1.Estimation of Hardness of water by complexometric method.

The estimation of hardness is based on complexometric titration. Hardness of water is determined by

titrating with a standard solution of ethylene diamine tetra acetic acid (EDTA) which is a complexing
agent. Ethylene Diamine Tetra Acetic acid (EDTA) is a reagent that forms EDTA-metal complexes with
many metal ions. In alkaline conditions (pH›9) it forms stable complexes with the alkaline earth metal
ions Ca2+ and Mg2+.EDTA is Ethylene Diamine Tetra Acetic acid. The structure of EDTA is as shown
below. Since, EDTA is insoluble in water, its disodium salt is used as a complexing agent.

Total hardness is due to the presence of bicarbonates, chlorides and sulphates of calcium and magnesium
ions. The total hardness of water is estimated by titrating the water sample against EDTA using
Eriochrome Black-T (EBT) indicator. Initially EBT forms a weak EBT- Ca2+ / Mg2+wine red coloured
complex with Ca2+ / Mg2+ions present in the hard water. On addition of EDTA solution, Ca2+ / Mg2+ions
preferably form a stable EDTA- Ca2+ / Mg2+ complex with EDTA leaving the free EBT indicator in
solution which is steel blue in colour in the presence of ammonia buffer. Thus the end point is the change
of colour from wine red to blue.

In EDTA methods, the known water sample is titrated against standard EDTA solution using EBT as
indicator in the presence of basic buffer solution (PH=9-10). At the end point the wine red colour changes
to blue.
Experimental procedure: - A known volume of Hardware sample is titrated with about 3 ml of buffer
solution and 4- 5 drops of EBT indicator. This solution is treated against a standard EDTA solution. The
end point is the colour change from wine –red to blue.
Let the titer value = v1 ml (End point)
1ml of EDTA (0.01m) = 1 mg of CaCO3
V1 ml of EDTA (0.01m) =v1 mg of CaCO3
So V1 mg of equivalent CaCO3 hardness is presented in v ml of hard water
The total hardness of sample = 𝑣1×1000 /𝑣 ppm
A known volume of water sample is taken in a beaker and boiled for half an hour, after cooling it is
filtered and the filtrate titrated against EDTA by adding EBT indicator & PH-(9-10) buffer solution.
Here the volume of EDTA consumed v2ml gives us the permanent hardness of water.
Permanent hardness of water = v2×1000/ 𝑣 ppm
The total hardness of water = (Temporary hardness + permanent hardness)
Temporary hardness = (Total hardness-permanent hardness)

2. Steps involved in the treatment of potable water and Break point Chlorination.
Specification of potable water/drinking water:
1.It should be sparkling clear and odourless.
2.It should be pleasant in taste.
3.It should be perfectly cool.
4.Its turbidity should not exceed 10ppm.
5.It should be free from objectionable dissolved gases like hydrogen sulphide.
6.It should be free from minerals such as lead, arsenic, chromium and manganese salts.
7.Its alkalinity should not be high.
8.Its pH should be about 8.0.
9.It should be free from disease-producing micro-organisms.
The treatment of water for drinking purpose mainly includes the following steps,

1. Screening:
The raw water is passed through screens having large number of holes in it, to remove floating
impurities.

2. Aeration:
The water is then passed through aerator which helps in exchange of gasses between water and
air, thereby increase of oxygen content in water takes place

3. Sedimentation with coagulation:

Sedimentation is a process of allowing water to stand in big tanks, and then the suspended and
colloidal impurities are allowed to settle under gravitation. the basic principle of this treatment
is to allow water to flow at a very slow velocity. So that the heavier particles settle down under
gravitation.
For setting of fine particles coagulants like alum [K2 SO4∙Al2 (SO4)3∙24H2 O], Sodium
aluminate ( NaAlO2) etc are added which produces floc.
1. Alum reacts in water in the presence of alkalinity of water.

Al2(SO4)3+ 3Ca(HCO3)2 2Al(OH)3↓ +3CaSO4 +6H2O+NaOH

Floc is gelatinous precipitate which attracts and helps accumulation of the colloidal
particles resulting in setting of the colloidal particles.
4. Filtration:
Filtration helps in removal of the colloidal and suspended impurities not removed by
sedimentation. Filtration is carried out by sand filters.In sand filter the filter bed consists of
three layers of sand of different particle size. A fine sand layer on the top supported by coarse
sand layer, which is supported by gravel. The colloidal impurities are retained by the fine
sand layer resulting the very slow filtration of water, the top layers of the fine sand layer is
scraped off, washed, dried and introduced into the filter bed for reuse.
5.Disinfestation of surface water / Removal of micro-organisms in water: Disinfestation:
The process of destroying/killing the disease producing Bacteria, microorganisms, etc. from
the water and making it safe for use, is called disinfection.
Disinfectants:The chemicals or substances which are added to water for killing the bacteria are
called disinfectants.The disinfection of water can be carried out by following methods:
a). Boiling:When water is boiled for 10-15 minutes, all the disease-producing bacteria are
killed and water becomes safe for use.
By using Bleaching power:Bleaching powder contains 80% chlorine. When bleaching powder
is mixed with water, the result of chemical reaction produces a powerful germicide called
hypochlorous acid. The presence of chlorine in the bleaching powder produces disinfecting
action, kills germs and purifies the drinking water effectively.
CaOCl2 + H2O → Ca(OH)2 + Cl2 H 2O + Cl2 → HCl + HOCl
By using Chlorine:
Chlorination is the process of purifying the drinking water by producing a powerful germicide
like hypochlorous acid. When this chlorine is mixed with water it produces hypochlorous acid
which kills the germs present in water.
H2O + Cl2 → HOCl + HCl
Chlorine is basic (means pH value is more than 7) disinfectant and is much effective over the
germs. Hence chlorine is widely used all over the world as a powerful disinfectant. Chlorinator
is an apparatus, which is used to purify the water by chlorination process.
By using chloramines:Chlorine is mixed with ammonia in 2:1 ratio by volume to produce a
stable compound chloramine which generates hypochlorous acid which is a a powerful
disinfectant.
Cl2+NH3 → ClNH2+HCl
ClNH2+H2O→HOCl+NH3
Ozonisation:Ozone is a powerful disinfectant and is readily dissolved in water. Ozone being
unstable decomposes by giving nascent oxygen which is capable of destroying the bacteria.
This nascent oxygen removes the colour and taste of water and oxidizes the organic matter
present in water.
O3 → O2 + [O]
The nascent oxygen is very powerful oxidizing agent and kills all the bacteria’s as well as
oxidizes the organic matter present in water. For carrying out the disinfection by ozone, ozone
is released/injected into the water and the two are allowed to come in contact in sterilizing tank.
The disinfected water is removed from the top. The contact period is about minutes and the
usual dose strength is 2-3 ppm.
Chlorine is a powerful disinfectant than chloramines and bleaching powder.
Calculated amount of chlorine must be added to water because chlorine after reacts with
bacteria and organic impurities or ammonia remains in water as residual chlorine which gives
bad taste, odour and toxic to human beings .so calculated amount of chlorine must be
added.
“The amount of chlorine required to kill bacteria and to remove organic matter is called break
point chlorination.”
The water sample is treated with chlorine and estimated for the residual chlorine in water and
plotted a graph which gives the break point chlorination.

