USC-101 (Theory) CHEMISTRY

Teaching Scheme Examination Scheme

L T P C Hrs/Week Theory Term Work Practical/ Total
Viva Marks
MS ES IA
3 0 -- 6 3 25 50 25 -- -- 100
Water & its
Treatment
UNIT I
Water and its Treatment: Introduction, sources of water Impurities in water, hard and soft
water, Degree of hardness, Types of hardness, Scale and sludge formation in boiler, Effect
of hardness in oil industry, Caustic embrittlement, Priming and Foaming, Softening of water
by Lime-Soda process, Zeolite process, Ion-exchange process and RO process. Biological
treatment of water, Potable water, COD & BOD.
Corrosion and its Control: Introduction, Theories of corrosion, Electrode potential, Types
of corrosion, Factors of corrosion, Protection of metals from corrosion – Isolation method,
Cathodic protection, Sacrificial method, Cathodic protection, ICCP.

UNIT II
Chemistry of Fuels and Lubricants:
Fuels: Origin, Classification and properties of Solid, Liquid, Gaseous Fules, Characteristics of
good fuel, Merits & demerits of solid, liquid and gaseous fuels, Proximate and Ultimate
analysis, Octane number (RON, MON) and Cetane number, Petrol and Diesel Engine, Fuel
Cell and Fuel Cell technology
Lubricants - General characteristics of lubricants, mechanism of lubrication, Classification
of lubricants, chemistry of lube oil and greases, Cutting fluids, Selection of lubricants,
Properties of lubricants, Biolubricant
UNIT III
Chemistry of Advanced Materials : Nanomaterial (Fullerenes, Carbon nanotube,
Nanowires, Graphene), Polymers & Resins including Geopolymer, Modern-age Catalysts
(Emission-control catalyst), Cement and cementing materials

UNIT IV
Instrumental Methods of Chemical Analysis
Principle, Instrumentation and Applications of FT-IR, UV-Vis, Chromatographic Techniques
(GC, etc), Thermal Analysis (TG-DTA-DSC); Electroanalytical techniques (pH-metry,
conductometry, potentiometry), Polarimeter
 SOURCES OF WATER
1. Physical States:
a. Solid: glaciers & ice caps
b. Liquid: oceans, rivers, lakes,
underground, clouds, & rain
c. Gas: water vapor in the atmosphere

2. Physical Location:
a. Surface water:: water located on the
surface of the Earth
b. Ground water:: water located beneath
the Earth’s surface
 CONTAMINATIONS OF WATER

Physical Chemical Biological

Color
Acidity Algae
Turbidity
Gases Fungi
Taste
Minerals Pathogens
Odor
 CONTAMINATIONS OF WATER
There is no pure water in nature, as it can contain
up to 90 possible unacceptable contaminants
Contaminant groups:
1. Inorganic compounds - magnesium carbonate,
calcium carbonate and sodium chloride
2. Organic compounds - detergent residues, solvents
etc.
3. Solids - clays, sols, and soils
4. Gases - nitrogen, carbon dioxide and oxygen
5. Micro-organisms – Algae, Bacteria, Protozoa
CONTAMINATIONS OF WATER

Treatment depends on water’s chemistry and

contaminants, influenced by:
1. Rainfall
2. Erosion
3. Pollution
CONTAMINATIONS OF WATER
Major constituents
1. Calcium and magnesium
2. Iron and manganese
3. Silicates
4. Carbon dioxide
5. Hydrogen sulfide
6. Phosphates
Others
1. Copper
2. Aluminium
3. Heavy metals
– Arsenic, lead, cadmium
4. Nitrates
 CONTAMINATIONS OF WATER

Micro-organisms
1. Algae
2. Protozoa
– Cryptosporidium
– Giardia
3. Bacteria
– Pseudomonas
– non-fermenting bacteria
– Escherichia coli and coli forms
 HARDNESS

Hardness is the characteristics that prevents lathering of soap.

Soap is a sodium or potassium salt of higher fatty acids like
palmitic, oleic or stearic acid.

