temperature, pressure and dissolved mineral content of water. Also polluted waters
acquire CO2 from the biological oxidation of organic matter. Its presence in water is of no
significance.
c) Concentration of dissolved atmospheric O2 in water depends on temperature, pressure
and salt content in water. Dissolved O2 in industrial waters is nuisance since it induces
corrosion reaction. On the other hand dissolved oxygen in water is essential to the life of
aquatic organisms such as fish.
d) Dissolved NH3 in water arises from the decomposition of nitrogenous organic matter.
Polluted waters and sewages contain nitrogen in the form of nitrogenous organic
compounds and urea which are partially converted to NH3.
e) Mineral matters have origin from rocks and industrial effluents. These include mineral
acids Ca2+, Mg2+, Na+, K+, Fe2+, Cl-, NO3-, F-, SiO2 etc.
f) Biological impurities are algae, pathogenic bacteria, fungi, viruses, pathogens, parasites
worms etc. The source of this contamination is discharge of domestic and sewage wastes,
excreta etc.
g) Micro organisms are usually abundant in surface waters, but their count is often quite low
or even nil in deep well waters. The commonest type of micro organism form the point of
treatment are algae, fungi and bacteria, which often form slime thereby causing fouling as
well as corrosion. The slime of formed logs the spray nozzles and screens of the
circulating pumps in air conditioning and other industrial plants.
h) Sediment or suspended matter: Insoluble particles of soil and other inorganic and organic
materials that become suspended in water and that in terms of total mass are the largest
sources of water pollution. Suspended particulate matter clouds the water reduces the
ability of some organisms to find food, reduces the photosynthesis by aquatic plants,
disrupts aquatic food webs, and carries pesticides bacteria and other harmful substances.
i) Radioactive substances: radioisotopes that are water soluble or capable of being
biologically amplified to higher concentrations as they pass through food chains and
webs. Ionizing radiation from such isotopes can cause birth defects, cancer and genetic
damage.

Potential Health Effects Sources of Contaminant in

Contaminant
from Ingestion of Water Drinking Water
Antimony Increase in blood cholesterol; Discharge from petroleum
decrease in blood sugar refineries; fire retardants;
ceramics; electronics; solder
Arsenic Skin damage or problems with Erosion of natural deposits;
circulatory systems, and may runoff from orchards, runoff
have increased risk of getting from glass &
cancer electronicsproduction wastes
Asbestos Increased risk of developing Decay of asbestos cement in
(fiber >10 micrometers) benign intestinal polyps water mains; erosion of
natural deposits
Barium Increase in blood pressure Discharge of drilling wastes;
discharge from metal
refineries; erosion of natural
deposits
Beryllium Intestinal lesions Discharge from metal
refineries and coal-burning
factories; discharge from
electrical, aerospace, and
defense industries
Cadmium Kidney damage Corrosion of galvanized pipes;
erosion of natural deposits;
discharge from metal
refineries; runoff from waste
batteries and paints
Chromium (total) Allergic dermatitis Discharge from steel and pulp
mills; erosion of natural
deposits
Copper Short term exposure: Corrosion of household
Gastrointestinal distress plumbing systems; erosion of
natural deposits
Long term exposure: Liver or
kidney damage

People with Wilson's Disease

should consult their personal
doctor if the amount of copper
in their water exceeds the
action level
Cyanide (as free cyanide) Nerve damage or thyroid Discharge from steel/metal
problems factories; discharge from
plastic and fertilizer factories
Fluoride Bone disease (pain and Water additive which
tenderness of the bones); promotes strong teeth; erosion
Children may get mottled of natural deposits; discharge
teeth from fertilizer and aluminum
factories
Lead Infants and children: Delays in Corrosion of household
physical or mental plumbing systems; erosion of
development; children could natural deposits
show slight deficits in
attention span and learning
abilities
 Adults: Kidney problems;
high blood pressure
Mercury (inorganic) Kidney damage Erosion of natural deposits;
discharge from refineries and
factories; runoff from landfills
and croplands
Nitrate (measured as Infants below the age of six Runoff from fertilizer use;
Nitrogen) months who drink water leaching from septic tanks,
containing nitrate in excess of sewage; erosion of natural
the MCL could become deposits
seriously ill and, if untreated,
may die. Symptoms include
shortness of breath and blue-
baby syndrome.
Nitrite (measured as Nitrogen) Infants below the age of six Runoff from fertilizer use;
months who drink water leaching from septic tanks,
containing nitrite in excess of sewage; erosion of natural
the MCL could become deposits
seriously ill and, if untreated,
may die. Symptoms include
shortness of breath and blue-
baby syndrome.
Selenium Hair or fingernail loss; Discharge from petroleum
numbness in fingers or toes; refineries; erosion of natural
circulatory problems deposits; discharge from
mines
Thallium Hair loss; changes in blood; Leaching from ore-processing
kidney, intestine, or liver sites; discharge from
problems electronics, glass, and drug
factories

