UNIT I UNIT I WATER TECHNOLOGY (9)

Introduction-Characteristics of water – Hardness – Types of hardness - Estimation by EDTA

(problems on hardness)- Alkalinity – Determination (problems on alkalinity) – Boiler feed water –
Requirements – Priming and foaming, Scales and sludges Caustic embrittlement and Boiler
corrosion – External conditioning (Ionexchange,zeolite) – Internal conditioning
(Carbonate,phosphate,calgon,sodiumaluminate conditioning) –– Brackish water treatment -
Reverse osmosis
Experiential Learning: Simulation of Monitoring the Water quality standards. (CSE Lab)
Industrial Application: Electrodialysis
Content beyond syllabus: Water quality standards - WHO,BIS and CPHEEO standards

Introduction:
Water is nature’s most wonderful, abundant and useful compound. Without food, human can
survive for a number of days, but water is such an essential that without it one cannot survive. Water
is not only essential for the lives of animals and plants, but also occupies a unique position in industries.
Probably, it’s most important use as an engineering material is in the steam generation. Water is also
used as coolant in power and chemical plants. Water is widely distributed in nature. It has been
estimated that about 75% matter on the earth’s surface consists of water. Besides visible water on
earth, there is large amount of water under earth to an average depth of over three kilometers. The air
consists 12 to 15% of volume of water vapour. Water is found in living things. The body of human being
consists of about 60% of water. Plants, fruits and vegetables contain 90 to 95% of water.
The main sources of water are
(i) rain
(ii) rivers and lakes (surface water)
(iii) wells and springs (underground water)
(iv) sea water.
Among the above sources of water, rain water is the purest form of water but it is very difficult
to collect whereas sea water is the most impure form. So, surface and underground water are normally
used for domestic and industrial purposes. Such water must be free from undesirable impurities. The
process of removing all types of impurities from water and making it fit for domestic or
industrial purposes is called water treatment/Water technology. Before treating the water, we
should know the nature as well as the amount of impurities.

1.1 Characteristics of water – Hardness – Types of hardness:

Characteristics of water

Physical properties of water:

1.Water is a colourless, odourless and tasteless liquid.
2.The freezing point falls down below 0°C.Freezing point of water decreases due to the presence of
impurities.
3.The boiling point of water is 100°C. Boiling point of water increases when the amount of dissolved
impurities increases.
4.The melting point of ice is 0°C. This temperature is constant till all the ice changes into liquid. But
here heat energy is stored within the water which is called ‘latent heat of fusion of ice’. Latent heat of
condensation of water is 540 calories/gm. It is the amount of heat energy liberated by converting 1 gm
of water vapor at 1000C.
5.When water is heated its temperature starts to increase. 1°C. The specific heat capacity of water is
1cal/gm. Due to high heat capacity of water it is used as coolant.
6.Water is an excellent solvent and therefore it helps in the transportation of ions and molecules
required for metabolism in living organisms.

Chemical properties of water:

Some significant reactions of water are as follows:

1.Stability: Water is a highly stable compound. Water does not decompose at ordinary temperatures.
On heating water to a very high temperature of about 2000°C, only 0.6% of it gets decomposed to form
hydrogen and oxygen.
2H2(g) + O2(g) → 2H2O(l )

2.Nature: Pure water is neutral towards litmus.

3.Catalytic Nature: Water acts as a catalyst in numerous reactions. For example, dry hydrogen and
chlorine gasses do not react even in the presence of sunlight unless some traces of water are added
to it.

4.Amphoteric Nature: This represents a capability to perform as a base as well as an acid.

Example:
Acidic Behavior: H2O(l)+NH3(aq) ⇌ NH4+(aq)+OH−(aq)
Basic Behavior: H2O(l)+H2S(aq)⇌ H3O+(aq)+HS−(aq)

5.Redox reactions pertaining to H2O

When water reacts with highly electropositive metals like sodium and hydrogen, it can be easily
reduced to dihydrogen.
Example: 2H2O(l)+2K(s)→2KOH(aq)+H2(g)

Water during photosynthesis is oxidized to O2

6.Reactions with metals: Water reacts with active metals like sodium and potassium and forms the
corresponding hydroxides.
For example, when a small piece of sodium is dropped into a trough of cold water,it reacts vigorously,
catches fire and burns with a golden-yellow flame and hydrogen gas is evolved. The reaction is.
2H2O(l)+2Na(s) ⇌ 2NaOH(s)+ H2(g)+Heat

HARDNESS:
Hardness of water:
The water which does not produce lather with soap is called hard water. Thus, hardness in water is
the characteristic, which “prevents the lathering of soap”.
 On the other hand, the water which produce lather easily on shaking with soap solution, is called
soft water.
Soap is sodium or potassium salt of higher fatty acids like stearic, oleic and palmetic acids. When
soap is mixed with soft water lather is produced due to stearic acid and sodium stearate.