When soap is applied in presence of hard water, it forms white
precipitate instead of lather, due to the formation of insoluble
salts of Calcium or Magnesium

Typical reaction in hard water:

2C17H35COONa + CaCl2 = (C17H35COO)2Ca ↓ + 2NaCl
Sodium stearate Calcium stearate

2C17H35COONa + MgSO4 = (C17H35COO)2Mg ↓ + Na2SO4

Magnesium stearate
 HARDNESS - TYPES
(1) Temporary Hardness:
Caused by the presence of dissolved bicarbonates of calcium,
magnesium and other heavy metals, and carbonates of iron
Can be removed by boiling

Ca(HCO3)2 → CaCO3 ↓ + H2O + CO2↑

Mg(HCO3)2 → Mg(OH)2 ↓ 2CO2↑

(2) Permanent Hardness:

Caused by the presence of chlorides and sulphates of Ca, Mg,
Fe and other heavy metals.
Cannot be removed by boiling
 HARDNESS - UNITS
(1) Parts per Million (ppm):
It is the parts of calcium carbonate equivalent hardness per 106
parts of water. [1 ppm = 1 part of CaCO3 eq hardness in 106 parts
of water]

(2) Milligrams per liter(mg/L):

It is the number of milligrams of CaCO3 equivalent hardness
present per liter of water
1 mg/L = 1 mg of CaCO3 eq hardness of 1 L of water
Now, 1 L of water = 1 Kg = 1000 g = 1000X1000 mg = 106 mg
Thus 1mg/L = 1 mg of CaCO3 eq per 106 mg of water
= 1 part of CaCO3 eq per 106 parts of water = 1 ppm
 HARDNESS - UNITS
(3) Clarke’s Degree (⁰Cl):
It is the number of grains (1/7000 lb) of CaCO3 equivalent
hardness per gallon (10lb) of water. Or, it is the parts of CaCO3
equivalent hardness per 70000 parts of water.
1⁰ Clarke = 1 grain of CaCO3 eq hardness per gallon of water
1⁰ Clarke = 1 part of CaCO3 eq hardness per 70000 parts of water

(4) Degree French (⁰Fr):

It is the parts of CaCO3 equivalent hardness per 105 parts of water
Thus 1⁰ Fr= 1 part of CaCO3 eq hardness per 105 parts of water

(5) Milliequivalent per liter (meq/L):

It is the number of milli equivalent of hardness per liter.
Thus, 1 meq/L = 1 meq of CaCO3 per L of water
 WATER HARDNESS RATING
mg/L as CaCO3 Degree of Hardness

0-60 Soft water

61-120 Moderately hard water

121-180 Hard water

>180 Very hard water

Q. How many grams of Ca(HCO3)2 dissolved per liter gives 100 ppm of hardness?

Q. Calculate the temporary and permanent hardness of a sample of water containing :

Mg(HCO3)2=7.3 mg/L
Ca(HCO3)2=16.2 mg/L
MgCl2=9.5 mg/L
CaSO4=13.6 mg/L

Temporary hardness= 5+10 mg/L

Permanent hardness=10+10 mg/L

Q. In a given water sample, the concentrations (in mg/L) of Ca(HCO3)2:

Mg(HCO3)2: CaCl2: Mg(NO3)2 : NaCl are in the ratio of 2.77: 2.50:
1.90: 2.53: 1.00. The total hardness (in CaCO3 equivalent) of the water
sample is 400 ppm. Calculate the concentrations of each of the
components in the water sample, the temporary hardness and the
permanent hardness of the water sample.
HARDNESS - DISADVANTAGES
Domestic
(1)Washing
(2)Bathing
(3)Cooking
(4)Drinking

Industrial
(1)Textile Industry
(2)Sugar Industry
(3)Dyeing Industry
(4)Paper Industry
(5)Laundry
(6)Concrete
(7)Pharma Industry
(8)Steam Generation in Boiler
 SALTS IN
FEED WATER

HARDNESS OR
NONE HARDNESS,
SOLUBLE SALTS SCALE FORMING
SALTS
SODIUM SALTS
CALCIUM AND
MAGNESIUM
SALTS
ALKALINE OR NON ALKALINE
SOLUBLE UNLESS TEMPORARY OR PERMANENT
VERY HIGH HARDNESS SALTS HARDNESS SALTS
CONCENTRATIONS
BI-CARBONATES
CHLORIDES,
CARBONATES,
SULPHATES
 METHODS OF DETERMINATION
1. Complete Cation Analysis
• Most accurate

• Calculation of the hardness caused by each ion

is performed by use of the general formula:

Hardness (mg/L) as CaCO3 = M2+ (mg/L) X 50

EW of M2+

where M2+ represents any divalent metallic ion

and EW represents equivalent weight
 SCALE & SLUDGE FORMATION IN BOILER

• Water evaporates continuously and the conc.