Radionuclides
Potential Health Effects Sources of Contaminant in
Contaminant
from Ingestion of Water Drinking Water
Alpha particles Increased risk of cancer Erosion of natural deposits of
certain minerals that are
radioactive and may emit a
form of radiation known as
alpha radiation
Beta particles and photon Increased risk of cancer Decay of natural and man-
emitters made deposits of

certain minerals that are

radioactive and may emit
forms of radiation known as
photons and beta radiation
Radium 226 and Radium 228 Increased risk of cancer Erosion of natural deposits
(combined)
Uranium Increased risk of cancer, Erosion of natural deposits
kidney toxicity

Drinking water standards comparative table

Parameters Units WHO ISI

standard Standard
pH 6.5-9.2 6.5-8.5
TDS (Total mg/l 500 500
dissolved salts)
Sulphate mg/l 200 200
Chloride mg/l 250 200
Cyanides mg/l 0.05 0.05
Fluride mg/l 1.5 0.6-1.2
Aluminium mg/l 0.2
Arsenic mg/l 0.01 0.01
Antimony mg/l 0.005
Barium mg/l 0.3
Boron mg/l 0.3
Cadmium mg/l 0.003 0.01
Lead mg/l 0.01 0.05
Mercury mg/l 0.001 0.001
Sodium mg/l 200
Zinc mg/l 3 5

Hard water:

Hard water is water that has high mineral content (in contrast with soft water). Hard water
minerals primarily consist of calcium (Ca2+), and magnesium (Mg2+) metal cations, and
sometimes other dissolved compounds such as bicarbonates and sulfates. Calcium usually enters
the water as either calcium carbonate (CaCO3), in the form of limestone and chalk, or calcium
sulfate (CaSO4), in the form of other mineral deposits. The predominant source of magnesium is
dolomite (CaMg(CO3)2). Hard water is generally not harmful to one's health.
The simplest way to determine the hardness of water is the lather/froth test: soap or toothpaste,
when agitated, lathers easily in soft water but not in hard water. More exact measurements of
hardness can be obtained through a wet titration. The total water 'hardness' (including both Ca2+
and Mg2+ ions) is read as parts per million (ppm) or weight/volume (mg/L) of calcium carbonate
(CaCO3) in the water. Although water hardness usually measures only the total concentrations of
calcium and magnesium (the two most prevalent, divalent metal ions), iron, aluminium, and
manganese may also be present at elevated levels in some geographical locations. Iron in this
case is important for, if present, it will be in its tervalent form, causing the calcification to be
brownish (the color of rust) instead of white (the color of most of the other compounds).

Hardness in water is defined as the presence of multivalent cations. Hardness in water can cause
water to form scales and a resistance to soap. It can also be defined as water that does not
produce lather with soap solutions, but produces white precipitate (scum). For example, sodium
stearate reacts with calcium:

2C17H35COONa + Ca2+ → (C17H35COO)2Ca + 2Na+

Hardness of water may also be defined as the soap-consuming capacity of water, or the capacity
of precipitation of soap as a characteristic property of water that prevents the lathering of soap.

Temporary hardness

Temporary hardness is caused by a combination of calcium ions and bicarbonate ions in the
water. It can be removed by boiling the water or by the addition of lime (calcium hydroxide).
Boiling promotes the formation of carbonate from the bicarbonate and precipitates calcium
carbonate out of solution, leaving water that is softer upon cooling.