When soap comes in contact with hard water, sodium stearate will react with dissolved calcium and
magnesium salts and produce calcium stearate or magnesium stearate which is white precipitate.

Types of hardness:
The hardness of water is caused by the presence of dissolved salts such as bicarbonates, sulphates,
chlorides and nitrates of divalent metal ions like calcium and magnesium. The different types of water
are commercially classified on the basis of hardness.

Hardness Name of water

0-70 mg/L Soft water

70-150 mg/L Moderate hard water

150-300 mg/L Hard water

>300 Very hard water

TYPES OF HARDNESS:
The hardness of water is two types;

1. Temporary hardness. 2. Permanent hardness.

1. Temporary hardness or Carbonate hardness:

This hardness is caused by two dissolved bicarbonate salts Ca(HCO 3)2 and Mg(HCO3)2. The
hardness is called temporary because, it can be removed easily by boiling. During boiling,
bicarbonates are decomposed to yield insoluble carbonates or hydroxides, which are deposited as
 a crust at the bottom of vessel.

2. Permanent hardness or non-carbonate hardness:

This hardness is due to the dissolved chlorides, sulphates and nitrates of calcium and magnesium.
These salts are CaCl2, MgCl2, CaSO4, MgSO4, Ca(NO3)2, Mg(NO3)2. It cannot be removed easily by
boiling. Hence, it is called permanent hardness. Only chemical treatment can remove this hardness.

Total Hardness = Temporary hardness + Permanent hardness

Expression of hardness:
Hardness of water is expressed in terms of calcium carbonate equivalents. The weights of different
salts causing hardness are converted to weights equivalent to that of CaCO3.
If a sample of water contains two or more than two salts, their quantities are converted in equivalent
to CaCO3 as mentioned above and then the sum will give the total hardness. CaCO 3 was selected
for expression of the degree of hardness because;

1. The Molecular Weight of CaCO3 is 100 g/mol, which is easy for calculation.

2. It is an insoluble salt, and all the dissolved salts of calcium are precipitated as CaCO 3.

Hardness causing salt Molecular weight (g/mol)

Ca(HCO3)2 162
Mg(HCO3)2 146
CaSO4 136
CaCl2 111
MgSO4 120
MgCl2 95
Ca(NO3)2 164
Mg(NO3)2 148

Thus, 120 parts by weight of MgSO4 would react with the same amount of soap as 100 parts
by weight of CaCO3. Hence, weight in terms of CaCO3 would be equal to weight of MgSO4 in water
multiplied by 100/120. The method of calculating hardness will be clear from the following formula.
 𝐴𝑚𝑜𝑢𝑛𝑡 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑡𝑜 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑐𝑎𝑢𝑠𝑖𝑛𝑔 𝑠𝑎𝑙𝑡

𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑡ℎ𝑒 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑐𝑎𝑢𝑠𝑖𝑔 𝑠𝑎𝑙𝑡

= 𝑋 100
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑐𝑎𝑢𝑠𝑖𝑛𝑔 𝑠𝑎𝑙𝑡

Units of hardness:

There are five units in which the hardness of water is expressed.

1. Parts per million. 2. Milligrams per litre. 3. Degree Clark. 4. Degree French. 5. meq per litre.

1. Parts per million (ppm):

It is the parts of calcium carbonate equivalent hardness per 106 parts of water.

i.e. 1ppm = 1 part of CaCO3 eq hardness in 106 parts of water.

2. Milligrams per litre (mg/L):

It is the number of milligrams of calcium carbonate equivalent hardness present per litre of water.
Thus,
1 mg/L =1 mg of CaCO3 eq hardness per1 L of water.
But 1 L water = 1 kg = 1000g = 106 mg
1 mg/L = 1 mg of CaCO3 eq per 106 mg of water
= 1 part of CaCO3 eq per 106 parts of water = 1 ppm
3. Degree Clark (0Cl):

It is the number of grains of CaCO3 equivalent hardness per gallon of water. (or) It is the parts
CaCO3 equivalent hardness per 70,000 parts of water.
10Cl = 1 grain of CaCO3 eq hardness per gallon of water 10Cl = 1 part of CaCO3 eq hardness
per 70,000 parts of water
4. Degree French (0Fr):

It is the parts of calcium carbonate equivalent hardness per 10 5 parts of water.

i.e. 10Fr = 1 part of CaCO3 eq hardness in 105 parts of water.

