Dr.

Vandana Rathore
Associate Professor
[email protected]

Unit-1
Engineering Chemistry

1
Unit-I: Water quality parameters: Physical, Chemical & Biological
Water significance, Hardness of water, disadvantages of using hard water
Treatment in boilers: Scale, sludge formation, disadvantages, prevention,
and treatment:
Organic Internal conditioning, phosphate, carbon and carbonate
Reactions conditioning methods,
External: Softening methods [Zeolite (permutit process) (Book
Notes p18-19), ion exchange methods, desalination, reverse
osmosis and domestic water treatment.
Introduction to reactions: involving substitution, addition,
elimination, oxidation, reduction, cyclization and ring openings.
Synthesis of a commonly used drug molecule.

2
 INTRODUCTION
• The nature’s most abundant supply i.e., water is essential for the survival of all the
living beings on earth i.e., man, animals and plants. Water is not only essential for
the survival of life, but it is also used for the operation in a large number of
industries as coolant, solvent, for steam generation, for air conditioning, fire-
fighting etc. Water is also used for all domestic purposes like bathing, drinking,
washing, sanitary, irrigation etc.
HARDNESS OF WATER
• “Hardness of water is the characteristic of preventing lather formation of water
• with soap”. Generally salts like chlorides, bicarbonates and sulphates of Ca2+,
Mg2+ and Fe2+ make water hard. This hard water on treatment with soap which
is stearic (C18H36O2) or palmitic acid (C16H32O2) salts of sodium or potassium
causes white precipitate formation of calcium or magnesium stearate or
palmitate.

3
Thus the cause of hardness is the precipitation of the soap and hence
prevents lathering at first. When the hardness causing ions are
removed as insoluble soaps, water becomes soft and forms lather.

4
6
• Parts per million (ppm): It is the number of parts of calcium carbonate equivalent
• hardness present in one million parts of water.
• 1 ppm = 1 part of CaCO3 equivalent hardness in 106 parts of water.
• 2. Milligram per lite (mg/L): It is the number of milligrams of Calcium carbonate equivalent
• hardness present in one litre of water.
• 1 mg/lit. = 1 mg of CaCO3 equivalent hardness in 1 litre of water.
• 3. Degree Clarke (oCl): It is the number of parts of CaCO equivalent hardness present in
• 70,000 parts of water.
• 4. Degree French (oFr): It is the number of parts of CaCO equivalent hardness present
• in 105 (1 Lakh) parts of water.
• 1oFr = 1 part of CaCO equivalent hardness in 105 parts of water.
• The above four units are correlated as given below:
• 1 ppm = 1 mg/L = 0.07oCl = 0.1oFr
• 1 ppm= 1 part of hardness
• 106 parts of water 7
Disadvantages of Hard Water
(a) In domestic uses.
 For washing and bathing, hard water creates difficulties, since it does not form
lather freely with soap. It also creates sticky precipitates that deposit on bath tub,
body, clothes etc. until all the Ca/Mg salts get precipitated. Thus a lot of soap gets
wasted .

 For cooking hard water creates similar difficulties by producing scum on the bottom
of the vessels. Due to the presence of hardness producing salts in hard water,
boiling point gets elevated and during cooking a lot of fuel is wasted. Pulses etc. do
not cook in hard water. Taste of tea, coffee becomes unpleasant.

 Drinking of hard water is also problematic since it affects the digestive system and at
the same time the possibility of deposition of calcium oxalate crystals in the urinary
tract is alarming.
8
(b) In industrial uses.
• For textile industry and dyeing industry, hard water
causes the usual problem of deposition of insoluble salts
that interfere with the proper dyeing and printing of the
fabrics. The stains of iron salts also are undesirable on
fabrics. Hard water also hampers the economy by wastage
of soap as it does not form good lather.
• For sugar industry, the salts responsible for hardness
create difficulties in sugar refining and crystallization of
sugar and the sugar becomes deliquescent.
• Calcium and magnesium salts also interfere with the
smooth and glossy finish of the papers in the paper
industry. Iron salts interfere with the colour of the paper.
9
• In laundry, hard water causes wastage of costly soap and also
interferes with the coloration due to the staining of iron salts.
• The hydration of cement and final hardening of cement are affected
by use of hard water in concrete making.
• Hard water is not suitable for preparing drug solutions in
pharmaceutical industry
• For steam generation in boilers, hard water creates many problems
like:
• (i) scale and sludge formation,
• (ii) corrosion,
• (iii) priming and foaming and
• (iv) caustic embrittlement. 10
ESTIMATION OF HARDNESS OF WATER BY EDTA

Eriochrome Black-T (EBT) is the metal ion indicator used in the determination
of hardness by complexometric titration with EDTA. This dye-stuff tends to
polymerize in strongly acidic solutions to a red brown product, and hence
the indicator is generally used in EDTA titration with solutions having pH
greater than 6.5. The sulphuric acid gropus loses its proton much before the
pH range of 7-12, which is of interest for metal ion indicator use.
The dissociation of the two hydrogen atoms of the phenolic groups only
should therefore be considered and hence the dye stuff may be represented
by the formula H D−. This functions as acid-base indicator with two colour
changes as follows:

Practical Problems………………..