The following is the equilibrium reaction when calcium carbonate (CaCO3) is dissolved in water:

CaCO3(s) + CO2(aq) + H2O ⇋ Ca2+(aq) + 2HCO3-(aq)

Upon heating, less CO2 is able to dissolve into the water . Since there is not enough CO2 around,
the reaction cannot proceed from left to right, and therefore the CaCO3 will not dissolve as
rapidly. Instead, the reaction is forced to the left (i.e., products to reactants) to re-establish
equilibrium, and solid CaCO3 is formed. Boiling the water will remove hardness as long as the
solid CaCO3 that precipitates out is removed. After cooling, if enough time passes, the water will
pick up CO2 from the air and the reaction will again proceed from left to right, allowing the
CaCO3 to "re-dissolve" into the water.
Permanent hardness

Permanent hardness is hardness (mineral content) that cannot be removed by boiling. It is usually
caused by the presence in the water of calcium and magnesium sulfates and/or chlorides which
become more soluble as the temperature rises. Despite the name, permanent hardness can be
removed using a water softener or ion exchange column, where the calcium and magnesium ions
are exchanged with the sodium ions in the column.

Hard water causes scaling, which is the left-over mineral deposits that are formed after the hard
water had evaporated. This is also known as lime scale. The scale can clog pipes, ruin water
heaters, coat the insides of tea and coffee pots, and decrease the life of toilet flushing units.

Similarly, insoluble salt residues that remain in hair after shampooing with hard water tend to
leave hair rougher and harder to untangle.

In industrial settings, water hardness must be constantly monitored to avoid costly breakdowns in
boilers, cooling towers, and other equipment that comes in contact with water. Hardness is
controlled by the addition of chemicals and by large-scale softening with zeolite
(Na2Al2Si2O8.xH2O) and ion exchange resins.

Unit of hardness:
Hardness is expressed in terms of equivalent of calcium carbonate. The reason for choosing
calcium carbonate as standard is that it is the most insoluble salt that can be precipitated in water
treatment.

Hence whatever dissolved salts are present in water they are first converted into calcium
carbonate equivalents. In general calcium carbonate equivalent of hardness is given by

= Wt. of the substance producing hardness X Eq.wt. of CaCO3

---------------------------------------------------------------
Eq.wt.of substance

Various units used to express hardness of water are as under

1. Parts per million (ppm)
2. Milligrams per liter (mg/L)
3. Degree French (oFr)

Parts per million (ppm)

It is defined as parts of calcium carbonate equivalent hardness present in 106 parts of water. This
is the most common unit for expressing the hardness of water.

Milligrams per liter (mg/L)

It is defined as the number of milligram of CaCO3 equivalent hardness present per liter of water.
Degree French
It is defined as parts of calcium carbonate equivalent hardness presnt in 105 parts of water.

Very Soft water 0-70 ppm of CaCO3

Soft water 70-140 ppm of CaCO3
Slightly hard water 140-210 ppm of CaCO3
Moderately hard 210-320 ppm of CaCO3
Hard water 320-530 ppm of CaCO3
Very hard water › 530 ppm of CaCO3

Determination of total hardness of water:

Total hardness includes both permanent and temporary hardness.

EDTA method:

It is the most important and more accurate method to determine the hardness of water.

The total hardness (permanent as well as temporary) in water is determined by titrating the
known volume of the water sample against standard ethylenediaminetetraacetic acid (EDTA)
solution in ammonia buffer solution having pH =10 using erichrome black-T (Erio T) as an
indicator. The calcium and magnesium ions present in water forms stable compound with EDTA
and less stable complex with erichrome black –T solution. The end point of the titration is clear
blue without any reddish tinge from wine red.

Principle

EDTA is a weak acid and has a structure as shown below.

HOOCH 2C CH2COOH
N CH2 CH2 N
CH2COOH
HOOCH 2C

1.a

- -
O OCH2C CH2COO
N CH2 CH2 N
-
- CH2COO
O OCH2C

1.b
a- The structure of EDTA
b- The structure of tetracarboxylate [EDTA]4- ion formed by the dissociation of EDTA
In aqueous solution buffered at pH 10 EDTA dissociate to form tetracarboxylate ion as shown in
figure 1.b. This ion is electron rich having six bonding sites. The four carboxylate groups and the
two nitrogen atoms. Each site has an electron pair available for bonding. The [EDTA]4- anion
wraps itself around a Ca2+ or Mg2+ ion so that all six electrons pairs are shared with the metal
ion as shown in the figure. In this manner [EDTA]4- forms strong 1:1 complexes known as
chelates with metal ions like Ca2+ and Mg 2+.

In an aqueous solution buffered at pH 10, Erio T also dissociate forming [H-Erio T ]2- ion a blue
ion that bonds with either Mg2+ or Ca 2+ ion to form a wine red complex. The reaction of [H-Erio
T]2- ion with Ca2+ and Mg2+ ions are reversible.