Relationship between various units of hardness:

1ppm = 1 mg/L = 0.1 0Fr = 0.07 0Cl = 0.02 meq/L

1.2: Estimation by EDTA (problems on hardness)
ESTIMATION OF HARDNESS (EDTA METHOD)
EDTA is ethylene diamine tetra acetic acid. The structure of EDTA is

Since EDTA is insoluble in water, its sodium salt is used as a complexing agent.

PRINCIPLE: Estimation of hardness by EDTA method is based on the principle that EDTA
forms metal complexes with hardness producing metal ions present in water. These
complexes are stable when the pH is maintained between 8-10. In order to maintain the pH,
buffer solution (ammonium chloride + ammonium hydroxide mixture) is added. The
completion of the complexation reaction is indicated by Eriochrome black-T indicator. When
this indicator is added to the sample water it forms indicator-metal unstable complexes of
wine red colour.

(Unstable complex, Wine red colour)

When this solution is titrated against EDTA, it replaces the indicator from the indicator
complex. When all the hardness causing ions are complexed by EDTA, the indicator is set
free and the end point is the sharp change in colour from wine red to steel blue. The total
hardness is thus determined.

(Stable complex) Steel blue

The temporary hardness is removed by boiling and after the removal of the precipitate by filtration;
the permanent hardness in the filtrate is determined by titration with EDTA as before.
Total hardness - permanent hardness = temporary hardness.
EXPERIMENTAL PROCEDURE:

TITRATION I: STANDARDISATION OF EDTA

A known volume of the standard hard water (Vml) is pipetted out and treated with 10 ml of
buffer solution and 2 to 3 drops of EBT indicator. The solution is then titrated against the
standard EDTA solution taken in the burette. The end point is the colour change from wine
red to steel blue.
Let the volume of EDTA consumed be V1 ml.

TITRATION II: ESTIMATION OF TOTAL HARDNESS

A known volume of the sample hard water is pipetted out and treated with 10 ml of buffer
solution and 2 to 3 drops of EBT indicator. The solution is then titrated against the standard
EDTA solution taken in the burette. The end point is the colour change from wine red to
steel blue.
Let the volume of EDTA consumed be V2ml.

TITRATION III: ESTIMATION OF PERMANENT HARDNESS

250 ml of the sample hard water is taken in a beaker. The solution is boiled till the volume
is reduced to 50 ml. The residue is filtered and the filtrate is made up to 250ml using distilled
water. From this made up solution a known volume is pipetted out and treated with 10 ml
of buffer solution and 2 to 3 drops of EBT indicator. The solution is then titrated against the
standard EDTA solution taken in the burette. The end point is the colour change from wine
red to steel blue.
Let the volume of EDTA consumed be V3 ml.

CALCULATION:
STANDARDISATION OF EDTA:
V1 ml of EDTA = V ml of std. hardwater
= V mg of CaCO3 eq.
(since 1 ml of std.hardwater = 1 mg. of CaCO3eq
Therefore, 1 ml of EDTA = V/V1 mg of CaCO3eq.
TOTAL HARDNESS:
V ml of unknown hard water sample consumes V2 ml of EDTA.
i.e., V ml of sample hardwater = V2 ml of EDTA.
= V2 x V/V1 mg of CaCO3eq.
(Since 1 ml of EDTA = V/V1 mg of CaCO3eq.)

Therefore, 1 ml of sample hardwater = mg of CaCO3eq

=V2/V1 mg of CaCO3 eq.

1000 ml of sample hard water = V2/V1x 1000 mg of CaCO3 eq.
Therefore, TOTAL HARDNESS = V2/V1x 1000 ppm.
 PERMANENT HARDNESS:
V ml of unknown boiled hard water sample consumes V3 ml
of EDTA. i.e., V ml of permanent hardwater = V3 ml of EDTA.
= V3 x V/V1 mg
of CaCO3 eq. (Since 1 ml of EDTA =
V/V1 mg of CaCO3 eq.)

Therefore, 1 ml of permanent hardwater = mg of CaCO3 eq

= V3 /V1 mg of CaCO3 eq.

Therefore, 1000 ml of permanent hard water = V3/V1x 1000 mg of CaCO3

eq.

Therefore, Permanent Hardness = V3/V1x 1000 ppm.

TEMPORARY HARDNESS:
Total = Temporary Hardness + Permanent
hardness Hardness
Temporary hardness =Total hardness – permanent hardness

x 1000 ppm.

Problems on Hardness:
1. 50ml of a sample water consumed 15ml of 0.01 EDTA before boiling and
5ml of the same EDTA after boiling. Calculate the degree of hardness,
permanent hardness and temporary hardness.

Solution: 50ml of water sample = 15ml of 0.01M EDTA

= 15x100 ml of 0.01EDTA= 300ml of 0.01M EDTA 50

= 2x300ml of 0.01 N EDTA (Molarity of EDTA=2xNormality of EDTA)

= 600 ml or 0.6 L of 0.01 eq. of CaCO3.

