Module – 1

1. Factors that control water characteristics: Hardness, DO,

TDS in water & their determination methods.
2. Estimation of hardness by EDTA method - Numerical
problems.
3. Disadvantages of hard water in Industries: scale, sludge,
priming, foaming, caustic embrittlement and boiler
corrosion.
4. Internal conditioning – Phosphate and Calgon
conditioning methods.
 Natural water is contaminated mostly by 3 major types of
impurities: Physical, Chemical and Biological impurities

Physical Chemical Biological

Color Acidity Micro-

Turbidity Gases organisms
Can be removed by
Taste Minerals chlorination.
Can be removed by
Odor Chemical treatment.
Can be removed by
Sedimentation, Coagulation,
Adsorption or Filtration

Municipal water supplied to Homes: Physical and Biological

impurities (major removal) + Chemical impurities (minor removal)
Water supplied to Industries: Physical and Chemical impurities
(major removal) + Biological impurities (negligibly removed)
 Disadvantage of hard water
• In domestic use
Washing: Hard water, when used for washing purposes, does not lather freely with soap.
Instead it produces sticky precipitates of calcium and magnesium soaps. Similar problem
exists in bathing.
Cooking: Due to the presence of dissolved hardness producing salts the boiling point of
water is elevated. Consequently more fuel is and time are required for cooking.
Drinking: Hard water causes bad effect on our digestive system. The possibility of forming
calcium oxalate crystals in urinary tracks is increased (Kidney stones).
• In Industrial use
Textile industry: Hard water cause much of the soap to go as waste. Precipitate of calcium
and magnesium soaps adhere to the fabrics. These fabrics, when dyed latter on, do not
produce exact shades of color.
Sugar industry: Water containing sulphates, nitrates, alkali carbonates, etc., if used in sugar
refining, causes difficulties in the crystallization of sugar. Moreover, the sugar so produced
may be deliquescent
Concrete making: Water containing chlorides and sulphates, if used for concrete making,
affects the hydration of the cement and the final strength of the hardened concrete.
• In steam generation in boilers
If the hard water is fed directly to the boilers, which led to the many problems such as
(i) scale and sludge formation (ii) corrosion (iii) priming and foaming and (iv) caustic
embrittlement
Dissolved Oxygen Cycle
 Total Dissolved Solids

o Recommended TDS for drinking water is 25-250 mg/L

o At any cost, drinking water TDS should not exceed 500 mg/L

o TDS for distilled water will be 0.5-1.5 mg/L

o TDS ranges from 100-20,000 mg/L in river water and will be

generally higher in ground water

o Sea water will have 3500 mg/L of TDS

o Lakes and streams will have a TDS of 20-250 mg/L

 Estimation of DO by Winkler’s method
Theory of Winkler’s Method:
o Oxygen in the water sample oxidizes iodide ion (I-) to iodine (I2)
quantitatively.
o The amount of iodine generated is then determined by titration with a
standard thiosulfate (S2O3-2) solution.
o The endpoint is determined by using starch as a visual indicator.
o The amount of oxygen can then be computed from the titre values
 Hardness of Water
Water that does not produce lather with soap solution readily but forms an
insoluble white precipitate is called HARD WATER.
Water that lathers easily on shaking with soap solution is called SOFT
WATER.
Hard water containing Mg , Ca or Fe salts when treated with soap
2+ 2+ 2+

(sodium or potassium salts of stearic acid) does not produce lather but forms
an insoluble white precipitate of calcium or magnesium stearate.