Chlorine Oxidation Process

• 'a' grams of chlorine oxidize water impurities.
• 'b' grams form chloramines and other compounds.
• 'c' grams destroy these compounds.
• 'd' grams contain residual chlorine.
• 'c' grams marks the breakpoint for chlorine addition to water.

3. Softening of water by ion-exchange Process.

Softening of water by Ion exchange resin process or deionization process or demineralization
process:
✓ The process of complete removal of all ions present in water is known as
demineralization process.
✓ The process is done by using ion exchange resin process.
✓ These resins are highly insoluble cross linked organic polymers with porous structure.
✓ They contain functional groups attached to the polymeric chains are responsible for ion
exchange property.
✓ The functional groups used is either acidic or basic in nature.
✓ Depending on functional groups Ion exchange resins are classified into two types.
Cation Exchange Resins:
1. These are mainly poly-styrene polymers which contain acidic functional groups.
2. The acidic functional group is capable of exchanging its H+ ions with cations present
in water.
Anion Exchange Resins:
 1. These are mainly poly-styrene polymers which contain basic functional groups.
2. The basic functional group is capable of exchanging its OH- ions with anions present
in water.

Cation Exchange Resins

2RH+ + Ca+2 → R2Ca+2 + 2H+
2RH+ + Mg+2 → R2Mg+2 + 2H+ (RH+ = cation exchange resin)
Anion Exchange Resins
2ROH + Cl-2 → 2RCl + 2OH-
2ROH- + SO4- → R2SO4-2 + 2OH-
2ROH +CO3-2 → R2CO3-2 +2OH-
Regeneration:
When cation exchanger losses capacity of producing H+ ions and anion exchanger losses
capacity of producing OH- ions, they are said to be exhausted. The exhausted cation exchanger
is regenerated by passing it through dilute sulphuric acid.
R2Ca+2 + 2H+ → 2RH+ + Ca+2
The exhausted anion exchanger is regenerated by passing a dilute solution of NaOH.
R2SO4-2 + 2OH- → 2ROH + SO4-2
Merits of Ion-exchange process:
1. This process can be used to soften highly acidic or alkaline water.
2. It produces water of very low hardness (2ppm). So it is very good for treating water for use
in high-pressure boilers.
3. The operational expenses are less because the resins can be regenerated.
Demerits of Ion-exchange process:
1. The equipment is costly and more expensive chemicals are needed.
2. If water contains turbidity, the output of the process is reduced. The turbidity must be below
10 ppm; else it has to be removed by coagulation and filtration.

4.Contruction and applications of Pb-acid battery.

Secondary cell: E.g.: Lead – Acid cell:
If a number of cells are connected in series, the arrangement is called a battery. The lead storage
battery is one of the most common batteries that are used in the automobiles. A 12 V lead
storage battery is generally used, which consists of six cells, each providing 2V. Each cell
consists of a lead anode and a grid of lead packed with lead oxide as the cathode. These
electrodes are arranged alternately, separated by a thin wooden piece and suspended in dil.
H2SO4 (38%), which acts as an electrolyte. Hence, it is called lead acid battery.
Anode: Pb
Cathode: PbO2
Electrolyte: H2SO4 (20-22%)
EMF = 2 V