= 0.6x0.01x50 g CaCO3 eq.

Hence total hardness= 0.30g or 300mg of CaCO3 eq= 300mg/L or ppm. Now 50ml of
boiled water = 5ml of 0.01M EDTA

∴1000ml of boiled water= 5x1000 ml of 0.01M EDTA

50

= 100mL of 0.01M EDTA

 = 200mLor 0.2 L of 0.01N EDTA

= 0.2x0.01x50g of CaCO3 eq

= 0.1g or 100mg of CaCO3 eq Hence permanent hardness =

100mg/L or ppm

∴Temporary hardness= 300-100=200ppm.

2. 0.5g of CaCO3 was dissolved in HCl and the solution made up to 500ml with
distilled water. 50ml of the solution required 48ml of EDTA solution for
titration. 50ml of hard water sample required 15ml of EDTA and after boiling
and filtering required 10ml of EDTA solution. Calculate the hardness.
Solution: 500ml of SHW = 0.5g or 500mg CaCO3 eq
∴1ml SHW= 1mg CaCO3 eq
Now 48ml of EDTA solution = 50/48 mg CaCO3 eq
∴1ml of EDTA solution= 50/48 mg CaCO3 eq Calculation of the total hardness of water:
50ml hard water = 15ml EDTA = 15x50/48 mg of CaCO3 eq
∴1000ml of hard water= (15.625x1000 )/50= 312.5 mg
Hence total hardness= 312.5mg/L or 312.5 ppm.

1.2: DETERMINATION OF ALKALINITY OF A WATER SAMPLE

Principle: Alkalinity of water means the total content of those substances in it which
causes an increased OH- ion concentration up on dissociation or due to hydrolysis. The
alkalinity of water is attributed to the presence of (i) Caustic alkalinity (Due to OH - and
CO 2-) (ii) Temporary hardness (Due to HCO32-) Alkalinity is a measure of ability of water
to neutralize the acids. Determination of OH-, CO32- and HCO3- can be titrated against
standard acid using phenolphthalein and methyl orange as indicators The
determination is based on the following reactions.

The titration of water sample against a standard acid up to phenolphthalein end

point (P) marks the completion of reaction (i) and (ii) only. This amount of acid used
thus corresponds to OH- plus one half of the normal CO32- present On the other hand,
titration of the water sample against a standard acid to methyl orange end point (M)
marks the completion of reaction (i), (ii) and (iii). Hence the total amount of acid used
represents the total alkalinity.

P = OH- + ½ CO 2- & M= OH- + CO 2- + HCO3-

Standardisation of HCI:
The burette is washed well with water and rinsed with the given hydrochloric acid solution.
It is then filled with the same upto zero mark. 20 ml of the standard sodium hydroxide
solution is pipetted out in a clean conical flask. 2-3 drops of phenolphthalein indicator is
added, the colour turned to pink colour. It is then titrated against the hydrochloric acid
taken in the burette. The end point is the disappearance of pink colour. The titration is
repeated to get concordant values. From the titre values, the normality of HCL is
calculated.
TITRATION-II (With Phenolphthalein indicator):
20 ml of the water sample is pipetted out in a clean conical flask. A drop of
phenolphthalein indicator is added. Pink colour is observed. This solution is titrated
against the standard HCl, already taken in the burette, until the pink colour disappears.
The end point is noted. This titre value corresponds to phenolphthalein end point (P).
TITRATION III (With Methyl orange indicator):
Few drops of methyl orange indicator is added to the same solution after the
phenolphthalein end point. The titration is continued until the solution becomes red
orange. The total titre value is noted. This titre value corresponds to methyl orange end
point (M). The titration is repeated for concordant values.
From the titre values the amount of each alkalinity present in given water sample is
calculated.
Sl.No. Condition OH- CO32- HCO3-
1 [P] = 0 0 0 [M]
2 [P] = [M] [P]or [M] 0 0
3 [P] = ½ [M] 0 2[P] or [M] 0
4 [P] > ½ [M] 2[P]-[M] 2[M] – 2[P] 0
5 [P] < ½ [M] 0 2[P] [M]-2[P]

Conclusion:

1.When P=0, both OH- and CO32- are absent and alkalinity is due to HCO3- only.

2. When p=1/2 M , only CO32- is present , half of carbonate neutralisation reaction takes
place (i.e. CO3 2- + H+ HCO3- ) with phenolphtahlein indicator.

Complete carbonate neutralization reaction

(i.e. CO32- + H+ HCO3-;

HCO3- + H+ H2O + CO2) occurs when methyl orange indicator is used.

Thus alkalinity due to CO32- is 2P.