Hardness in water is caused by the presence of certain dissolved salts such

as bicarbonates, chlorides, and sulfates of Ca2+, Mg2+ or Fe2+ which under
certain conditions of temperature, pressure or reactions with other chemicals
results in the formation of insoluble scales and sludges.
Whereas, hardness in water is not caused by the salts of Na+ or K+ ions. Eg.: Na2CO3
(washing soda) is used as a water softener to reduce the hardness in water. They are
soluble in water under all conditions except when they reach the saturation level.
 Types of Water Hardness
Water hardness is of two types:
(i) Temporary hardness or carbonate hardness: is caused by the presence
of dissolved bicarbonates of Ca2+ and Mg2+ and carbonate of Fe2+.
Temporary hardness can be removed by just boiling the water. The dissolved
bicarbonates in the water are decomposed into insoluble carbonates or
hydroxides which are deposited as crust (as scales) at the bottom of vessel.

soluble
Calcium bicarbonate Calcium carbonate
▲
Mg(HCO3)2 Mg(OH)2 + 2CO2
soluble insoluble
Magnesium bicarbonate Magnesium hydroxide
(ii) Permanent or non-carbonate hardness is due to the presence of
chlorides and sulfates of Ca, Mg, Fe. Cannot be removed by boiling. Can
be removed through zeolite, Lime-soda, ion-exchange processes.
Sludge and Scale
 Scale and Sludge formation in boilers
In boilers, water evaporates continuously (for steam production) and the
concentration of the dissolved salts also increases continuously. When their
concentration reaches a saturation point, they precipitate in the form of scales and
sludges.
• Sludge is a soft, loose and slimy precipitate formed within the boiler.
• Sludge can be easily scrapped off with the wire brush.
• It is formed comparatively colder portions of the boiler and collects in the
bends where the flow rate is slow
• Sludges have greater solubility in hot water than in cold water, Ex., MgCO3,
MgCl2, MgSO4, CaCl2, etc.
Disadvantage of sludge formation
• Sludges are poor conductor of heat, so they tend to waste a portion of heat
generated.
• If sludges are formed along with scales, the sludges get entrapped in the scales
and both get deposited as scales.
• Excessive sludge formation disturbs the working of the boiler by settling in regions
of poor water circulation (bends, connection points) thereby choking the pipe line.

Prevention of sludge formation

By using well softened water and by frequent blow-down operation (drawing off
a portion of the concentrated water)
 Scales
 Scales are hard deposits, which stick very firmly to the inner surface of the boiler.
 Scales are the main source of boiler troubles.
Formation of scales may be due to:
(1) Decomposition of calcium bicarbonate (soft scales, low-pressure boiler)
(2) Deposition of calcium sulphate (hard scales, high pressure boiler)
(3) Hydrolysis of magnesium salts (soft scales, low-pressure boiler)
(4) Presence of Silica

Decomposition of calcium bicarbonate

• Scale composed chiefly of calcium carbonate is soft and is the main cause
of scale formation in low-pressure boilers.

Scale
• But in high-pressure boilers, CaCO3 is soluble.
CaCO3+ H2O Ca(OH)2 (Soluble) + CO2
 Deposition of Calcium Sulphate
• The solubility of CaSO4 in water decreases with increase of temperature.
• CaSO4 is soluble in cold water, but almost completely insoluble in super-
heated water.
Temperature Solubility of CaSO4

15oC 3200 ppm

230oC 55 ppm
320oC 27 ppm

• CaSO4 gets precipitated as hard scale on the heated portion of the boiler,
whereas, it is relatively dissolved in the colder portion of the boiler. This is
the main cause of scales in high-pressure boilers.
Hydrolysis of magnesium salts
Dissolved magnesium salts undergo hydrolysis to produce magnesium
hydroxide precipitate which forms a soft type of scale.
MgCl2 + 2H2O Mg(OH)2 + 2HCl
 Presence of Silica
Presence of silica even in small quantities deposits as calcium silicate (CaSiO3) or
magnesium silicate (MgSiO3). These deposits stick very firmly on the inner side of the
boiler surface and are very difficult to remove. Important source of silica in water is the
sand filter.
What are the disadvantages of scale formation?
1. Wastage of fuel: Due to low thermal conductivity of the scales, the rate of heat
transfer from boiler to inside water is greatly decreased. Hence, over-heating is
done which causes wastage of fuel.
Thickness of scale in (mm) 0.325 0.625 1.25 2.5 12