Lead storage cells: To increase the current output of each cell, the cathode and the anode plates
are joined together, keeping them in alternate positions. The cells are connected parallel to each
other.
The cell is represented as
Pb/PbSO4(s), H2SO4/PbSO4(s),Pb
In the process of discharging, i.e., when the battery produces current, the reactions at the
electrodes are as follows:
Discharging reactions:
At anode: Pb → Pb2+ + 2e-
Pb2+ + SO42- → PbSO4
At cathode: PbO2(s) + 4H+ + 2e- → Pb2+ +2H2O
Pb2+ + SO42- → PbSO4
Therefore, the overall reaction is:
Pb(s) +PbO2+4 H2SO4 (aq) → 2 PbSO4 (s) + 2H2O + Energy
During discharging the battery, H2SO4 is consumed, and as a result, the density of H2SO4 falls.
When it falls below 1.20 g/cm3, the battery needs recharging. In discharging, the cell acts as a
voltaic cell where oxidation of lead occurs.
Recharging: During recharging, the cell is operated like an electrolytic cell, i.e. electrical
energy is supplied to it from an external source. The electrode reactions are the reverse of those
that occur during discharge.
PbSO4 + 2e- → Pb + SO42- (Reaction at cathode)
PbSO4 + 2H2O → PbO2 + 2H2SO4 + 2e- (Reaction at anode)
-------------------------------------------------------------------------
2 PbSO4 + 2H2O + Energy → Pb + PbO2 + 2 H2SO4
During this process, lead is deposited at the cathode, PbO2 is formed at the anode and H2SO4
is regenerated in the cell.
Advantages:
Lead-acid batteries are used for supplying current to railways, mines, laboratories, hospitals,
automobiles, power stations, telephone exchange, gas engine ignition, UPS. Other advantages
are its recharge ability, portability, and relatively constant potential and low cost.
Disadvantages: Use of conc. H2SO4 is dangerous. Use of lead battery is fragile.
5. Construction and applications of hydrogen-oxygen fuel cell.
The basic principle of fuel cell is as same as that of an electrochemical cell. The fuel cell
operates like a galvanic cell. The only difference is that the fuel and the oxidant are stored
outside the cell. Fuel and oxidant are supplied continuously and separately to the electrodes at
which they undergo redox reaction. Fuel cells are capable of supplying current as long as
reactants are replenished.
Fuel + Oxidant → Oxidation products + Electric Energy
Examples: 1. H2-O2 fuel cell
2. CH3OH-O2 fuel cell
Hydrogen oxygen fuel cell:
This cell is a common type of fuel cell. Similar to a galvanic cell, fuel cell also has two half
cells. Both half cells have porous graphite electrode with a catalyst (platinum, silver or a metal
oxide). The electrodes are placed in the aqueous solution of NaOH or KOH which acts as an
electrolyte. Hydrogen and oxygen are supplied at anode and cathode respectively at about 50
atmospheric pressure, the gases diffuse at respective electrodes. The two half-cell reactions are
as follows

At anode: 2H2 (g) + 4OH- (aq) --------- 4H2O + 4e-

At cathode: O2 (g) + 2H2O (l) + 4e- -------- 4OH- (aq)

The net reaction: 2H2 (g) + O2 (g) ---------- 2H2O (l)

The EMF of this cell is measured to be 1.23V. A number of such fuel cell are stacked together
in series to make a battery.
Advantages:
1. The energy conversion is very high (75-82%).
2. Fuel cell minimizes expensive transmission lines and transmission losses.
3. It has high reliability in electricity generation.
4. The by-products are environmentally acceptable.
5. Maintenance cost is low for these fuels.
6. They save fossil fuels.
7. Noise and thermal pollution are very low.
8. They have low maintenance cost.
9. They have quick start system.
Disadvantages:
1. The major disadvantage of the fuel cell is the high cost and the problems of durability and
storage of large amount of hydrogen.
2. The accurate life time is also not known.
APPLICATIONS:
1. The most important application of a fuel cell is its use in space vehicles, submarine or
military vehicles.
2. The product H2O is valuable source of fresh water by the astronauts.
3. It is hoped that fuel cell technology will bring a revolution in the area of energy production.
4. Fuel cell batteries for automotive will be a great boom for the future.
Limitations:
1. The life time of fuel cells is not accurately known
2. It cannot store electricity
3. Electrodes are expensive ad short lived.
4. Storage and handling of H2 gas is dangerous because it is inflammable.
6. Mechanism of Electrochemical corrosion.
Wet Corrosion or Electrochemical Corrosion
✓ The direct chemical action of environment on the surface of metal in presence of
conducting liquid with the formation of electrochemical cells.
 ✓ It a common type of corrosion which occurs usually in aqueous corrosive environment
✓ Occurs when metal comes in contact with a conducting liquid.
✓ Formation of galvanic cell on the surface of metal generating anodic and cathodic areas
✓ At anode oxidation takes place liberating electrons.
✓ Electrons at anode are transported to cathodic area where H+ or O2 and H2O consumes
the electrons generating non-metallic ions like OH- or O2-
✓ Metallic (M+) and non metallic (OH- or O2-) diffuse towards each other and results in
the formation of corrosion product in between the anodic and cathodic area.

Mechanism: Electrochemical corrosion involves flow of electrons between anode and cathode.
The anodic reaction involves dissolution of metal liberating free electrons.

The cathodic reaction consumes electrons with either evolution of hydrogen or absorption of
oxygen which depends on the nature of corrosive environment.
Wet corrosion takes place in two ways.
1. Evolution of Hydrogen
2. Absorption of Oxygen
Evolution of Hydrogen:
This type of corrosion occurs in acidic medium.
Eg: Rusting of iron metal in acidic environment
takes place in the following way:
At Anode dissolution of iron to ferrous ion takes
place with the liberation of electrons
The electrons released at anode flow through the
metal from anode to cathode, whereas H+ ions of
acidic solution take up these electrons and
eliminated as hydrogen gas. This type of corrosion
causes “displacement of hydrogen ions from the
acidic solution by metal ions.

In hydrogen evolution type corrosion, the anodic areas are large and cathodic areas are small.
Absorption of Oxygen:
This type of corrosion takes place in basic or neutral medium in presence of oxygen.
For example, rusting of iron in neutral or basic aqueous solution of electrolyte in presence of
atmospheric oxygen.
Usually, the surface of iron is coated with a thin film of iron oxide.
If the film develops cracks, anodic areas are created on the surface and the rest of the metal
surface acts as cathodes.
It shows that anodic areas are small and the cathodic areas are large.
The released electrons flow from anode to cathode through iron metal.

If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide and then
to hydrated ferric oxide which is known as rust.
4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3

The product called rust corresponds to Fe2O3.3H2O.