Ca 2+ (aq) + [ H-Erio T]2-(aq,blue) + H2O [Ca-Erio T]-(aq,wine red)

+H3O (aq)

Mg 2+ (aq) + [ H-Erio T]2-(aq,blue) + H2O [Mg-Erio T]-(aq,wine red)

+H3O (aq)

Complexes of Ca2+ and Mg2+ ions with [EDTA]4- and [H-Erio T]2- ions have different stability.
When the indicator is added to properly buffered hard water Ca2+ and Mg2+ ions form unstable
complexes with the indicator and turns the solution to wine red. The color persists until the end
point is reached during the titration with EDTA. When the end point is reached [EDTA]4- anion
breaks up the wine red [Mg-Erio T]- and [Ca-Erio T]- complexes releasing the [ H-Erio T]2- ion
and hence the solution changes from wine red to permanent blue color.

[Ca-Erio T]-(aq,wine red) +H3O (aq) +[EDTA]4- [Ca-EDTA] aq +

[ H-Erio T]2-(aq,blue) + H2O

[Mg-Erio T]-(aq,wine red) +H3O (aq) +[EDTA]4- [Mg-EDTA] aq +

[ H-Erio T]2-(aq,blue) + H2O
To determine the temporary hardness another sample of the same volume of water is boiled to
convert the bicarbonate to carbonate and the precipitated calcium carbonate is filtered off. The
filtrate after cooling is titrated against EDTA in the same way as above. This gives the
permanent hardness. The difference between the total and hardness and the permanent hardness
gives the temporary hardness.

Procedure:

Total hardness: Pipette out 50 ml of the sample of water into a clean titration flask, add 1 ml of
NH3-NH4Cl buffer solution and 3-4 drops of indicator. Titrate against 0.01 M EDTA till the
color changes from wine red to clear blue without any reddish tinge. Let the volume of EDTA
required be v1 ml.

Permanent hardness:

Transfer 50 ml of the sample of water into a clean 5oo ml beaker and boiled gently for 20-
30minutes. Cool and filtered it directly into a 250 ml conical flask. Add 1 ml of buffer solution
followed by 3-4 drops of indicator. Titrate against standard 0.01 M EDTA as described above.
Let the volume of EDTA required be v2 ml.

Calculation :

1000ml of 1 M EDTA = 100g CaCO3 ( Mol.weight of CaCO3 =100g)

1ml of 1 M EDTA = 100/ 1000 g of CaCO3

V1 ml of 0.01 M EDTA = V1 X 0.01 X 100

-------------------------- g of CaCO3
1000

50 ml of water sample contains = V1 X 0.01 X 100

-------------------------- g of CaCO3
1000

106 ( 1 million ) ml of water sample contains = V1 X 0.01 X 100 X 106

----------------------- g of CaCO3
1000 X 50
Similarly
Permanent hardness = V2 X 0.01 X 100 X 106
----------------------------- g of CaCO3
1000 X 50
Softening of water:

Internal treatment:

In this process (also called sequestration) an ion is prohibited to exhibit its original character by
complexing or converted into other more soluble salt by adding appropriate reagent. An internal
treatment is accomplished by adding a proper chemical to the boiler water either
a) To precipitate the scale forming impurities in the form of sludges
b) To convert them into compounds which will stay in dissolved form in water

Phosphate conditioning:

In high pressure boilers scale formation can be avoided by adding sodium phosphate which
reacts with hardness of water forming non-adherent and easily removable soft sludge of calcium
and magnesium phosphate which can be removed by blow down operation

3CaCl2 + 2Na3PO4 Ca3 (PO4)2 + 6NaCl

The main phosphate used are NaH2PO4, sodium dihydrogen phosphate (acidic), Na2HPO4,
disodium hydrogen phosphate (weakly alkaline) Na3PO4, trisodium phosphate (alkaline).

The choice of salt depends upon the alkalinity of the boiled water. Calcium cannot be
precipitated below a pH 9.5. Trisodium phosphate is most suitable for treatment when alkalinity
is low and disodium phosphate is used when the water alkalinity is sufficient. Monosodium
phosphate is used when the alkalinity of boiler water is too high.

Calgon conditioning:

It involves in adding calogen (Sodium hexa meta phosphate (NaPO3)6 to boiler water. It
prevents the scale and sludge formation soluble complex compound with CaSO4.