Wastage of fuel 10% 15% 50% 80% 150%

2. Lowering of boiler safety: Due to over-heating, the boiler material becomes softer
and weaker, may explode under high-pressure conditions.
3. Danger of explosion: When thick scales crack, water comes in contact with over-
heated boiler surface. This results in the formation of large amounts of steam which
will increase the boiler pressure and may cause even explosion.
4. Decrease in efficiency: Scales deposit in the boiler parts and block the flow of heat
and water, resulting in reduced efficiency of the boiler.
 Removal of Scales
1. If they are loosely adhered, remove with a scraper or wire brush or
frequent blow-down operation.
2. If they are brittle, apply thermal shock (heating the boiler and then
suddenly cooling with cold water).
3. If they are adherent and hard to dissolve, remove them with the help of
chemicals.
– CaCO3 scales can be dissolved by using 5-10% HCl.
– CaSO4 scales can be dissolved by adding EDTA with which they form
soluble complex.
What is called back-wash?
Back-wash is the passing of softened water in the direction opposite to the
usual water flow to remove sludges and soft scales.
What is a blow-down operation?
blow-down operation is the partial removal hard water at the bottom of
boiler when the concentration of dissolved ions becomes very high.
Make-up water is the addition of fresh softened water to boiler after blow-
down operation. 16
 Disadvantages of hard water
1. Caustic embrittlement
2. Boiler Corrosion
3. Priming and Foaming

1. Caustic embrittlement: is a type of boiler corrosion, caused by

using highly alkaline water in boiler.
o During softening of hard water by lime [Ca(OH)2]-soda [Na2CO3] process,
the excess Na2CO3 present in softened water decomposes to NaOH and
CO2 in high pressure boilers.

Na2CO3 + H2O  2 NaOH + CO2

o This NaOH makes the water caustic.

o The NaOH containing water flows into minute cracks present in the boiler
by capillary action.
o As water is boiling, it evaporates and the conc. of NaOH increases slowly.
o This caustic soda attacks the boiler and forms sodium ferroate (Na2FeO2)
which makes the boiler parts brittle (embrittlement).
Concentration cell formed during caustic embrittlement
Caustic attack on boiler parts can be represented as:
+ _

Iron at rivets, Conc. NaOH Dil. NaOH Iron at

bends, joints, soln. soln. plane
etc. surfaces

o The iron in contact with dil. NaOH becomes cathode and the iron in
contact with conc. NaOH becomes anode. The anodic part slowly
corrodes and dissolves.
o Caustic embrittlement can be avoided by adding:
a) sodium phosphate (Softening agent, added instead of Na2CO3)
b) tannin or lignin (Blocks hair line cracks)
c) sodium sulphate (Blocks hair line cracks); With increasing boiler
pressure, the amount of Na2SO4 added is also increased.

Na2SO4 /NaOH conc. 1:1 2:1 3:1

Pressure 10 atm 20 atm >20 atm
 Boiler corrosion
o Decay of boiler material by chemical or electrochemical attack by
surrounding environment. Reasons for boiler corrosion are:
a) Dissolved oxygen
b) Dissolved carbon dioxide
c) Acids from dissolved salts
a) Dissolved oxygen (DO):
2 Fe + 2 H2O + O2  2 FeII(OH)2 (ferrous hydroxide)

Rust or corrosion
4 Fe(OH)2 + O2  2[FeIII2O3.2H2O]

DO can be removed by adding calculated qty. of sodium sulphite or

hydrazine or sodium sulphide:
2 Na2SO3 + O2 → 2 Na2SO4
N2H4 + O2 → N2 + 2H2O
Na2S + 2O2 → Na2SO4
Hydrazine removes O2 without increasing the concentration of dissolved solids. The
products (N2 and H2O) are also harmless. Hence, hydrazine is the most efficient
internal
DO can betreatment
removedchemical for theaeration
by mechanical removalalso.
of dissolved oxygen.
Water spraying in a perforated plate-fitted
tower, heated from sides and connected to Vacuum pump. High temperature, low pressure
and large exposed surface reduces dissolved oxygen in water.
 Boiler corrosion
b) Dissolved CO2:
o Dissolved CO2 from the below reaction is hydrolyzed to form
carbonic acid (H2CO3) which corrodes the boiler.