3. When P=M only OH- is present, alkalinity due to OH- =P=M.

4. When P> ½ M, besides CO32- , OH- ions are also present. Now half of CO32- is (i.e.

HCO3- + H+ H2O + CO2 is equal to (M-P).

 So, alkalinity due to complete CO32- =2(M-P)

& alkalinity due to OH- is M-2(M-P) =(2P-M)

5. When P<1/2 M, besides CO32- , HCO3- ions are also present. Now alkalinity due to
CO32- = 2P & alkalinity due to HCO3- = (M-2P).

Problems on Alkalinity
I. 100ml of raw water sample on titration with N/50 H 2SO4 require 12ml of the acid
to Phenolphthalein endpoint and 15.5ml of the acid to methyl orange indicator.
Determine the type and amount of alkalinity present in the water sample.
Solution:
Given that;
Volume of water sample = 100ml
Volume of H2SO4 for Phenolphthalein endpoint = 12ml
Volume of H2SO4 for methyl orange endpoint = 15.5ml

P> 1/2M, so the water sample must contain only OH- and CO32- alkalinities and there
cannot be any HCO3- .
1) Alkalinity due to OH-
The volume of N/50 H2SO4 equivalent to OH- present in 100ml of the raw water
sample = 2P –M
= (2x12.0) ml -15.5ml = 8.5ml
Volume of the acid consumed V1` = 8.5ml
Normality of the acid N1 = N/50 = 0.02N
Volume of the raw water sample V2 = 100ml
Normality of the raw water sample N2 =?
Therefore, according to volumetric analysis V1N1 = V2N2
𝑉1𝑁1
𝑁2 =
𝑉2
Substituting in the equation, we have
8.5 1
N2 = 100 = 50 = 0.0017𝑁
Normality of OH- = 0.0017N
Amount of OH- interms of CaCO3 = N2 x equivalent weight of CaCO3
= 0.0017N x 50g x 1000ml = 85ppm

2) Alkalinity due to CO32-

The volume of N/50 H2SO4 equivalent to CO32- - present in 100ml of the raw
water sample = 2(M-P)
= 2(15.5 -12.0) = 7.0ml
Volume of the acid consumed V1` = 7.0ml
Normality of the acid N1 = N/50 = 0.02N
Volume of the raw water sample V2 = 100ml
Normality of the raw water sample N2 =?
Therefore, according to volumetric analysis V1N1 = V2N2
𝑉1𝑁1
𝑁2 =
𝑉2
 Substituting in the equation, we have
7.0 1
N2 = 100 = 50 = 0.0014𝑁
Normality of CO32- = 0.0014N
Amount of CO32- in terms of CaCO3 = N2 x equivalent weight of CaCO3
= 0.0014N x 50g x 1000ml = 70ppm
Total alkalinity = Alkalinity due to OH- + Alkalinity due to CO32-
= 85 + 70 = 155ppm

II. A water sample is not alkaline to phenolphthalein but 100 ml of the sample on
titration with N/50 HClrequired 16.7ml to methyl orange endpoint. What are the
types and amounts of alkalinity present in the sample?
Solution:
Given that;
Volume of water sample = 100ml
Volume of HCl for Phenolphthalein endpoint = 0 ml
Volume of HCl for methyl orange endpoint = 16.7ml

Since P= 0, the alkalinity of water sample is only due HCO3-

Alkalinity due to HCO3-

Volume of the acid consumed V1` = 16.7ml

Normality of the acid N1 = N/50 = 0.02N
Volume of the raw water sample V2 = 100ml
Normality of the raw water sample N2 =?
Therefore, according to volumetric analysis V1N1 = V2N2
𝑉1𝑁1
𝑁2 =
𝑉2

Substituting in the equation, we have

16.7 1
N2 = 100 = 50 = 0.00334𝑁
Normality of HCO3- = 0.00334N
Amount of HCO3-interms of CaCO3 = N2 x equivalent weight of CaCO3
= 0.00334N x 50g x 1000ml = 167ppm.

1.4: Boiler feed water – Requirements – Priming and foaming, Scales and sludges
Caustic embrittlement and Boiler corrosion:

Boiler troubles: There are four important boiler troublers.

(1) Scale and sludge formation (2) Corrosion (3) Priming and foaming (4) Caustic
embrittlement.

1. Scale and sludge formation:

In boilers, water evaporates continuously and the concentration of the dissolved

salts increase progressively. When their concentration 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 and slimy precipitate, it is called sludge

On the other hand, if the precipitated matter forms a hard adhering coating on the inner
walls of the boiler, it is called scale.
Sludge: It 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 colder portions of the boiler. Sludge is
formed b y substances which have greater solubilities in hot water than cold water.