11
• BOILER TROUBLES
• Scale and Sludge
• When hard water is used for boilers, on continuous
evaporation, the salts present in the hard water gets
saturated and are finally deposited in the areas where
the flow is slow. When the precipitates formed are
loose and slimy in nature, it is called sludge, whereas
when the precipitates formed are hard and adhere
strongly on the inner walls of the boiler, they are called
scale.
12
• Sludge can be easily removed by scrapping with a brush. Sludge is formed
by the presence of MgCO3, MgSO4, MgCl2, CaCl2 etc. These salts are
more soluble in hot water.
• Disadvantages of sludge formation are:
• (i) poor heat conduction due to the presence of sludge on the surface;
• (ii) difficulty in the operation of the boiler;
• (iii) if sludge is formed along with the scale and is trapped within the
scale formed and so it is difficult to remove and
• (iv) it clogs the pipe lines and other connections to the vessel near the
places where water circulation rate is slow.

13
14
• Removal of Sludge
• Sludge formation can be prevented by:
• (i) using soft water for boiler operation and
• (ii) removing the concentrated salty water from time to
time so that deposition of sludge is prevented. Scales are
the hard deposits on the inner surface of the boilers which
are difficult to remove.
• This scale formation takes place due to the following
reasons:

15
(a) In low pressure boilers scale formation occurs due to the formation of
CaCO3 from Ca(HCO3)2 calcium hydrogen carbonate/calcium
bicarbonate.
• Ca(HCO3 )2 ⎯⎯→ CaCO3 ↓ + H2O + CO2
scale
(b) In high pressure boilers this CaCO3 gets converted to soluble calcium
hydroxide Ca(OH)2. But here CaSO4 forms the hard scale. Since the
solubility of CaSO4 decreases with increase in temperature, and at high
temperature the precipitated CaSO4 forms hard scale. Similar hard scales
are formed when SiO2 is present in the hard water. It deposits as calcium
silicate CaSiO3 or MgSiO3. These calcium or magnesium silicate scales
are very difficult to remove. Dissolved magnesium salts also precipitate as
Mg(OH)2 forming soft type of scale.
16
• Disadvantages of scale formation are similar to sludge formation but the
severity is more, since its removal is more difficult.
• Disadvantages include
• (i) Poor heat transfer from boiler to water leading to increase in fuel consumption.
The increase in thickness of the scale from 1.25 mm to 12 mm leads to increase in
fuel consumption from over 50% to 150%.
• (ii) Due to the overheating of the boiler, different parts of the boiler become weak
and distorted and so the operation of the boiler becomes unsafe, particularly the
high pressure boilers. The thick scales may sometimes lead to explosion due to
sudden development of high pressure.
• (iii) Valves and condensers of the boilers are chocked due to scale formation and
Boiler efficiency decreases.

17
• Removal of scales can be done by:
• (i) Wooden scraper or wire brush, suitable for removing
loose scales.
• (ii) Blow down operations for loose scales. The operation
actually involves the removal of very hard water from a tap
at the bottom of the boiler and replenishing the water
with softened water called ‘make up’ water.
• (iii) Giving thermal shocks, which involve alternate heating
and cooling to make the scales brittle.
• (iv) Chemical treatment with 5-10% HCl for carbonates and
EDTA treatment for Ca/Mg salts forming complexes

18
19
Q. (1) What are boiler troubles? Explain Scales and Sludge formation.