7. Metallic coatings- Galvanisation and Tinning

Methods of application of metallic coatings:
Hot dipping:
Hot dipping process is applicable to the metals having higher melting point than the coating
metal.It is carried out by immersing a well cleaned base metal in a bath containing molten
coating metal and a flux layer.The flux cleans the surface of the base metal and prevents the
oxidation of the molten coating metal. Eg: Coating of Zn, Pb, Al on iron and steel surfaces.
The most widely used hot dipping processes are
✓ Galvanizing
✓ Tinning
Galvanizing:
Galvanizing is a process in which the iron article is protected from corrosion by coating it with
a thin layer of zinc.
It is the anodic protection offered by the zinc.In this process, at first iron or steel is cleaned by
pickling with dil.H2SO4 solution for 15- 20 minutes at 60-900 oC. In pickling any scale, dirt,
oil, grease or rust and any other impurities are removed from the metal surface.
The article is washed well and then dried.It is then dipped in bath of molten zinc maintained at
425-430oC.The surface of bath is kept covered with ammonium chloride – flux to prevent oxide
formation. The article is covered with a thin layer of zinc when it is taken out of bath.It is then
passed through a pair of hot rollers, which removes any excess of zinc and produces a thin film
of uniform thicknessThen it is annealed and finally cooled slowly.
Applications: Galvanizing is widely used for protecting iron exposed to the atmosphere (roofs,
wire fences, pipes etc.) Galvanized metallic sheets are not used for keeping eatables because
of the solubility of zinc.

Tinning
The process of coating tin over the iron or steel articles to protect them from undergoing
corrosion is known as tinning.
Tin is a noble metal and therefore it possesses more resistance to chemical attack. It is the
cathodic protection offered by the tin. In this process, iron sheet is treated in dilute sulphuric
acid (pickling) to remove any oxide film, if present.A cleaned iron sheet is passed through a
bath of ZnCl2 molten flux followed by molten tin and finally through a suitable vegetable oil.
The ZnCl2 flux helps the molten metal to adhere to the base metallic surface.Palm oil protects
the tin coated surface against oxidation.Finally, the sheet is passed through rollers to remove
excess of tin and produce thin coat of tin of uniform thickness

Applications:
✓ Tin metal possesses good resistance against atmospheric corrosion. Tin is non-toxic
and widely used for coating steel, copper and brass sheets
✓ The containers coated with tin are used for storing food stuffs, ghee, oil etc and packing
food materials.
✓ Tinned copper sheets are used for making cooking utensils and refrigeration equipment.
8.Mechanism and Properties of Lubrication.
Lubricants:
A lubricant may be defined as a substance which reduces the friction when introduced between
two surfaces and the phenomenon is known as lubricants.
Criteria of a good lubricant: -
Any substance which shows the process of lubricants must satisfy certain key functions. They
are
✓ The lubricant should keep moving parts apart.
✓ The foremost function of a lubricant is to reduce friction.
✓ It should prevent rust and corrosion and there by reduces the maintenance and running
cost of the machines.
✓ It carries away contaminates and debris which would otherwise damage the surfaces of
the machinery.
✓ It acts as a seal.
✓ It should also reduce the loss of energy in the form of heat.
✓ As the use of lubricant minimizes the lubricants of frictional heat, the expansion of the
metals can be reduced.
Mechanism: -
There are 3 types mechanisms by which lubrication takes place. They are
1. Fluid film lubricants (or) hydrodynamic lubrication
2. Boundary lubricants (or) Thin film lubrication.
3. Extreme pressure lubrication.
Fluid film lubrication:
In this type of lubrication, the moving or sliding surfaces are separated from one another by a
thick film of lubricant, so that there is no direct contact between them. The fluid film lubrication
based on the properties of the lubricant particularly on its viscosity. These are generally blended
with selected long chain polymers in order to maintain the viscosity of the oil as constant in all
seasons. The viscosity of hydrocarbon oils increases with increasing molecular weight. But this
fraction generally contains small quantity of unsaturated hydrocarbons which get oxidized
under operating conditions, forming gums. Hence it is essential that antioxidants to be blended
with hydrocarbon oils.

E.g. light machines like sewing machines, watches, clocks, and scientific instruments are
provided with fluid film lubrication.
2) Boundary lubrication (or) Thin film lubrication: -
A thin layer of lubricant is adsorbed on the metallic surfaces due to physical (or) chemical
forces. This adsorbed layer helps to avoid a direct metal contact between the rubbing surfaces.
The conditions of the lubricant which ought to be satisfied for boundary lubrication are:
✓ Long hydrocarbon chains.
✓ Polar groups to promote wetting (or) spreading over the surface.
✓ High viscosity index.
✓ Good oiliness.
✓ Low pour point and oxidation.
Active functional groups which can form chemical bonds with the metals or other surfaces.
3) Extreme pressure lubrication: -
Normally under heavy load and high-speed operating conditions, a special type of lubricants
called high-pressure lubricants are to be employed in order to withstand the high temperature
generated due to frictional heat. Chlorinated esters, sulphurised oils and tri crystal phosphate
are example of such additives. These additives react with metallic surfaces, at prevailing high
temperature, to form metallic chlorides, sulphide or phosphides, in the form of durable films.
These films can withstand very high loads and high temperatures (because of high metallic
points). Hence, they serve as good lubricant under extreme-pressure and extreme-temperature
conditions. Extreme pressure additives are used in wire drawing of titanium, in cutting fluids
in machining of tough metals, and for typhoid gears used in rear axle drive of cars.
Properties of lubricants: -
Viscosity: viscosity is the properly of a fluid that determines its resistance to flow. It is an
indicator of flow ability of a lubricating oil i.e. the lower the viscosity, greater the flow of
ability.
The unit of viscosity is “poise” or Newton/sec/m2.
Coefficient of viscosity may be defined as the force per unit area required to maintain a unit
velocity gradient between two parallel layers.
A good lubricating oil must have moderate viscosity. If the viscosity of the lubricating oil is
due to the excessive friction movement of the machine is restricted. On the other hand, if the
lubricating oil is having low viscosity, the liquid film cannot be maintained under heavy load
or pressure.
Flash and Fire-points: -
Flash point is the lowest temperature up to which the oil lubricant is heated to produce sufficient
vapours that ignite for a moment or produce a flash when a test flame is brought near it.
Fire point is the lowest temperature up to which the oil lubricant is heated to produce sufficient
vapours that burn continuously at least for 5 seconds when a test flame is brought near it.
Cloud and pour points: -
The temperature at which the lubricating oil becomes cloudy or hazy on cooling is known as
the cloud point.
The temperature at which the lubricating oil ceases to flow on cooling is known as the pour
point. Machines working at low temperatures, lubricants with low cloud and pour point are
preferred.
9.One component system.
Phase rule is crucial for quantifying equilibrium systems. We can forecast the conditions
needed for a system to be in equilibrium. Two or more phases in equilibrium comprise a
“heterogenous system”. Phase rule studies this system.
J. Willard Gibbs introduced the phase rule in 1876 using thermodynamics.
This rule qualitatively predicts temperature, pressure, and concentration effects on
heterogenous equilibrium.
A phase (P) is a homogeneous system separated from other phases by a boundary. This
system component is physically and mechanically separate. The phase must have these
criteria:
A component (C) It is an element or a compound present in a system. The concentration of
the component can undergo independent variation. It does not stand for the total number of
constituents of the system. The number of components of a system at equilibrium is defined
as the minimum number of molecular species in terms of which the composition of each
phase may be expressed quantitatively.
The degree of freedom or variance (F) is the fewest number of independent variables like
pressure, temperature, and concentration needed to fully characterise the system. System
degrees of freedom might be one, two, three, or zero. Thus, uni-variant, bi-variant, tri-variant,
and non-variant systems exist.