of dissolved salts increases
• At saturation points salts become insoluble
and forms precipitate on the inner walls of
boiler
• Loose & Slimy precipitate – SLUDGE
• Hard precipitate / coating - SCALE
 SLUDGE
• Loose and slimy ppt formed within the boiler
• Can be easily scrapped using wire mesh
• Forms in colder parts of boiler and bends
• At saturation points salts become insoluble
and forms precipitate on the inner walls of
boiler
• Formed by solids* which are more soluble in
hot water than cold water
• *Examples – MgCO3, MgCl2, MgSO4, CaCl2
 SLUDGE – DISADVANTAGES & PREVENTION

• Poor conductor of heat, wastage of heat

generated
• Can be formed along with scales to becomes
unmovable
• Can be deposited in poor water circulated
regions, and tend to choke pipes
• Can be prevented from forming by using
softened water or drawing of part of
concentrated water
 SCALES - FORMATION
1) Decomposition of calcium bicarbonate (for low pressure boilers)
Ca(HCO3)2  CaCO3 ↓+ H2O + CO2 ↑

2) Deposition of calcium sulphate (for high pressure boilers)

CaSO4 is more soluble in cold water than hot water and almost
insoluble in very hot water; thus, gets precipitated in heated part of
boiler
3) Hydrolysis of magnesium salts
MgCl2 + 2H2O  Mg(OH)2 ↓ + 2HCl ↑
4) Presence of silica
SiO2 deposits as calcium or Magnesium silicate (CaSiO3 or MgSiO3).
Vey difficult to remove from boiler inner surface
 SCALES – DISADVANTAGES & REMOVAL
Thickness (mm) 0.325 0.625 1.25 2.5
DISADVANTAGES
Wastage (%) 10 15 50 80
• Wastage of fuels
• Lowering of boiler safety-----overheating softens
• Danger of explosion (after scales crack)
• Decrease in efficiency----deposit in valves etc.
REMOVALS
• by scrapping with wood or wire mesh (if loose)
• By giving thermal shocks
• By dissolving with addition of chemicals (eg, CaCO3
is removed by 5-10% HCl)
• EDTA treatment
 SCALES – PREVENTION OF FORMATION
External Treatment
Softening of water
Internal Treatment (ion is prohibited to exhibit
Its original character)
Addition of a proper chemical to boiler to
precipitate the scale-forming impurities in the
form of sludge or convert them to soluble
compounds
 SCALES – PREVENTION WITH INTERNAL TREATMENT

1) Colloidal conditioning
Addition of organic matters (tannin, agar-agar) get coated over scale-forming ppt,
yielding non-sticky, loose deposits, which can be removed

2) Phosphate conditioning
Addition of phosphates of sodium (NaH2PO4, Na2HPO4, Na3PO4) helps forming
easily removable Ca & Mg phosphates
3CaCl2 + 2Na3PO4  Ca(PO4)2 ↓ + NaCl [requires >9.5 pH)

3) Carbonate conditioning
Addition of sodium carbonate helps forming easily removable CaCO3
CaSO4 + Na2CO3 ⇔ CaCO3 ↓ + Na2SO4
 SCALES – PREVENTION WITH INTERNAL TREATMENT

4) Calgon conditioning
Addition of calgon (sodium hexa meta phosphate) prevents scale and sludge
formation by forming soluble complex with CaSO4
Na2[Na4(PO3)6] ⇔ 2Na+ + [Na4P6O18]2-
2CaSO4 + [Na4P6O18]2-  [Ca2P6O18]2- + 2Na2SO4

(soluble complex ions)

5) Sodium Aluminate Treatment

Sodium aluminate hydrolyses to yield NaOH and gelatinious Al-hydroxide.
NaOH precipitates Mg-salts as Mg-hydroxide. The hydroxides thus forms
entrap suspended and colloidal impurities (e.g., silica), which can be removed
easily.
NaAlO2 + 2H2O  NaOH + Al(OH)3 ↓
MgCl2 + 2NaOH  Mg(OH)2 ↓ + 2NaCl
 SCALES – PREVENTION WITH INTERNAL TREATMENT

6) Electrical conditioning
Mercury containing sealed glass tubes are connected to battery and rotated
inside the boiler. When water boils, Hg bulb emits electrical discharge, thereby
preventing scale forming particles adhering together
7)Radioactive conditioning
Tablets containing radioactive salts are kept inside the boiler water, and the
radiation emission prevents scale formation
8) Complexometric method
Addition of alkaline EDTA solution helps EDTA binding with the scale-forming
cations yielding stable, soluble complex. Also, it prevents deposition of Fe-
oxide formation inside the boiler
 CAUSTIC EMBRITTLEMENT
• Caustic embrittlement is a type of boiler corrosions caused by
using highly alkaline water in the boiler and also due to stress.
Water softened by lime soda process may contain NaOH which is
formed by the hydrolysis of Na2CO3.