Boiler troubles are 1) Priming & foaming 2) Sludge & Scales3) Caustic
embrittlement 4) Boiler corrosion
• Sludge & Scale formation
• In a boiler, water is continuously evaporated and converted into steam. As a
result the water becomes saturated due to increase in the concentration of
dissolved impurities. Finally a stage is reached where the ionic products of these
salts exceeds their solubility product and are thrown out as precipitates on the
inner walls of the boiler.
• Sludge:
 Soft, loose and slimy precipitate formed within the boiler.
 Formed at comparatively colder portions of the boiler and are collected at the
bends.
 Formed by substances which have greater solubility in hot water than in cold
water, e.g., MgCO3, MgCl2, CaCl2, MgSO4, etc
 Easily removed with wire brush
20
• Disadvantages of sludge formation
• Sludges are poor conductors of heat, so they tend to waste a portion of heat
generated.
• Excessive sludge formation disturbs the working of the boiler.
• Sludge can be removed by using 1) Softened water 2) by blow down operation
i.e. drawing off a portion of the concentrated water.
• Scales:
• Hard deposits firmly sticking to the inner walls of the boiler.
• Difficult to remove, even with the help of hammer & Chisel.
• Formed due to:
• i) Decomposition of Calcium bicarbonate:
• Ca (HCO3)2 CaCO3↓ + H2O+CO2
Scale (Soft, formed mainly in low pressure boilers)
• In high pressure boilers, CaCO3 is soluble due to formation of Ca (OH)2
• CaCO3 + H2O Ca (OH)2 + CO2↑ 21
ii) Deposition of CaSO4:
Solubility of CaSO4 decreases with increase in temperature.
It is completely insoluble in super heated water.
Hard scale formation takes place in high pressure boilers
iii) Hydrolysis of Magnesium salts:
Soft scale formation due to hydrolysis of Mg salts in high pressure boiler.
MgCl2 + 2H2O Mg (OH)2↓ + 2HCl
iv) Presence of silica:
Even very small amounts of silica leads to deposits of Ca/Mg
silicates(CaSiO3 & MgSiO3), which adheres firmly to the inner boiler
walls. It is difficult to remove.
22
Disadvantages of scale formation:
i) Wastage of fuel:
Rate of heat transfer is greatly reduced due to poor conductivity of scales
Overheating is required for steady supply of heat hence fuel consumption
increases.

ii) Lowering of boiler safety:

To supply steady heat overheating is required, which makes the boiler
material weak &soft. Results in distortion of boiler tube & makes the boiler
unsafe to bear the high pressure.
iii) Decrease in efficiency of boiler:
Deposition of scales in valves and condensers choke them partially&
decreases the efficiency of boiler

iv) Danger of Explosion:

Due to uneven expansion the thick scales gets cracked, results in formation of
large steam & develops high pressure. It may cause explosion of boiler. 23
Removal of scales:
 Mechanical/chemical method
 Loosely adhering scales are removed with the help Scraper/wire brush
 Brittle scales are removed by giving Thermal shocks
 Loosely adhering scales are removed by frequent blow down operation
(frequently removing precipitates)
Adherent & hard scales are removed by dissolving them by adding chemicals
CaCO3 scales - 5-10% HCl
CaSO4 scales – EDTA

24
2. Explain internal treatment methods for removal of scales.
Internal treatment (Sequestration):
In this method some chemicals reagents are added directly to the boiler water
for removing dangerous scale forming salts.
The chemicals convert the scale forming impurities into sludge or more
dissolved compounds.
This method is generally followed by blow down operation.
Important internal conditioning/treatment methods:
A. Carbonate conditioning:
Reagent added is sodium carbonate.
In low pressure boilers scale formation can be avoided by adding sodium
carbonate to boiler water
CaSO4 +Na2CO3 CaCO3↓ +Na2SO4
Sludge
Deposition of CaSO4 as scale doesn’t takes place and calcium is precipitated as
loose sludge of CaCO3 which can be removed by blow down operation.
25
B. Phosphate conditioning:
• Reagent added is sodium phosphate.
• In high pressure boilers scale formation can be avoided by
adding sodium phosphate. It reacts with hardness of water
forms non adherent, easily removable soft sludge of Ca / Mg
phosphates.
• 3CaCl2 +2Na3PO4 Ca3 (PO4)2 ↓+ 6NaCl
• Sludge
• We can use different phosphates based on PH of water
• Na3PO4 (alkaline in nature) is used when alkalinity is low.
• Na2HPO4 (weakly alkaline) is used when alkalinity is sufficient.
• NaH2PO4 (acidic) is used when alkalinity is high

26
3. Calgon conditioning:
• Reagent added is Calgon.
• Calgon = sodium hexa meta phosphate
• The process involves the addition of calgon to boiler water.
• It prevents scale and sludge formation by forming highly
soluble calcium hexa meta phosphate complex compound
with CaSO4.
• Na2 [Na4(PO3)6] 2Na+ + [Na4(PO3)6]2-
• 2CaSO4 + [Na4(PO3)6]2- [Ca2(PO3)6]2- + 2 Na2SO4
Highly Soluble
complex ion
27
Introduction to reactions involving substitution, addition,
elimination, rearrangement:
• addition reaction
• elimination reaction
• rearrangement reaction
• substitution reaction
First, we identify four broad classes of reactions based solely on
the structural change occurring in the reactant molecules.