Willard Gibbs derived the phase rule from thermodynamics in 1876. This rule links the
number of degrees of freedom (F), components (C), and phases (P) in an equilibrium
heterogeneous system. This is the relationship:
F = C– P +2
Single-Component System: The Water System
Normally, ‘water’ is a three-phase, one-component system. This system balances water
vapours, water, and ice. Chemically, all three phases are H2O. Thus, it is one-component. If
three phases coexist, P = 3, C = 1, and the phase rule applies.
F=C–P+2=1–3+2=0
So the system has no degrees of freedom. The system is non-variant or invariant since none
of the variables—pressure, temperature, concentration—can be changed without one phase
vanishing. Thus, the three phases can only coexist at one temperature and pressure.
Univariant systems have one degree of freedom and two phases, such as ice and water or
water and vapour.
This indicates that changing one degree of freedom, like temperature, does not change the
number of phases:
F = C – P + 2 With C = 1 and P = 2, F = 1 – 2 + 2 = 1.
The areas-represented system has two degrees of freedom and is bivariant when pressure and
temperature are needed to characterise it:
The formula for F is: F = C – P + 2 C = 1 P = 1 F = 1 – 1 + 2 = 2
The vaporisation curve (OA) illustrates equilibrium between liquid water and vapour at
various temperatures: Liquid water vapour curves from ‘0’, the freezing point, to A, the
critical temperature, 374°C. Beyond point A, liquid water and vapour mix, hence it takes two
phases since they exist along the curve OA. Pressure and temperature are fixed for any given
temperature and vapour pressure, respectively. Any point on this curve has 1 degree of
freedom or is univariant, F = 1. Thus, F = C – P + 2 = 1 – 2 + 2 = 1
OB is the sublimation or vapour pressure curve of common ice. The two solid ice phases and
vapour are in equilibrium along this curve. This graph displays ice vapour pressure at
different temperatures. The curve begins at O and ends at B, or absolute zero (–273°C). No
vapour can exist at this stage, therefore only ice exists. The opposing side of OB balances ice
and vapour. Thus, two phases have 1 degree of freedom each.
F = C – P + 2 = 1 – 2 + 2 = 1Maintaining vapour pressure requires a constant temperature.
Ice melting point or fusion curve OC. It shows how pressure affects ice melting. Because the
OC curve slopes towards pressure Increased pressure lowers ice melting point. Ice and liquid
water are balanced on curve OC. The system is univariant and has one degree of freedom.
The melting point must be quantified.
Triple Point O—OA, OB, and OC converge at O. In this area, ice, water, and vapour
coexist. Since there are three phases and one component, P = 3. Thus, F = C – P + 2 = 0 (1 –
3 + 2)Ice at the triple point makes the system non-variant. This happens at 0.0075°C and 4.5
mm Hg. Changing temperature and pressure would eliminate phase and one of the
phases.Only vapour occurs in AOB and only water in AOC. Three regions in BOC are
bivariant, therefore temperature and pressure must be determined to identify any point.
F=C–P+2=1–1+2=2
Areas AOC, AOB, BOC Under a single phase–ice water or vapour, the regions between the
curves demonstrate steady temperature and pressure.Area AOC symbolises stable water (one-
phase) conditions. Area AOB depicts one-phase water vapour conditions. The region BOC
depicts ice, a one-phase system. In all three regions, with one phase and one component, we
have: F = C – P + 2 F = 1 – 1 + 2 = 2Thus, water, water vapour, and ice are bivariant systems
with two degrees of freedom.

10.Two component System

In a two-component system with a single phase, the number of degrees of freedom is F= 2 – 1
+ 2 = 3, meaning one component's temperature, pressure, and concentration must be defined.
In the space model or solid model, a two-component system phase diagram may employ one
concentration coordinate in addition to temperature and pressure variables.
Considering different equilibria individually simplifies a two-component system. These
equilibria are liquid–gas, solid–gas, liquid–liquid, and solid–liquid. All crystallisation
difficulties include solid–liquid systems, making them crucial.
Without a gas phase, these systems are unaffected by modest pressure changes. The gas phase
is absent in condensed systems. The solid–liquid equilibrium of condensed systems is
measured at atmospheric pressure. Phase rule: F= C– P+ 1.
The reduced phase rule is easier to apply to a solid–liquid two-component condensed system.
Temperature and ingredient concentration are variables. Temperature composition graphs
show solid–liquid equilibrium.
Easy eutectic regime
Eutectic means meltable. Eutectic systems are binary systems in which two components react
chemically and lower each other's freezing point. A eutectic system is a binary system with
two separate, fully immiscible components in solid and miscible in liquid without chemical
contact.
Eutectic mixture is the solid solution of a two-component system with the lowest freezing
point. Eutectic point is the lowest melting point of eutectic mixture.
The eutectic mixture melts at a certain temperature and composition. It is not a compound
since (1) its components are not stoichiometric and (2) when inspected under a microscope,
they appear as distinct crystals.
Consider a two-component system with A and B. These components are totally miscible in
liquid form and solidify to pure A or Bas when cooled. Figure 7.3 shows the freezing point
curve of A, Curve AC. The freezing point of A lowers along curve AC when B is added to A.
Solid A is in equilibrium with Bin A's liquid solution along this curve.
The freezing point curve of B is BC. Adding A to B lowers the curve's freezing point. This
curve shows solid Bis in equilibrium with Ain B's liquid solution.The shortened phase rule
equation yields F= 2 - 2 + 1 = 1.The degree of freedom is 1, hence both equilibria are
monovariant.