E.g. MgCO3, MgCl2, CaCl2, MgSO4, etc.

Disadvantages of sludge formation:

(a) Sludges are poor conductors of heat, so they tend to waste a portion of heat
generated.

(b) If sludges are formed along with scales, then former gets entrapped in the latter
and both get deposited as scales.
(c) Excessive sludge formation disturbs the working of the boiler. It settles in the
regions of poor water circulation such as pipe connections.

Prevention of sludge formation:

(a) By using well softened water which is free from MgCO3, MgCl2, CaCl2, MgSO4
salts.

(b) By frequent “blow-down” operation, i.e. drawing off a portion of the concentrated
water.

Scale:

These 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. These are main sources of boiler
troubles. Formation of scales may be due to;

(a) Decomposition of calcium bicarbonate:

Due to high temperature and pressure present in the boilers, the calcium
bicarbonate salt decomposes in to CaCO3, which is an insoluble salt, forms scale.

(scale)
 (b) Deposition of calcium sulphate:

The solubility of calcium sulphate in water decreases with rise of temperature.

Thus, solubility of CaSO4 is 3,200 ppm at 150C and it reduces to 55 ppm at 230 0C 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.

(c) Hydrolysis of magnesium salts:

Dissolved magnesium salts undergo hydrolysis to form magnesium hydroxide
precipitate, which forms a soft type of scale.

(d) Presence of silica:

SiO2, even present in small quantities, deposits as calcium silicate (CaSiO3) and
magnesium silicate (MgSiO3). These deposits stick very firmly on the inner side of the
boiler surface and are very difficult to remove.

Disadvantages of scales:
(a) Wastage of fuel:Scales have a low thermal conductivity, so the rate of heat
transfer from boiler to inside water gradually 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 of scale.

Thickness of scale mm) 0.325 0.625 1.25 2.5 12

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

(b) 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. This 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.

(c) Danger of explosion:

When thick scales crack, due to uneven expansion, the water comes suddenly in
contact with overheated iron plates. This causes in formation of a large amount of steam
suddenly. So sudden high pressure is developed, which even cause explosion of the
boiler.

Removal of scales:
(i) With the help of scraper or wire brush, we can remove the scales, if they are loosely
adhering.
 (ii) By giving thermal shocks, we can remove the scales, if they are brittle.
(iii) Calcium carbonate scales can be dissolved by using 5-10% HCl. Calcium sulphate
scales can be dissolved by adding EDTA, with which they form soluble complexes.
(iv) By frequent blow-down operation, if the scales are loosely adhering.

2. Boiler corrosion:
Boiler corrosion is “the decay of boiler material by a chemical or electro-chemical
attack by its environment”.

Main reasons for boiler corrosion are:

(i) Dissolved oxygen. (ii) Dissolved carbon dioxide. (iii) Acids from dissolved salts.

(i) Dissolved oxygen:

Water usually contains about 8 ppm of dissolved oxygen at room temperature. At high
temperature this D.O. can attack boiler material.

Removal of dissolved oxygen:

By adding calculated quantity of sodium sulphite or hydrazine or sodium sulphide. Thus;
(ii) Dissolved carbon dioxide:

Carbon dioxide is also released inside the boiler, if water used for steam
generation contains bicarbonates.

Removal of dissolved carbon dioxide:

By adding calculated quantity of ammonium hydroxide.

(iii) Acids from dissolved salts:

Water, containing dissolved magnesium salts, liberate acids on hydrolysis.

The liberated acid reacts with iron (of the boiler) in chain- like reactions, producing HCl
again and again. Thus;

Consequently, presence of even a small amount of MgCl 2 will cause corrosion of iron
to a large extent. The HCl produced is neutralised with NaOH and removed as NaCl.

3. Priming and foaming:

Priming:
When a boiler is 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 caused by:

i. The presence of large amount of dissolved solids.

ii. High steam velocities.
iii. Sudden boiling.
iv. Improper boiler design.
v. Sudden increase in steam-production rate.
Priming can be avoided by:

a. Fitting mechanical steam purifiers.

b. Avoiding rapid change in steam rate.
c. Maintaining low water levels in boilers.
d. Efficient softening and filtration of boiler- feed water.

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

Foaming can be avoided by:

a. Adding anti- foaming chemicals like castor oil.
b. Removing oil from boiler water by adding compounds like sodium aluminate.

Dis-advantages of priming and foaming:

(i) Dissolved salts in boiler water are carried by the wet steam to 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, thereby decreasing the life of the machinery.
(iii) Actual height of the water levels cannot be judged properly, thereby making The
maintenance of boiler pressure becomes difficult.

4. Caustic embrittlement:
Caustic embrittlement is “a type of boiler corrosion, caused by using highly alkaline
water in the boiler”.During softening process of water (in 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. This
makes the boiler water ‘caustic’.

