UNIT I Water Technology

R23 Syllabus: Soft and hard water, Estimation of hardness of water by EDTA Method, Estimation of dissolved Oxygen -
Boiler troubles –Priming, foaming, scale and sludge, Caustic embrittlement, Industrial water treatment – Specifications for
drinking water, Bureau of Indian Standards (BIS) and World health organization (WHO) standards, Ion-exchange processes
- desalination of brackish water, reverse osmosis (RO) and electro dialysis.

Soft Water: The water which gives more lather with soap is called soft water.

C17H35COONa + H2O → C17H35COOH + NaOH

Soap (Soluble)

Hard Water: The water which do not give lather with soap is called soft water.
Hardness of Water: It is the property of hard water which prevent the lathering of soap. This is due to presence of certain
salts like Ca+2, Mg+2 and other heavy metals dissolved in water. When a sample of hard water treated with soap gives a white
curdy precipitate, due to the formation of insoluble soaps of calcium and magnesium.

2C17H35COONa + CaCl2 (C17H35COO)2 Ca + 2NaCl

(Soap) (Insoluble Soap)

Hardness of water is mainly two types:

1. Temporary Hardness 2. Permanent Hardness

1. Temporary Hardness: Temporary Hardness mainly caused by the presence of dissolved bicarbonates of
Calcium, Magnesium (Ca (HCO3)2, Mg (HCO3)2). Temporary Hardness can be largely removed by boiling of
water.

2. Permanent Hardness: It is due to the presence of dissolved Chlorides, Nitrates and Sulphates of Calcium,
Magnesium, Iron and other metals. Permanent hardness responsible salts are CaCl 2, MgCl2, CaSO4, MgSO4,
FeSO4, Al2(SO4)3. Permanent Hardness cannot be removed by boiling but it can be removed by the use of chemical
agents.
Expression of Hardness:

The expression of hardness producing salts usually expressed in terms of an equivalent amount of CaCO3.
Calcium Carbonate is chosen as a standard because:
i. Its molecular weight (100) and equivalent weight (50) is a whole number, so the calculations in water
analysis can be simplified.
ii. It is the most insoluble salt that can be precipitated in water treatment.

The conversion of the hardness causing salts into CaCO3 equivalents can be achieved by using the following
formula:
Units of Hardness:

1. Parts per Million (ppm): The number of parts of calcium carbonate equivalent hardness presents in 106 parts
of water.
1ppm = 1 part of CaCO3 eq hardness in 106 parts of water.
2. Milligrams per litre (mg/l): The number of milligrams of calcium carbonate equivalent hardness
presents in litre of water.
1 mg/L = 1 mg of CaCO3 eq hardness in one litre of water.
But one litre of water weights =1 kg =1000g = 1000 x 1000 mg = 106 mg = 1 ppm.

3. Clark’s degree (°Cl): The number of parts of calcium carbonate equivalent hardness presents in 70,000 or
(7×104) parts of water.
1° Clarke = 1 part of CaCO3 eq hardness per 70,000 parts of water.

4. Degree French (°Fr): The number of parts of calcium carbonate equivalent hardness presents in 105 parts of
water.
1° Fr = 1 part of CaCO3 hardness eq per 105 parts of water.

Relationship between various units of hardness:

1 ppm = 1 mg/L = 0.1° Fr = 0.07° Cl
1 mg/L = 1 ppm = 0.1° Fr = 0.07° Cl
1 ° Cl = 1.433° Fr = 14.3 ppm = 14.3 mg/L
1 ° Fr = 10 ppm = 10 mg/L = 0.7° Cl