• Na2CO3 + H2O→2NaOH + CO2

• The NaOH containing water flows through small pores in the

stressed areas like bends, joints hair-cracks etc. When water
evaporates the concentration of NaOH increases and it corrodes
the surrounding area by forming sodium ferroate (Na2FeO2). This
causes embrittlement of boiler parts particularly stressed parts
causing even failure of the boiler.
The corrosion cell can be represented as
Fe (under stress) / conc. NaOH / dil. NaOH/ Fe (stress free)
Anode Cathode
 PRIMING & FOAMING
Priming
When a boiler is producing steam rapidly some particles of the water liquid
carried along with the steam. This process of ‘Wet Steam’ formation is called
priming.

Causes of Priming
(1) the presence of large amount of dissolved solids
(2) high steam velocities.
(3) sudden boiling
(4) improper boiler design
(5) sudden increase in steam-production rate.

Prevention of Priming
(1) By improving boiler design.
(2) By fitting mechanical steam purifiers.
(3) By maintaining low water level in boilers
(4) By using soft water.
 PRIMING & FOAMING
Foaming
It is the production of foam or bubbles in boiler which do not break easily.

Causes of Foaming :
It is due to the presence of oily substances in water.

Prevention of Foaming :
(1) By the addition of anti-foaming chemicals like castor oil, Gallic acid, tannic
acid etc.
(2) removing oil from boiler water by adding compounds like sodium aluminate.

Disadvantages of Priming and foaming

(1) Dissolved salt in boiler water are carried out by the wet steam to turbine
blades which reduces their efficiency.
(2) Dissolved salts may enter the parts of other machinery may decrease the life
of the machinery.
(3) Actual height of the water column cannot be judge properly, thereby making
the maintenance of the boiler pressure becomes difficult.
 External Treatment
It can be done by the following methods.
(1)Lime-Soda process (2) Zeolite process (3) Ion-
exchange process.
Lime – Soda process
The basic principle behind this method is the chemical
conversion of all the soluble hardness causing impurities
into insoluble precipitates which may be removed by
settling and filtration.

This method consists of simultaneous addition of

calculated quantities of both lime and soda into hard
water followed by removal of the precipitates.
 Cold lime-Soda process
• This involves mixing of calculated quantities of lime and soda
with water at room temperature.
• The precipitates formed are finely divided and do not
precipitate easily.
• Small amount of coagulants (alum, Al-sulfate, Na-aluminate)
are added, which hydrolyse to flocculent, gelatinous ppt of Al-
hydroxide and entraps the fine particles
• Cold L-S process results in residual hardness of 50-60 ppm