The NaOH containing water flows into the minute hair-cracks, present in the inner
side of boiler, bycapillary action. Here water evaporates and the dissolved caustic soda
(NaOH) concentration increases progressively. This caustic soda attacks the surrounding
area, thereby corroding the iron of boiler as sodium ferrate.

This causes embrittlement (cracking) of boiler parts, particularly stressed parts

(like bends, joints), causing even failure of the boiler.
 Caustic embrittlement can be explained by considering the following
concentration cell;

The iron surrounded by the dilute NaOH becomes the cathodic side; while the iron in
contact with concentrated NaOH becomes anodic part, which consequently corroded.

Prevention of caustic embrittlement:

(i) By using sodium phosphate as softening reagent, instead of sodium carbonate.
(ii) By adding tannin or lignin to boiler water, which blocks the hair-cracks,
thereby Preventing infiltration of caustic soda solution in cracks.

(iii) By adding sodium sulphate to boiler water:

Na2SO4 also blocks hair-cracks, thereby preventing infiltration of caustic soda

solution in these cracks. It has been observed that caustic embrittlement can be
prevented, if Na2SO4 is added to boiler water so that the ratio:

NaOH concentration /Na2SO4concentration

is kept as 1 : 1, 2 : 1 and 3 : 1 in boilers working respectively at pressures up to 10, 20
and above 20 atmospheres.

1.5: External conditioning (Ionexchange, zeolite)

Internal conditioning (Carbonate, phosphate, calgon, sodiumaluminate
conditioning)

Softening methods:

Water used for industrial purpose (such as fir steam generation) should be
sufficiently pure. Therefore, it should be freed from hardness producing salts before put
to use. The process of removing hardnessproducing salts from water, is known as
softening of water.

In industry, main methods employed for softening of water are two types.

Softening of water

Internal treatment External treatment

Internal treatment: (Or) Conditioning of water:

The softening of water carried out inside the boiler is called internal treatment of water.
In this process the hardness causing salts are removed
1. By complexing the hardness causing soluble salt by adding appropriate reagents.

2. By precipitating the scale forming impurities in the form of sludge which can be
removed by blow down operation.
3. By converting the scale forming salts into other compounds which stay in ‘dissolved
form and do not cause any trouble to the boilers.

The important internal conditioning methods are;

(a) Colloidal conditioning: The scale formation in low pressure boilers can be
prevented by the addition of kerosene, tannin, agar agar etc. which will be get coated
over the scale forming precipitates. These forms loose, non-sticky deposits (sludge)
that can be removed by blow down. This type of conditioning is called colloidal
conditioning.

(b) Phosphate conditioning: In this process, the permanent hardness causing salts in
high pressure boilers will be removed by reacting with sodium phosphate. The
complex formed is soft, non-adherent and easily removable.

The three phosphates employed in this process are Na3PO4 – tri-sodium phosphate
(alkaline), Na2HPO4 – disodium hydrogen phosphate (weakly alkaline) and NaH 2PO4
–
sodium di- hydrogen phosphate (acidic).

(c) Carbonate conditioning: The hard and strong adherent scales formed due to
CaSO4 are avoided by the addition of sodium carbonate to boiler water and this is
called carbonate condition.

The CaSO4 is converted to CaCO3, which is loose sludge and it can be removed by
blow down.

(d) Calgon conditioning: Sodium hexameta phosphate Na2[Na4(PO3)6 or (NaPO3)6

is called calgon. This forms solublecomplex compounds with CaSO4.The treatment
of boiler water with calgon is called calgon conditioning.

(e) Treatment with sodium aluminate (NaAlO2): Sodium aluminate is hydrolysed in boiler
to give NaOH. The formed NaOH immediately precipitates by the reaction with some of
the magnesium salts as Mg(OH)2

External treatment:
The treatment given to water for the removal of hardness causing salts before it is taken
into the boiler is called ‘external treatment’.

Zeolite process (Or) Permutit process:

Zeolite is hydrated sodium alumina silicate, which is capable of exchanging
 reversibly its sodium ions for hardness-producing ions in water. Chemical formula of
sodium zeolite may be represented as;
Na2O.Al2O3.x SiO2.y H2O where x = 2 – 10 and y = 2 – 6 Zeolites are two types;
a. Natural zeolites: These are non-porous. Eg: Natrolite Na2O.Al2O3.4 SiO2.2 H2O
b. Synthetic zeolites: These are porous and prepared by heating together china clay,
feldspar and soda ash. Such zeolites possess higher exchange capacity per unit
weight than natural zeolites.