Problem-1: A sample of water is found to contains following dissolving salts in milligrams per litre
Mg(HCO3)2 = 73, CaCl2 = 111, Ca(HCO3)2 = 81, MgSO4 = 40 and MgCl2 = 95. Calculate temporary and
permanent hardness and total hardness.
Solution:
Name of the hardness Amount of the hardness Molecular weight of Amounts equivalent to
causing salts causing salts(mg/Lit) hardness causing salts CaCO3 (mg/Lit)
Mg(HCO3)2 73 146 73×100/146 = 50
CaCl2 111 111 111×100/111 = 100
Ca(HCO3)2 81 162 81×100/162 = 50
MgSO4 40 120 40×100/120 = 33.3
MgCl2 95 95 95×100/95 = 100
Temporary hardness = Mg(HCO3)2 + Ca(HCO3)2
= 50 + 50 = 100mgs/Lit.
Permanent hardness = CaCl2 + MgSO4 + MgCl2
= 100 + 33.3 + 100 = 233.3mgs/Lit.
Total hardness = Temporary hardness + Permanent hardness
= 100 + 233.3 = 333.3mgs/Lit.
Problem-2: A sample of water is found to contains following dissolving salts in milligrams per litre
Mg(HCO3)2 = 16.8, MgCl2 = 12.0, MgSO4 = 29.6 and NaCl = 5.0. Calculate temporary and permanent
hardness of water.
Solution:
Name of the hardness Amount of the hardness Molecular weight of Amounts equivalent to
causing salts causing salts(mg/Lit) hardness causing salts CaCO3 (mg/Lit)
Mg(HCO3)2 16.8 146 16.8×100/146 = 11.50
MgCl2 12.0 95 12.0×100/95 = 12.63
MgSO4 29.6 120 29.6×100/120 = 24.66
NaCl 5.0 NaCl does not contribute any hardness to water
hence it is ignored.

Temporary hardness = Mg(HCO3)2 = 11.50 mg/Lit.

Permanent hardness = MgCl2 + MgSO4 = 12.63 + 24.66 = 37.29 mg/Lit.

Problem-3: A sample of water is found to contains following analytical data in milligrams per litre
Mg(HCO3)2 = 14.6, MgCl2 = 9.5, MgSO4 = 6.0 and Ca(HCO3)2 = 16.2. Calculate temporary and
permanent hardness of water in parts per million, Degree Clarke’s and Degree French.
Solution:
Name of the hardness Amount of the hardness Molecular weight of Amounts equivalent to
causing salts causing salts(mg/Lit) hardness causing salts CaCO3 (mg/Lit)
Mg(HCO3)2 14.6 146 14.6×100/146 = 10
MgCl2 9.5 95 9.5×100/95 = 10
MgSO4 6.0 120 6.0×100/120 = 5
Ca(HCO3)2 16.2 162 16.2×100/162 =10

Temporary hardness [Mg (HCO3)2 + Ca (HCO3)2] = 10 + 10 = 20mg/Lit

= 20ppm
= 20×0.07°Cl = 1.4°Cl
= 20×0.1°Fr = 2°Fr
Permanent hardness [MgCl2 + MgSO4] = 10 + 5 = 15mg/Lit
= 15ppm
= 15×0.07°Cl = 1.05°Cl
= 15×0.1°Fr = 1.5°Fr
Problem-4: Calculate the amount of temporary and permanent hardness of a water sample in Degree
Clarke’s, Degree French and Milligrams per Litre which contains following impurities.
Ca(HCO3)2 = 121.5 ppm, Mg(HCO3)2= 116.8 ppm, MgCl2 = 79.6 ppm and CaSO4 = 102 ppm.
Solution:
Name of the hardness Amount of the hardness Molecular weight of Amounts equivalent to
causing salts causing salts (ppm) hardness causing salts CaCO3 (ppm)
Ca(HCO3)2 121.5 162 121.5×100/162 = 75
Mg(HCO3)2 116.8 146 116.8×100/146 = 80
MgCl2 79.6 95 79.6×100/95 = 3.37
CaSO4 102 136 102×100/136 = 75
Temporary hardness [Mg (HCO3)2 + Ca (HCO3)2] = 75 + 80 = 155 ppm
= 155×0.07°Cl = 10.85°Cl
= 155×0.1°Fr = 15.5°Fr
=155×1mg/Lit = 155 mg/Lit
Permanent hardness [MgCl2 +CaSO4] = 10 + 5 = 15mg/Lit
= 15ppm
= 15×0.07°Cl = 1.05°Cl
= 15×0.1°Fr = 1.5°Fr

Estimation of hardness of water by EDTA Method or Complexometric Method:

Principle: The determination of hardness is carried out by titrating water sample with Sodium salt of
Ethylene Diamine Tetra Acetic Acid (EDTA) using Eriochrome Black-T as an indicator and keeping the
pH of the water at 9.0 - 10.0. The end point is the change in colour from wine - red to blue, when the
EDTA solution complexes the calcium and magnesium salt completely.