The curves AC and BC cross at the eutectic point C, where solid Ag, solid Pb, and solution
are in equilibrium. The system Ag/Pb/solution is non-variant at the eutectic point C, since
reduced phase rule yields F= C– P+ 1 = 2 – 3 + 1 = 0.Fixed variables are temperature (303°C)
and content (97.4% Pb, 2.6% Ag). Above eutectic temperature, solid phases Ag and Pb
vanish, while below it, only solid Ag/Pb persists without a solution phase. Above-AOC area:
This area is single-phase. Molten Ag-Pb solution exists. The condensed/reduced phase rule
yields F= 2 – 1 + 1 = 2.Therefore, Ag/Pb system is bivariant. Below AC is the Ag+ solution
and below BC the Pb+ solution. Below 303°C are solid Ag+ and Pb. All regions have two
phases and one degree of freedom.
F= C– P+ 1 = 2 – 2 + 1 = 1

11.Free radical addition polymerization with mechanism

It is defined as the process of linking or joining together smaller molecules i.e monomers to
make large molecule.
There are mainly two types of polymerization reactions.
I. Chain polymerization (or) Addition Polymerization.
II. Step polymerization (or) Condensation polymerization.
I. Chain polymerization (or) Addition polymerization:
A chain Polymerization is a reaction that yields a polymer product which is exact multiple of
monomers. Thus, the mechanism is also called addition polymerization.
Characteristics:
• The functionality of the monomer is two or bifunctional.
• The polymerization takes place by self-addition of the monomer molecules to each
other.
• An initiator is required to start the polymerization reaction.
• The conversion of “=” to” –“takes place during the polymerization liberating 20
Kcal/mole of energy. Hence it is exothermic reaction.
• The molecular weight of the polymer is the exact multiple of the monomers.
• This mechanism is carried out in three steps. i.e.
Initiation. ii)Propagation. iii)Termination.
Chain polymerization is of three types
1. Free radical chain polymerization.
2. Ionic chain polymerization.
3. Co-ordination chain polymerization.
1) Free radical chain polymerization: The homolytic fission of a bond gives free radicals
a.) Initiation: Initiators are unstable compounds and undergo homolytic fission to produce free
radicals which reacts with π electrons of the monomer to produce monomer free radicals.

I2 hv/ I* I*

I* + H2C CH I CH2 CH
X X
Monomer free radical
b.) Propagation: The monomer free radicals react with a number of monomers rapidly resulting
the chain growth with free radical site at the end of the chain producing a living polymer.

I CH2 CH + H2C CH I CH2 CH CH2 CH

X X X X
GROWINGCHAIN

I CH2 CH CH2 CH + nH2C CH I CH2 CH CH2 CH CH2 CH

X
n X
X X X X
Livingpolymer
By adding fresh monomer to the living polymer with free radical site again chain growth starts.
Hence it is known as living polymer
c) Termination: Termination takes place in two ways.
1).Self termination: In this step one growing polymer combine with other growing polymer
produce a dead polymer.

I CH2 CH CH2 CH CH2 CH + HC CH2 CH CH2 CH CH2 I

n X X n
X X X X

I CH2 CH CH2 CH CH2 CH HC CH2 CH CH2 CH CH2 I

n X X n
X X X X
Dead polymer

2) Termination by disproportionation: Hydrogen from the growing chain is abstracted by the

other growing chain, utilizing the lone electron for getting stabilized.

I CH2 CH CH2 CH CH2 CH + HC CH2 CH CH2 CH CH2 I

n X X n
X X X X

I CH2 CH CH2 CH C CH + H2C CH2 CH CH2 CH CH2 I

nH X n
X X X X X
12.preparation, Properties and applications of Bakelite and Nylon6,6
Bakelite or (Phenol- Formaldehyde Resin):
Bakelite is an important Thermoset resin. It is prepared by the step polymerisation of phenol
with formaldehyde in presence of an acid or alkali as a catalyst.The polymerization takes place
in three stages: Stage-i: Phenol is made to react with formaldehyde in presence of acid/alkali
to produce mono, di, tri methylol phenols depending on the phenol formaldehyde ratio (P/F
ratio)
 OH OH
CH2OH
P/Fratio
+ CHOH 1:1

phenol formaldehyde monomethylol phenol

OH OH
CH2OH
P/Fratio
+ CHOH 1:2

phenol formaldehyde dimethylol phenol

CH2OH
OH OH
HOH2C CH2OH
P/Fratio
+ CHOH 1:3

phenol formaldehyde Trimethylol phenol

CH2OH
Stage-ii:
The mono, di, and tri methylol phenols are heated to produce two types of straight chain resins
by condensation of the methyl group with hydrogen atom of benzene ring or another methyl
group.

OH
OH OH OH
CH2OH H CH2OH
CH2OH CH2
n
-nH2O
+ n
n

'A' Stage resin / Novolac

 OH OH OH OH
CH2OH HOH2C CH2 O CH2
n + n -nH2O
n
CH2OH CH2OH CH2OH CH2OH
'B'Stageresin/ Resol

Stage iii:
This stage of preparation includes heating of ‘A’ stage resin and ‘B’ stage resin together which
develops cross linking and produce Bakelite plastic resin.