Na2[Na4(PO3)6] 2Na+ + [Na4P6O18]2-

2CaSO4 + [Na4P6O18]2- [Ca2P6O18]2- + 2Na2SO4

soluble complex ion

Lime soda process:

In this method the soluble calcium and magnesium salts in water are chemically converted into
soluble compound by adding calculated amount of lime Ca(OH)2 and soda Na2CO3. Calcium
carbonate and magnesium hydroxide so precipitated are filtered off.
Hot lime soda process:

This process involves in treating water with softening chemicals at a temperature of 80 to 1500C.
Since hot process is operated at a temperature close to the boiling point of the solution i) the
reaction proceeds faster ii) softening capacity is increased to many fold iii) the precipitate and
sludge formed settle down rapidly and hence no coagulant are needed iv) much of the dissolved
gases driven out o water v) viscosity of soften water is lower so filtration of water becomes
easier. Vi) this process produces water of comparatively low residual hardness 15 to 30 ppm.

Hot lime soda plant consists essentially of three parts (a) a reaction tank in which raw water,
chemical and steam are thoroughly mixed (b) a conical sedimentation vessel in which sludge
settles down and (c) a sand filter which ensures complete removal of sludge from the softened
water.

Advantages of lime soda process:

i) It is very economical
ii) If the process is combined with sedimentation with coagulation lesser amounts of coagulants
shall be needed.
iii)The process increases the pH of the treated water thereby corrosion reduced.
iv) In addition to the removal of hardness, the quantities of minerals in the water are reduced.
v) Due to alkaline nature of treated water amount of pathogenic bacterias in water is
considerably reduced.

Disadvantages of lime soda process:

i) For efficient and economical softening careful operation and skilled supervision is required.
ii) Disposal of large amount of sludge poses a problem.
iii) This can remove hardness upto 15 ppm which is not good for boilers.
Boiler feed Water: Scales and Sludges

In boilers, water evaporates continuously and the concentrations of the dissolved salts
increase progressively. When their concentrations reach saturation point, they are thrown out of
water in the form of precipitates on the inner walls of the boiler. If the precipitation takes place
in the form of loose slimy precipitate, it is called sludge. On the other hand, if the precipitated
matter forms a hard, adhering crust/coating on the inner walls of the boiler, it is called Scale.

Sludge is a soft, loose and slimy precipitate formed within the boiler. Sludge can easily
be scrapped off with a wire brush. It is formed at comparatively colder portion of the boiler and
collects in areas of the system, where the flow rate is slow or at a bends. Sludge’s are formed by
substances which have greater solubility’s in hot water than in cold water, e.g., MgCO3, MgCl2,
CaCl2, MgSO4, etc.

Disadvantages of sludge formation 1) Sludge’s are poor conductor of heat, so they tend
to waste a portion of heat generated. (2) If sludge’s are formed along-with scales, then former
gets entrapped in the latter and both get deposited as scales. (3) Excessive sludge formation
disturbs the working of the boiler. It settles in the regions of poor water circulation such as pipe
connection, plug opening, gauge-glass connection, thereby causing even choking of the pipes.

Prevention of sludge formation: (1) By using well softened water (2) By frequently
‘blow-down operation’, i.e., drawing off a portion of the concentrated water.

Scales are hard deposits, which stick very firmly to the inner surfaces of the boiler.
Scales are difficult to remove, even with the help of hammer and chisel. Scales are the main
source of boiler troubles. Formation of scales may be due to:

(1)Decomposition of calcium bicarbonate:

Ca (HCO3)2------->CaCO3 +H2O +CO2

However, scale composed chiefly of calcium carbonate is soft and is the main cause of
scale formation in low-pressure boilers. But in high-pressure boilers, CaCO3 is soluble.
 CaCO3 + H2O-------> Ca (OH) 2 (soluble) + CO2

(2) Deposition of Calcium Sulphate: The solubility of calcium sulphate in water decrease
with rise of temperature. Thus, solubility of CaSO4 is 3,200 ppm at 150C and it reduces to 55
ppm at 2300C and 27 ppm at 3200C. In other words, CaSO4 is soluble in cold water, but almost
completely insoluble in super-heated water. Consequently, CaSO4 gets precipitated as hard scale
on the heated portions of the boiler. This is the main cause of scales in high pressure boilers.

Note: Calcium sulphate scale is quite adherent and difficult to remove, even with the help
of hammer and chisel.