28
29
In an addition reaction the number of σ-bonds in the substrate molecule
increases, usually at the expense of one or more π-bonds. The reverse is true
of elimination reactions, i.e. the number of σ-bonds in the substrate
decreases, and new π-bonds are often formed.
Substitution reactions, as the name implies, are characterized by
replacement of an atom or group (Y) by another atom or group (Z). Aside
from these groups, the number of bonds does not change.
A rearrangement reaction generates an isomer, and again the number of
bonds normally does not change.
The examples illustrated above involve simple alkyl and alkene systems, but
these reaction types are general for most functional groups, including those
incorporating carbon-oxygen double bonds and carbon-nitrogen double and
triple bonds. Some common reactions may actually be a combination of
reaction types.
DOMESTIC DRINKING WATER TREATMENT
Requirements of drinking ( potable) water:
i. Free from colour, odour, bacteria, dissolved gases
ii. Should have pleasant taste
iii. Dissolved oxygen should be below 10 ppm
iv. Chloride content should be below 250 ppm.
v. Flouride content should be below 1.5 ppm.
vi. Hardness salt content should be below 500 ppm.
vii. PH should be in the range of 6.5 – 8.0
To get these properties, the water is treated properly.

31
32
33
Filtration:
• Filter bed consists of four layers i.e., Fine sand, coarse sand, fine gravel and coarse
gravel.
• When water is passed through this, all the colour, odour, part of bacteria are removed.
The
• bed needs periodic regeneration.

34
Sterilisation:
Removal of bacteria is sterilization or disinfection. There are four important sterilization
methods.
1. Boiling 2. Using ozone 3. UV treatment 4. Chlorination
a. Passing Chlorine gas or solution
b. Adding chloramines salt
c. Adding bleaching powder
1. By boiling for 10 – 15 minutes, water can be sterilized . But it affects the taste and
can not be used for higher volume water.
2. By using Ozone,(with the usual dosage of 2-3ppm for 10 – 15 miuntes in disinfection tank) we
produce nascent oxygen which is powerful disinfectant.Its excess is not harmful, since it is
unstable and decomposes into oxygen. But, it is costly. It cannot be used and stored for long time
as it is unstable.
O3 O2 + [ O] , this nascent (atomic form of) oxygen kills bacteria.

3. By passing UV radiations from mercury vapour lamp, the swimming pool water can be
sterilized. But it is costly and turbid water cannot be treated.
35
36
Breakpoint chlorination:
The point at which the added chlorine completely removes bacteria, NH3, Organic and
inorganic impurities is known as “Breakpoint chlorination”.
The water contains: a)Bacteria b)Ammonia c)Organic impurity (sewage) d)Inorganic salt
impurities ( Effluents, H2S , Fe salts)
1. When we add chlorine, first it kills bacteria and oxidizes some inorganic impurities.
2. The added chlorine is completely consumed. (a).
3. Further addition of chlorine is used to combine with ammonia to form chloramines
compounds. So, the residual chlorine content is increased upto (b).
4.As saturation level is attained, the chloramines begin to decompose to release
chlorine
which is utilized to remove all the types organic and inorganic impurities. So, residual
chlorine level decreases. (c).
5.At point (c), the added chlorine removes all the types of impurities. So, the point is
known as “ Break point chlorination”.
6. After this point, further addition of chlorine is not at all utilized and simply increases
the residual chlorine content.(along cd) 37
Diagram for Breakpoint chlorination

Advantages of break point chlorination: (Significance)

i)It is used to remove Bacteria , Ammonia ,Organic impurity (sewage) ,Inorganic salt
impurities ( Effluents, H2S , Fe salts) from water.
ii)It prevents the growth of any weeds in water.
38
Questions:
1. Discuss characteristics and consequent effects of impurities in water in three heads
(Physical, Chemical and Biological impurities).
2. Write a brief note on hardness of water.
3. Give the characteristics and its purpose for water used in industries.
4. Why should natural water not be fed to boiler?
5. Write two balance equations to describe what occurs when hard water is heated.
6. Explain why water containing Ca2+ (aq) and HCO3- (aq) ions is said to be hard.
7. Explain Scale & sludge formation in boilers. Discuss prevention, treatment disadvantages of it.
8. Explain softening of water and discuss any process of it (LS/Zeolite process).
9. Explain essential requirement of municipal water/drinking water.
10. Illustrate various treatment processes which are employed for purification of water for domestic
use. i Removal of suspended impurities, ii Removal of micro-organism
11. Write a note on Break point chlorination. Depict graphically its different stages.
12. Explain internal treatment methods for removal of scales.
13. What are boiler troubles? Explain Scales and Sludge formation.

39