Sodium Salt of Ethylene Diamine Tetra Acetic Acid (EDTA)

Chemicals Required:
i. Preparation of standard hard water (0.01M): Dissolve 1g of pure, dry CaCO3
in minimum quantity of [Link] and then evaporate the solution to dryness on a
water bath. Dissolve the residue in distilled water to make 1 Litre solution. Each
ml of this solution thus contains 1mg of CaCO3 equalent hardness.

ii. Preparation of EDTA solution: Dissolve 4 g of pure EDTA crystals + [Link] MgCl2
in 1 Litre of distilled water.

iii. Preparation of Indicator (EBT): Dissolve 0.5 g of Eriochrome Black−T in 100mL

alcohol.

iv. Preparation of Buffer solution: Add 67.5g of NH4Cl to 570 ml of Con. Ammonia
solution and then dilute with distilled water to 1 Litre.
Various steps involved in this method:
1. Standardization of EDTA solution: Rinse and fill the burette with EDTA solution.
Pipette out 20 ml of standard hard water (M1) in a conical flask. Add 4ml of buffer
solution and 2 drops of EBT indicator. Titrate with EDTA solution till wine-red colour
changes to clear blue. Let volume used by
‘X’ ml.
M1 V1 = M2 V2

Where, M1 = Molarity of Standard hard water (0.01M),

V1 = Volume of Standard Hard water (20 ml),
M2 = Molarity of EDTA, V2 =
Volume of EDTA (Xml).

2. Determination of Total Hardness: Rinse and fill the burette with EDTA solution.
Pipette out 20 ml of sample water (V3) in a conical flask. Add 4 ml of buffer solution
and 2 drops indicator. Titrate with EDTA solution till wine-red colour changes to clear
blue. Let volume used by ‘Y’ ml.
M2 V2 = M3 V3

Where, M2 = Molarity of EDTA,

V2 = Volume
of EDTA
(Yml). M3 =
Molarity of
sample water,
V3 = Volume of Sample water (20 ml).
Total Hardness = M3 × Molecular weight of CaCO3 (100) × One Litre (1000ml)
= M3 × 105 ppm

3. Determination of Permanent Hardness: Take 100 ml of sample water in 250 ml

beaker. Boil it to remove temporary hardness to about half of its volume and cool to
room temperature, filter through filter paper to remove insoluble salts. Make up the
volume to the original 100ml by adding distilled water. Now Pipette out 20 ml of this
solution (V4) in a conical flask. Add 4 ml of buffer solution and 2 drops indicator.
Titrate with EDTA solution till wine-red colour changes to clear blue. Let volume used
by ‘Z’ ml.
M2 V2 = M4 V4

Where, M2 = Molarity of EDTA,

V2= Volume of EDTA (Z ml).

M4 = Molarity of Permanent hard water,

V4 = Volume of Permanent hard water (20 ml)
Permanent Hardness = M4 × Molecular weight of CaCO3 (100) × One Litre (1000ml)
 = M4 × 105 ppm

4. Determination of Temporary Hardness:

Temporary Hardness = Total Hardness - Permanent Hardness

Problem-1: 50 ml of standard hard water containing 1 gram of pure CaCO3 per liter consumed 20 ml
of EDTA. 50 ml of hard water consumed 25 ml of same EDTA solution EBT indicator. Calculate the
total hardness of water sample in ppm.
Boiler or Steam boiler:

A boiler is a closed vessel in which water under pressure is transformed into steam by the application
of heat. The steam is used in industries to generation of power. A boiler feed water should correspond
with the following composition:

• Its hardness should be below 0.2 ppm.

• Its caustic alkalinity (due to 𝑂𝐻 − ) should lie between 0.15 ppm to 0.45 ppm.

• It should be free from dissolved gases like O2, CO2, in order to prevent boiler corrosion.

Boiler Troubles:

1. Priming and Foaming

2. Scale and Sludge formation

3. Caustic Embrittlement

1. Priming and Foaming

Priming: Priming is defined as the formation of water droplets in a steam.

Causes:

• High water level in the boiler.