(3) Hydrolysis of magnesium salts: Dissolved magnesium salts undergo hydrolysis (at prevailing
high temperature inside the boiler) forming magnesium hydroxide precipitate, which forms a soft
type of scale, e.g. .,

MgCl2 +2H2O------> Mg(OH)2 +2HCl

(Scale)

(4) Presence of silica: (SiO2), even present in small quantities, deposits as calcium silicate (C
aSiO3) and / or magnesium silicate (MgSiO3). These deposits stick very firmly on the inner side
of the boiler surface and are very difficult to remove. One important source of silica in water is
the sand filter.

Disadvantages of scale formation:

(1) Wastage of fuel: Scales have a low thermal conductivity, so the rate of heat transfer from
boiler to inside water is greatly decreased. In order to provide a steady supply of heat to water,
excessive or over-heating is done and this causes increase in fuel consumption. The wastage of
fuel depends upon the thickness and the nature of scale:

Thickness of 0.325 0.625 1.25 2.5 12

scale(mm)
Wastage of fuel 10% 15% 50% 80% 150%

(2) Lowering of boiler safety: Due to scale formation, over heating of boiler is to be done in
order to maintain a constant supply of steam. The over -heating of the boiler tube makes the
boiler material softer and weaker and this causes distortion of boiler tube and makes the boiler
unsafe to bear the pressure of the steam, especially in high -pressure boilers.

(3) Decrease in efficiency: Scales may sometimes deposit in the valve and condensers of the
boiler and choke them partially. This results in decrease in efficiency of the boiler.
(4) Danger of explosion: When thick scales crack, due to uneven expansion, the water comes
suddenly in contact with over-heated iron plates. This causes in formation of a large amount of
steam suddenly. So sudden high- pressure is developed, which may even cause explosion of the
boiler.

Removal of scales: (i) With the help of scraper or piece of wood or wire brush, if they
are loosely adhering. (ii) By giving thermal shocks (i.e., heating the boiler and then suddenly
cooling with cold water), if they are brittle. (iii) By dissolving them by adding them chemicals, if
they are adherent and hard. Thus calcium carbonate scales can be dissolved by using 5-10% HCl.
Calcium sulphate scales can be dissolved by adding EDTA (ethylene diamine tetra acetic acid),
with which they form soluble complexes. (iv)By frequent blow -down operation, if the scales are
loosely adhering.

Prevention of scales formation :( 1) External Treatment includes efficient ‘softening

of water’ (i.e., removing hardness-producing constituents of water). These will be discussed
separately.

(2)Internal Treatment: In this process (also called sequestration), an ion is prohibited to

exhibit its original character by ‘complexing’ or converting it into other more soluble salt by
adding appropriate reagent. An internal treatment is accomplished by adding a proper chemical
to the boiler water either: (a) to precipitate the scale forming impurities in the form of sludges,
which can be removed by blow-down operation, or (b) to convert them into compounds, which
will stay in dissolved form in water and thus do not cause any harm.

Notes: (i) Blow down operation is partial removal of hard water through top at the
bottom of boiler, when extent of hardness in the boiler becomes alarmingly high.

(ii) ‘Make up’ water is addition of fresh softened water to boiler after blow down
operation.

Internal Treatments methods are, generally, followed by ‘blow-down operation’, so that

accumulated sludge is removed. Important internal conditioning/ treatment methods are:

(i) Colloidal conditioning: In low-pressure boilers, scale formation can be avoided by

adding organic substances like kerosene, tannin, agar-agar (a gel),etc., which get coated over the
scale forming precipitates, thereby yielding non-sticky and loose deposits, which can easily be
removed by pre-determined blow-down operations.

(ii)Phosphate Conditioning: In high- pressure boilers, scale formation can be avoided

by adding sodium phosphate, which reacts with hardness of water forming non-adherent and
easily removable, soft sludge of calcium and magnesium phosphates, which can be removed by
blow down operation, e.g.,

3CaCl2 + 2Na3PO4------>Ca3 (PO4)2 +6NaCl

 The main phosphates employed are: (a) NaH2PO4, sodium dihydrogen phosphate
(acidic); (b) Na2HPO4, disodium hydrogen phosphate (weakly alkaline); (c) Na3PO4, trisodium
phosphate (alkaline).

Note: The choice of salt depends upon the alkalinity of the boiler –feed water. Calcium
cannot be precipitated properly below a pH 9.5, so select a phosphate that adjusts pH to optimum
value (9.5-10.5). Trisodium phosphate is most suitable for treatment, when the alkalinity of
boiler water is low, as it is most alkaline in nature. If boiler water’s alkalinity is sufficient, then
disodium phosphate is more preferred. But if the alkalinity of boiler is too high and requires to be
reduced, then monosodium phosphate, being acidic in nature, is preferred.