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 (Ca2+,
Mg2+) are retained by the zeolite as CaZe and MgZe; while the outgoing water contains
sodium salts. Reactions taking place during the softening process are;

Regeneration:

After some time, the zeolite is completely converted into calcium and magnesium
zeolites and it ceases to soften water, i.e. it gets exhausted. At this stage, the supply of
water is stopped and the exhausted zeolite is reclaimed by treating the bed with brine
solution (10% NaC l solution).

The washings (containing CaCl2 and MgCl2) are led to drain and the regenerated
zeolite bed thus obtained is used again for softening purpose.

Limitations of Zeolite process:

(1) If the supplied water is turbid, the suspended matter must be removed, before the
 water is admitted to the zeolite bed; otherwise the turbidity will clog the pores of
zeolite bed, thereby making it inactive.
(2) If water contains large quantities of coloured ions such as Mn2+ and Fe2+, they
must be Removed first, because these ions produce manganese and iron zeolites,
which cannot be easily regenerated.
(3) Mineral acids, if present in water, destroy the zeolite bed and, therefore, they must
be neutralised with soda, before admitting the water to the zeolite softening plant.

Advantages of zeolite process:

(1) It removes the hardness almost completely, and water of about 10 ppm hardness
is produced.
(2) The equipment used is compact, occupying a small space.
(3) No impurities are precipitated, so there is no danger of sludge formation in the
treated water at a large scale.
(4) The process automatically adjusts itself for variation in hardness of incoming water.
(5) It requires less time for softening.

Disadvantages of zeolite process:

(1) The treated water contains more sodium salts than in lime-soda process.

(2) The method only replaces Ca2+ and Mg2+ ions by Na+ ions, but leaves all the
acidic Ions (HCO 3 and CO-2 3) as such in the softened water. When such
softened water (containing NaHCO3 and Na2CO3) is used in boilers for steam
generation, sodium bicarbonate decomposes producing CO2, which causes
corrosion; and sodium carbonate undergoes hydrolysis to sodium hydroxide,
which causes caustic embrittlement.
(3) High turbidity water cannot be treated efficiently by this method, because fine
impurities get deposited on the zeolite bed, thereby creating problem for its
working.

Ion exchange process (or) de- ionisation (or) de- mineralization process:
Ion exchange resins are insoluble, cross- linked, long chain organic polymers
with a micro porous structure, and the ‘functional groups’ attached to the chains are
responsible for the ion- exchange properties. Resins containing acidic functional groups
(-COOH, -SO3H) are capable of exchanging their H+ ions with other cations, which
comes in their contact. Resins containing basic functional groups (amino groups) are
capable of exchanging their anions with other anions, which comes in their contact.
Thus, ion-exchange resins may be classified as follows;

i. Anion exchange resins (R’OH-):

These are styrene-divinyl benzene or amineformaldehyde copolymers, which contain
amino or quarternary ammonium or quarternary phosphonium or tertiary sulphonium
groups as an integral part of resin matrix. These, after treatment with dil. NaOH solution,
become capable to exchange their OH anions with anions in water.
 ii. Cation exchange resins (RH+):

These are mainly styrene-divinyl benzene copolymers, which on sulphonation or

carboxylation, become capable to exchange their hydrogen ions with the cations in their
water.

Process:

The hard water is passed first through cation exchange column, which removes
the cations like Ca2+ and Mg2+ etc from it, and equivalent amount of H+ ions are released
from the column to water. Thus;

After cation exchange column, the hard water is passed through anion exchange
column, which removes all the anions like SO42-, Cl-, CO3`2- etc. present in the water and
equivalent amount of OH ions are replaced from this column to water. Thus;

H+ and OH- ions (released from cation exchange and anion exchange columns
respectively) get combined to produce water molecule.
1.6: Brackish water treatment- Reverse osmosis

Desalination of brackish water:

The process of removing common salt (sodium chloride) from water, is known
as desalination. The water containing dissolved salts with a 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;

1. Electro dialysis. 2. Reverse osmosis.

Reverse osmosis:
When two solutions of unequal concentrations are separated by a
semipermeable membrane, 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 diluted side across the membrane. This is the principle of reverse
osmosis. Thus, in reverse osmosis method, pure solvent is separated from its
contaminates, rather than removing contaminates from water. This membrane filtration
is sometimes also called superfiltration or hyper-filtration.
Advantages:
1. This process removes, ionic as well as non- ionic, colloidal and high molecular weight
organic matter.

2. It removes colloidal silica, which is not removed by demineralization process.

3. The life time of membrane is quite high, about 2 years.

4. The membrane can be replaced within a few minutes, thereby providing nearly
uninterrupted water supply.
5. Due to low cost, simplicity and high reliability, the reverse osmosis is gaining ground
at present for converting sea water into drinking water.