Mg(HCO3)2 Mg(OH)2 + 2 CO2

o CO2 + H2O H2CO3
o CO2 is removed by adding calculated quantity of aq. ammonia:
2 NH4OH + CO2 (NH4)2CO3 + H2O
o It is also removed by mechanical aeration along with oxygen.

c) Acids from dissolved salts:

o Dissolved magnesium salts hydrolyze to form acids:
MgCl2 + 2 H2O  Mg(OH)2 + 2 HCl
o This acid reacts with boiler in chain-like reactions producing HCl:
Fe + 2 HCl FeCl2 + H2
FeCl2 + 2 H2O Fe(OH)2 + 2 HCl

o Even a small quantity of magnesium salts will cause large amount

of boiler corrosion.
a) Priming:
o When a boiler is steaming rapidly, some particles in the liquid water are
carried along with the steam. This process of “wet steam” formation is
called PRIMING.
o Priming is caused by (a) large amounts of dissolved solids (salts), (b)
high steam velocities, (c) sudden boiling, (d) improper boiler design,
and (e) sudden increase in steam production rate.
o Priming can be avoided by (a) fitting mechanical steam purifiers, (b)
avoiding rapid change in steam rate, (c) maintaining low water level in
boilers, (d) efficient softening, and (e) filtration of the boiler-feed
water.

b) Foaming:
o Foaming is the production of persistent foam or bubbles in boilers which
do not break easily.
o Foaming is due to the presence of oils (which reduce the surface tension
of water).
o Foaming can be avoided by adding anti-foaming agents like castor oil or
removing oil from the boiler feed water by adding sodium aluminate.

Disadvantages of Priming and Foaming: Dissolved salts enter the

machinery parts thereby decreasing the life of machinery; actual height
of water in the column cannot be judged properly, thereby making the
boiler maintenance difficult.
Internal treatment methods for boiler feed water

o Method is also called as Sequestration in which an ion is prohibited

from exhibiting its original character by complexing (to form
precipitates) or converting it into a more soluble salt by adding
appropriate reagents.
o Internal treatment is carried out to by adding a proper chemical to
the boiler water either to:
a) precipitate the scale forming impurities into sludges (or)
b) convert the scale forming impurities into compounds with higher
solubility so that they remain in water and cause no harm.

Usually, Internal treatment methods are followed by “blow-down

operation” so that the accumulated sludges are removed.
o The two important methods are:
a) Phosphate conditioning and b) Calgon conditioning.
Q: Elaborate the phosphate and calgon conditioning methods of water softening
process.
a) Phosphate conditioning:
o In high pressure boilers, scales are avoided by adding sodium phosphate.
o This converts the scale forming impurities into non-adherent, easily
removable soft sludge of calcium and magnesium phosphate which can be
removed by blow down operation.
3 CaCl2 + 2 Na3PO4  Ca3(PO4)2 + 6 NaCl
o The phosphates used (depending on boiler water alkalinity) are:
i) NaH2PO4 (acidic) – for highly alkaline water
ii) Na2HPO4 (weakly alkaline) – for medium acidic/alkaline water
iii) Na3PO4 (alkaline) – for highly acidic water

b) Calgon conditioning:
o Sodium hexa meta phosphate (NaPO3)6 is Calgon.
o When added to water, it prevents formation of scales and sludges by
forming a soluble complex with CaSO4.
Na2[Na4(PO3)6] 2 Na+ + [Na4P6O18]2-
2 CaSO4 + [Na4P6O18]2- [Ca2P6O18]2- + 2 Na2SO4
Soluble complex ion