NaAlO2 + 2H2O → 2NaOH + Al(OH)3 ↓

2Al3+ + 3Ca(HCO3)2 → 2Al(OH)3 + 3Ca2+ + 6CO2 ↑

 • The cold lime soda process
consists of a steel tank with two
chambers, having separate inlets
for raw water and chemicals.
• The inner chamber is provided
with a paddle stirrer for proper
mixing of chemicals and water.
• The outer chamber is provided
with a fibre filter. As raw water and
chemicals are flow down, stirring
and mixing is done by operating the
stirrer.
2
• Water get softened and the
resulting sludge get deposited at
the bottom of the outer chamber.
• The softened water moves
upward through the filter to ensure
complete removal of sludge.
 Hot lime-Soda process
• This involves treating water with softening chemicals at temp
>80 ⁰C
• Hot condition makes the reaction faster
• Softening capacity increases
• Precipitate and sludge settle down faster thus no coagulant
needed
• Much of the dissolved gases escape
• Viscosity of softened water is lower, thus filtration become
easier
• Hot L-S process results in residual hardness of 15-30 ppm
Hot Lime Soda Process
 Reactions in Lime-Soda Process
S.No Constituent Reaction Need
1 Ca2+ (Perm Ca) Ca2+ + Na2CO3 CaCO3 + 2Na+ S
2 Mg2+ (PermMg) Mg2+ + Ca(OH)2 Mg(OH)2 + Ca2+
Mg2+ + Na2CO3 MgCO3 + 2Na+ L+S
-
3 Bicarbonate(HCO3 2 HCO3- + Ca(OH)2 CaCO3 + H2O + CO3 2- L –S
Ca(HCO3)2 + Ca(OH)2 2 CaCO3 + 2 H2O L
Mg(HCO3)2 + 2Ca(OH)2 2 CaCO3 + 2 H2O 2L
+ 2 Mg(OH)2
4 CO2 CO2 + Ca(OH)2 CaCO3 + 2 H2O L
5 H+ +
2 H + Ca(OH)2 Ca2+ + 2 H2O
Ca2+ +Na2CO3 CaCO3 + 2Na+ L+S
6 NaAlO2 NaAlO2 + H2O Al(OH)3 + NaOH -L
2NaOH is equal to Ca(OH)2
7 FeSO4 Fe2+ + Ca(OH)2 Fe(OH)2 + Ca2+
2Fe(OH)2 + H2O + O2 2Fe(OH)3
2+
Ca + Na2CO3 CaCO3 + 2Na+ L+S
8 Al2(SO4)3 2Al3+ + 3Ca(OH)2 2Al(OH)3 + 3Ca2+
3Ca2+ + 3Na2CO3 3CaCO3 +6Na+ L+S
 PERMUTIT (ZEOLITE) PROCESS
• Zeolites are hydrated sodium aluminosilicates
NaO.Al2O3.xSiO2.yH2O. They work as water
softener by replacing the calcium and magnesium
ions in water with the sodium ions in zeolite.
• (x=2-10; y=2-6)
• In this process hard water is allowed to pass
through a bed of zeolite at a specified rate. Then
the sodium ions present in the zeolite bed
continuously replace the calcium and magnesium
ions present in water and hence the water
becomes soft.
Na2Ze + Ca(HCO3)2 → CaZe + 2NaHCO3
Na2Ze + Mg(HCO3)2 → MgZe + 2NaHCO3
Na2Ze + CaCl2→ CaZe + 2NaCl
Na2Ze + MgCl2 (or MgSO4) → MgZe +
2NaCl (or Na2SO4)
Zeolite
Na2Ze + Mg(HCO3)2→ MgZe + 2NaHCO3
Na2Ze + Ca(HCO3)2 → CaZe + 2NaHCO3
When the zeolite bed becomes exhausted it requires regeneration. This is
achieved by passing 10% NaCl solution through it.
CaZe + 2Nacl → Na2Ze + CaCl2

Limitations: (1) turbid water can’t be treated

(ii) Water containing Mn2+, Fe2+ must be removed
(iii) acid waters can’t be treated

Advantages
Almost complete removal of hardness
It is compact
Requires only less time for softening

Disadvantages
More sodium salt concentration in softened water.
Causing caustic embrittlement
 ION EXCHANGE METHOD
• Ion exchange resins are insoluble cross linked long chain organic polymers having
a micro porous structure where acidic or basic functional groups attached to the
chain are responsible for the ion exchange capacity. Cation exchange resins
contain acidic functional groups like –COOH, -SO3H etc. while anion exchange
resins contain basic functional groups like –OH, -NH2 etc.
• The hard water is allowed to pass through a cation exchange column to remove
all the cations like Ca2+, Mg2+ etc.
• 2RH+ + Ca2+ → R2Ca2+ + 2H+
• 2RH+ + Mg2+ → R2 Mg2+ + 2H+
• Afterwards the water is allowed to pass through an anion exchange resin column
to remove anions like SO42-, Cl- etc.
• ROH- + Cl- → RCl- + OH-
• The H+ and OH- ions so produced from the cation and anion exchange resins
combine to become water
• H+ + OH- → H2O
• Water thus coming out of the ion exchanger will be free from both cations and
anions and hence called demineralised water.
 DEMINERALISATION PROCESS BY ION-EXCHANGE

Advantage
Produce water of very low hardness (2 ppm)

Disadvantage
The equipment and chemicals are very costly
 REVERSE OSMOSIS
Reverse osmosis is a technique used for the
purification of sea water in to drinking water.

This method is based on the principle that if a

hydrostatic pressure greater than the osmotic
pressure is applied on the more concentrated
solution side then the solvent molecules begin
to move through a semi-permeable membrane
in a direction opposite to that predicted by
natural osmosis.
• The solvent molecules begin to move from the
concentrated solution side to diluted solution
and hence the name reverse osmosis.
• In actual process the sea water which is to be
purified is taken in a chamber separated by a
cellulose-acetate membrane. A pressure of
about 15 to 40 Kg cm-2 is applied on the sea
water side in order to force the pure water
alone present in it through the semi
permeable membrane leaving behind all the
dissolved salts.
• .