OH OH OH OH
CH2 CH2OH CH2 O CH2
+
n n
CH2OH CH2OH
'A'Stageresin/ Novolac
'B'Stageresin/ Resol

OH OH

H2C CH2 CH2

CH2 CH2

H2C CH2 CH2

OH OH n

Bakelite

Properties: -
• Bakelite is hard, rigid and strong, it is a scratch resistant and water-resistant polymer.
 • It is resistant to chemicals but it is attacked by alkalis due to presence of OH group.
• Bakelite is an excellent electrical insulator and has very good corrosion resistance.
• It is a good anion exchange resin, exchanges –OH group with any other anion.
Applications:
• It is used for making electrical insulator parts like switches, heater handles.
• It is used for molded articles like telephone parts, cabinets for radio and television.
• It is used for making bearings used in propeller shafts, paper industry and rolling mills.
• It is used in paints and varnishes
Nylon 6:6
Nylon 6:6 is produced by the co-polymerization of hexamethylene diamine with adipic acid.
O O
nH2N CH2 6NH2 +nHOOC CH24 COOH -nH2O HN CH2 6NH C CH24 C
hexamithylene Adipicacid n
diamine Nylon6:6

Properties:
• Nylon possesses high strength, hardness and high melting point. The high melting point
of the nylon is due to the hydrogen bonding between the hydrogen atom of the amide
group and oxygen of c = o groups.
• Nylon possesses good chemical resistance and electrical resistance.
• Nylon possesses good resistance to environmental conditions.
• They are good insulators.
Applications:
• The major application is in the textile industry.
• Because of its high thermal and abrasion resistance nylons are used in mechanical
engineering applications like gears, bearings etc.
• Flexible tubing’s for conveying petrol etc. are made from nylons.
• Nylons are used as electrical insulators.
• Nylon 6 is used for making tire cords.
• Nylons are used in automobile industry and telecommunication industry for making
radiator parts and coil formers respectively.
13.Mechanism of doping in polyacetylene
Conducting polymers
The polymers which conduct electricity is called conducting polymers. The conduction of the
polymers may be due to unsaturation or due to the presence of externally added ingredients in
them.
The conducting polymers can be classified in the following way.
 Conducting polymers

Intrinsic conducting polymers Extrinsic conducting polymers

Intrinsic polymer Doped conducting Conductivity Blended

conducting with conjugation Polymer Element
polymer

Doped conducting polymers: -

The conductance of a polymer can be increased by introducing a positive charge or negative
charge on polymer backbone by oxidation reduction. This process is similar to semiconductor
technology and is called doping.
Doping is two types: -
1. Creating a positive site on polymer backbone called p-doping.
2. Creating a negative site on the polymer backbone called n-doping.
Doping and conductivity of polyacetylene
P-doping: -
P-doping is done by oxidation of a conducting polymer like polyacetylene with a Lewis acid
or iodine vapors.
This is also called oxidative doping.
+ -
HC CHn + 2FeCl3 HC CHn FeCl4 + FeCl2
1.
+ -
2.
HC CHn + 3I2 HC CHn I3
In the above reaction the Iodine molecules attract an electron from polyacetylene chain and
-
I
become 3 now the polyacetylene becomes positively charged and termed as radical cat ion or
polaron.
-e
+ I2 CCl
4
Polyacetylene Polaron
The polarons on doping forms solitons i.e. . Further oxidations of polaron give solitons.
-e
+ I2 CCl
4
Polaron Bi Polaron
 Bi Polaron solition

N-doping:
N-doping is carried out by reduction process by the addition of an electron to polymer backbone
by using reducing agents like sodium naphtalide Na+(C10H8). Formation of polaron, bipolaron
takes place in two steps, followed by recombination of radical which yields two charge carriers
on the polyacetylene chain responsible for conduction as shown below

Na(C10H8)
Polyacetylene e Polaron

The electron added to polyacetylene by reductive doping doesn’t go into the conductivity band
but goes into an intermediate electronic state within the band gap of radical anion (polaron).

Na(C10H8)
Polaron e Bi Polaron
Na(C10H8)
BiPolaron e solition
The bi anion lowers the energy by segregating into two negative solitons at the midgap energy
levels. This leads to the generation of conduction pathways. As a consequence, the conductivity
increases significantly.
14.Analysis of coal-Proximate and ultimate analysis and their significance
Analysis of Coal:
The analysis of coal is helpful in its ranking. The assessment of the quality of coal is carried
out by these two types of analysis
i) Proximate analysis
ii) Ultimate analysis
(I) PROXIMATE ANALYSIS: In this analysis, the %c is indirectly determined.
This analysis includes %moisture, volatile substance, ash content and carbon.
i. Moisture:
A known mass of finely powered coal is taken in a crucible. It is heated up to 1100C for
an hour and cooled to room temp. in a desiccator. The moisture is removed as water vapors and
the process is repeated till the consent wt. is obtained.
𝑙𝑜𝑠𝑠 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙
% Of moisture= × 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙
ii. Volatile matter:
The above sample is taken and heated at 9500 C in the absence of air for 7min. It is
then cooled to room temp. and weighted. The loss of wt. is noted as volatile matter and is
removed from coal.
𝑙𝑜𝑠𝑠 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 𝑑𝑢𝑒 𝑡𝑜 𝑟𝑒𝑚𝑜𝑣𝑎𝑙 𝑜𝑓 𝑣𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑚𝑎𝑡𝑡𝑒𝑟
% Of volatile matter = × 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙

iii. Ash Content:

Coal free from moisture and volatile matter is heated in a crucible at about 7000C in presence
of air.It undergoes combustion and results formation of ash. Crucible is cooled room temp. and
weighted .The mass of ash is then determined.
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑠ℎ
% of ash =𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐𝑜𝑎𝑙 × 100

iv. Carbon:
Since main component of coal is carbon, it can be determined by subtracting the sum of the %
of moisture, volatile substance and ash content from 100.
% C = 100 – (% of moisture + % of volatile matter + % of ash)
Significance Of Analysis:
Moisture:
high moisture content in the fuel reduces the calorific value, increases the cost of transportation
and causes wastage of heat. Hence lesser the moisture content the better is the quality of fuel.
Volatile Matter:
A coal containing high volatile matter burns with long flame, high smoke and low calorific
value .Volatile matter also influence the design of the furnace since the higher the volatile
matter, larger is the combustion space required.
Ash:
Ash reduces heating value of coal. Ash content increases cost of transportation, handling,
storage and disposal. it determines the quality of coal. Hence lesser % of ash, the better is the
quality of coal.
Fixed Carbon:
Higher the fixed carbon in a coal, greater is its calorific value.
II.ULTIMATE ANALYSIS:
This analysis includes % of C, H, O, S, N and ash content in coal.
1. C and H determination:
A known mass of carbon is taken and burnt in an apparatus. The C change in to CO2 and H
changes in to HO2.The vapors of CO2 and H2O are then passed through KOH and CaCl2.the
CO2 is absorbed by KOH and H2O is absorbed by CaCl2 There by weight of KOH and CaCl2
increases which is then measured.
C +O2 CO2
H2 + 1/2 O2 H2 O
2KOH+CO2 K2CO3+H2O
CaCl2 + 7H2O CaCl2 7H2O

𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑤𝑡 𝑜𝑓 𝐾𝑂𝐻 12
% of C = × 44 × 100
𝑤𝑡 𝑜𝑓 𝐶𝑜𝑎𝑙

𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑤𝑡 𝑜𝑓 𝑐𝑎𝑐𝑙2 2
% of H = × 18 × 100
𝑤𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙

Significance:
Higher the % of C and H, the better is the quality of coal and higher is the calorific
value. % C helps in assessing the ranking of the coal.
2. Nitrogen:
The estimation of N is done by kjeldahls method. About 1g of finely powdered coal sample is
heated with conc. H2SO4 along with K2SO4 catalyst in a kjeldahls flask. N in the coal is
converted in to (NH4)2SO4.
2N+3H2+H2SO4 (NH4)2SO4
(NH4)2SO4 is heated with excess of NaOH and the liberated NH3 is distilled over and absorbed
by a known vol. of std. acid sol. The untreated acid is back titrated with std. NaOH. The amount
of acid neutralized by liberated ammonia is determined.
(NH4)2SO4 + 2NaOH 2NH3+Na2SO4+2H2O
NH3+ HCl NH4Cl
From this the % of N is calculated.
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐻2𝑆𝑂4×𝑛𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦
% of N = × 1.4
𝑤𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙

Significance:
N does not have any calorific value. It has no significance.
3. Sulphur:
It is estimated gravimetrically in terms of BaSO4.sulphur is converted into soluble sulphate
by incinerating coal with 1:2 mixture of Na2CO3 and MgCO3. Then treated with BaCl2 sol. So
that sulphates are precipitated as BaSO4 .From the wt. of BaSO4 obtained, the S present coal
in is calculated.
𝑤𝑡 𝑜𝑓 𝐵𝑎𝑆𝑂4 32
% of S = × 233 × 100
𝑤𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙

Significance:
 • S increases calorific value
• The product of combustion SO2 , SO3 have corrosive effect on equipment and cause air
pollution.
• S is undesirable in the preparation metallurgical coke.
4. Oxygen:
The % of O2 is determined by subtracting the sum of % of C, H , S and N from 100.
% Of O2 = 100 – (% of C+%H+%N+%S)
Significance:
High O2 coal contains high inherent moisture and low calorific value. A quality coal should
contain low % of O2.
15.Petroleum and its Refining
Refining of crude petroleum:
The crude oil is a mixture of several chemicals. They are separated by three steps. This process
of separating various fractions of crude oil is called refining and industry is called oil refineries.
1) Separation of water (Cottrell’s process):
The crude oil is an emulsion of oil and water. Water is separated by allowing the crude
oil to flow through two highly charged electrodes. The colloidal water is separated from
oil in the form of big droplets.

2) Removal of Sulphur compounds:

The crude oil is treated with copper oxide which gives black CuS precipitation can be removed
by filtration.
3) Fractional distillation:
Crude oil obtained after 1 and 2 steps then heated at about 400°C in an iron retort. All
volatile constituents are evaporated leaving behind some residence (asphalt or
petroleum coke). The hot vapors are passed through different fractionating columns.
The apparatus is a long cylindrical vessel with several trays, each having chimney
covered with a loose cap.
16.Synthetic petrol- Fisher-Tropsch process
Petrol is mainly obtained from crude oil from oil wells but can also be obtained from synthetic
process. There are two types of synthetic processes. They are,
1. Fisher-Tropsch process
2. Bergius process
1. Fisher-Tropsch process:
This process was developed in Germany by F. Fisher and H. Tropsch in 1923. In this process
coal is converted to coke. Coke is then treated with steam to obtain water gas.
nCO + (2n+1) H2 CnH2n+2 + nH2O
nCO + 2nH2 C 2H2n + nH2O
Water gas produced by passing steam over heated coke is treated with hydrogen in the presence
of group VIII metals (Fe, Co, Ni) which give gasoline and fuel oil.

In order to remove H2S and organic S compounds, the gas is passed through Fe2O3 and then
into a mixture of Fe2O3+Na2CO3. Pure gas is then compressed at 5-25 atm and led to a convertor
(packed with mixture of 100 parts of Co, 5 parts of Ni, 8 parts of MgO and 200 parts of
Keiselguhr earth. The hot gaseous mixture is then cooled and fractionated and the heavy oil
fraction is cracked to get gasoline.These reactions take place at 30 atm pressure at 200-300° C
temperature. The gasoline formed by this process has low anti-knock value.