(iii)Carbonate Conditioning: In low pressure boilers, scale- formation can be avoided by

adding sodium carbonate to boiler water, when CaSO4 is converted into calcium carbonate in
equilibrium.

CaSO4 +Na2CO3 → CaCO3 + Na2SO4

Consequently, deposition of CaSO4 as scale does not take place and calcium is
precipitated as loose sludge of CaCO3, which can be removed by blow-down operation.

(iv)Calgon Conditioning: involves in adding calgon [sodium hexa meta phosphate

(NaPO3)6 to boiler water. It prevents scale and sludge formation by forming soluble complex
compound with CaSO4.

Na2[Na4(PO3)6] → 2Na+ +[Na4P6O18]2-

Calgon

2CaSO4 +[Na4P6O18]2-------->[Ca2P6O18]2- +2Na2SO4

Soluble complex ion

(v)Treatment with sodium aluminate (NaAlO2): Sodium aluminate gets hydrolyzed yielding
NaOH and a gelatinous precipitate of aluminium hydroxide. Thus:

NaAlO2 + 2H2O----->NaOH +Al[OH]3

Sod.meta-aluminate (Gelatinous ppt.)

The sodium hydroxide, so-formed, precipitates some of the magnesium as Mg (OH) 2, i.e.

MgCl2 + 2NaOH -------> Mg (OH) 2 + 2NaCl

The flocculent precipitate of Mg (OH) 2 and Al [OH] 3 produced inside the boiler, entraps finely
suspended and colloidal impurities, including oil drops and silica. The loose precipitate can be
removed by pre-determined blow-down operation.

Note: sodium aluminate in thick solution form is available in plenty and at a cheap rate
from bauxite refining units and this can be used as such for boiler-water treatment.

(vi) Electrical conditioning: sealed glass bulbs, containing mercury connected to a

battery, are set rotating in the boiler. When water boils, mercury bulbs emit electrical discharges,
which prevents scale forming particles to adhere/stick together to form scale.

(vii) Radioactive conditioning: Tablets containing radioactive salts are placed inside the
boiler water at a few points. The energy radiations emitted by these salts prevent scale formation.

(viii) Complexometric method: involves adding 1.5% alkaline (pH=8.5) solution of EDTA to
feed water. The EDTA binds the scale-forming cations to form stable and soluble complex. As a
result, the sludge and scale formation in boiler is prevented. Moreover this treatment:

(i) Prevents the deposition of ion oxides in the boiler

(ii) Reduces the carry over oxides with steam, and

(iii) Protects the boiler units from corrosion by wet steam (steam containing liquid water).

Priming and Foaming

When a boiler is steaming (i.e., producing steam) rapidly, some particles of the liquid
water are carried along-with steam. This process of ‘wet steam’ formation is called Priming.
Priming is caused by: (i) the presence of large amount of dissolved solids (ii) high steam
velocities; (iii) Sudden boiling (iv) Improper boiler design and (v) Sudden increase in steam-
production rate

Foaming is the production of persistent foam or bubbles in boilers, which do not break
easily. Foaming is due to presence of substances like oils (which greatly reduce the surface
tension of water).

Priming and foaming usually occur together. They are objectionable because (i)
Dissolved salts in boiler water are carried by the wet steam to super-heater and turbine blades,
where they get deposited as water evaporates. This deposit reduces their efficiency (ii) Dissolved
salts may enter the parts of other machinery, where steam is being used, there by decreasing the
life of the machinery(iii) Actual height of the water column cannot be judged properly, there by
making the maintenance of the boiler pressure becomes difficult.
 Priming can be avoided by (i)fitting mechanical steam purifiers;(ii)avoiding rapid
change in steaming rate(iii) Maintaining low water levels in boilers and;(iv) efficient softening
and filtration of the boiler-feed water.

Foaming can be avoided by (i) Adding anti-foaming chemicals like castor oil

(ii)Removing oil from boiler water by adding compounds like sodium aluminate.

WASTE WATER TREATMENT

Desalination of brackish water by reverse osmosis and electrodialysis

There are many countries in the world where the demand for fresh water far exceeds the
availability of natural water. There are some countries like Kuwait, which have no fresh water,
and have to look inevitably to the ocean for their fresh water demand. But high salt content of
sea water prohibits its use for human consumption and other uses of water. There are three
grades of water based on the level of dissolved salts, as given below.

(a) Fresh water with dissolved salts less than 1000mg/L.

(b) Brackish water with dissolved salt between1000-35,000mg/L.

(c) Sea water with dissolved salts greater than 35,000mg/L.

Definition

The process of removal of dissolved salts from sea water (or brackish water)to the extent, that
water becomes usable is described as ‘Desalination ‘ or desalting’. OR The process of
removing common salt (sodium chloride) from the water is known as desalination.

Desalination is a very expensive process and is used in places experiencing an acute

shortage of fresh water. The water containing dissolved salts with the peculiar salty (or brackish)
taste is called brackish water. Sea water containing on an average about 3.5% salts, comes under
this category. Brackish water is totally unfit for drinking purpose. Commonly used methods for
the desalination of brackish water are:

(a) Reverse Osmosis

(b) Electro dialysis

(a)Reverse osmosis: When two solutions of unequal concentrations are separated by a semi
permeable membrane (which selectively does not permit 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 however 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 side across the membrane. This is the principle of reverse osmosis. Thus, in reverse
osmosis methods, pure solvent (water) is separated from its contaminates, rather than removing
contaminants from the water. This membrane filtration is sometimes also called “super -
filtration” or “hyper filtration”.

Method: In this process, pressure (of the order 15 to 40kg cm-2) is applied to the sea
water /impure water (to be treated) to force its pure water out through the semi permeable
membrane; leaving behind the dissolved solids (both ionic as well as non-ionic). The principle of
reverse osmosis, as applied for treating saline/ sea water, is illustrated in figure. The membrane
consists of very thin films of cellulose acetate, affixed to either side of perforated tube. However,
more recently superior membranes made of polymethacrylate and polyamide polymers have
come into use.

Advantages(i)Reverse osmosis possesses a distinct advantage of removing ionic as well

as non –ionic , colloidal and high molecular weight organic matter (ii)It removes colloidal silica
which is not removed by demineralization.(iii) The maintenance cost is almost entirely on the
replacement of the semi permeable membrane(iv) The life time of membrane is quite high, about
two years(v) The membrane can be replaced within a few minutes there by providing nearly
uninterrupted water supply.(vi) Due to low capital cost, simplicity, low operating cost and high
reliability, the reverse osmosis is gaining ground at present for converting sea water into
drinking water and for obtaining water for very high-pressure boilers.

(b)Electro dialysis is method in which the ions (of the salts present) are pulled out of the salt
water by passing direct current, using electrodes and thin rigid plastic membrane pair (natural or
synthetic) Fig. illustrates the method of desalination by electrodialysis. When direct electric
current is passed through saline water, the sodium ions (Na+) start moving towards negative pole
(Cathode); while the chloride ions start moving towards the positive pole (anode), through the
membrane. As a result, the concentration of brine decreases in the central compartment; while it
increases in two side compartments. Desalinated brine (or pure water) is removed from the
central compartment from time to time; while concentrated brine (in the side compartments) is
replaced by fresh brine or sea water.
For more efficient separation, usually, ions-selective membranes are employed. An ion-
selective membrane has permeability for only one kind of ions with specific charge. For example
a cation-selective membrane is permeable to cations only, because of the presence of charged
fixed (inside the membrane) functional groups (such as RSO3-, RCOO-) reject anions (having the
same charge as that of fixed functional groups). Similarly anion-selective membrane has
positively charged fixed functional groups such as R4N+Cl-.

An electro dialysis cell (in fig) consists of a large number of paired sets of rigid plastic
membranes. Saline water is passed under a pressure (of about 5-6 kg m-2) between membrane
pairs and an electric field is applied perpendicular to the direction of water flow. Just as magnets
of like charges repel each other, the fixed positive charges inside the membrane repel positively
charged ions (Na+), yet permit negatively charge ions (Cl-) to pass through. Similarly, the fixed
negative charges inside the other type of membrane repel negatively charge ions (Cl -), yet permit
positively charged ions (Na+) to pass through. Therefore water is one compartment of the cell is
deprived of its salts: While the salt concentration in adjacent compartments is increased. Thus,
we get alternate streams of pure water and concentrated brine.

Advantages (1) It is most compact unit

(2) The cost of installation of the plant and its operation is economical.

(3) If electricity is easily available, it is best suited.