• Sudden increase in steam demand.

• Presence of dissolved salts in boiler water.

• Impurities like oil or organic matter.

• Improper design of boiler or steam outlet.

Prevention:
 • Maintain correct boiler water level.

• Use proper steam separators or steam traps.

• Regular blowdown to control dissolved salts.

• Avoid sudden steam demand changes.

• Treat boiler feed water properly.

Foaming: Foaming is the formation of stable bubbles or froth on the surface of boiler water,
preventing efficient steam-water separation.

Causes:

• Presence of oil and grease in feed water.

• High concentration of dissolved or suspended solids.

• Alkalinity of boiler water.

Prevention:

• Proper chemical treatment of boiler water (anti-foaming agents).

• Prevent oil and grease from entering boiler feed water.

• Frequent boiler blowdown to remove excess salts.

• Maintain proper alkalinity levels.

2. Sludge and Scale formation

Sludge: Sludge is the soft, loose and slimy precipitate that forms in boilers. It generally settles down
at the bottom of the boiler.

Causes of Sludge Formation

• Presence of salts like magnesium chloride, magnesium carbonate, calcium

chloride, etc., which are more soluble in hot water.

• Poor quality of feed water.

• Inadequate water treatment before feeding into the boiler.

Effects of Sludge

• Wastage of fuel due to poor heat transfer.

• Overheating of boiler material, leading to reduced efficiency.

• Blockage of pipes and valves.

• Corrosion of boiler parts.

• Difficulty in cleaning and maintenance.

 Prevention/Control of Sludge

• Proper water softening before feeding into boiler.

• Blowdown operation (removal of concentrated boiler water at intervals).

• Use of chemical treatment to prevent precipitation of salts.

• Regular cleaning and maintenance of boiler.

Scale: Scale is a hard, adherent deposit formed on the inner surfaces of boiler tubes.

Causes of Scale Formation

• Calcium salts:

o Calcium sulfate (CaSO₄) – solubility decreases with rising temperature.

o Calcium carbonate (CaCO₃) – formed by decomposition of bicarbonates.

• Magnesium hydroxide (Mg(OH)₂) – formed when Mg salts decompose at high

temperature.

• Silica (SiO₂) – combines with calcium or magnesium to form hard scales.

• Poor water treatment and presence of dissolved solids in feed water.

Effects of Scale

• Poor heat transfer → wastage of fuel.

• Overheating and potential damage (even bursting) of boiler tubes.

• Reduced efficiency and carrying capacity of boiler.

• Frequent breakdowns and higher maintenance costs.

• May cause localized stress and cracks in metal.

Prevention methods of scaling:

Scaling can be minimized by proper treatment of boiler feed water. Since scaling is
mainly due to the presence of calcium and magnesium salts, water treatment is the best
preventive method. The two main methods of water treatment are

1. Internal Treatment (Sequestration) (inside the boiler)

o Aim: Add chemicals directly into the boiler so that scale-forming salts
are converted into soft, non-adherent sludge instead of hard scale.

o Examples:

▪ Calgon conditioning (sodium hexametaphosphate prevents

Ca²⁺/Mg²⁺ precipitation by sequestration).
 ▪ Phosphate conditioning (Na₃PO₄ reacts with Ca²⁺/Mg²⁺ to form
soft sludge).

▪ Colloidal Conditioning: When the organic substances like

kerosene, tannin, agar-agar, starch are added to boiler water,
they act as protective colloids. i.e., They form a protective colloid
coat around the scale-forming particles (like CaSO₄, Mg(OH)₂,
etc.). This prevents the salt from sticking to the boiler wall,
keeping it suspended as soft sludge that can be removed by
blowdown.

2. External Treatment (before water enters the boiler)

o Aim: Remove hardness and dissolved salts outside the boiler.

o Methods:

▪ Lime-soda process

▪ Zeolite process

▪ Ion-Exchange method

o Prevents scale-forming salts from entering the boiler at all.

Ion-Exchange Method: Ion exchange process is also known as demineralization 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-exchanging
properties.

• Resins with acidic functional group are capable of exchanging 𝐻 + ions with other
cations.
 • Resins with basic functional groups are capable of exchanging 𝑂𝐻 − ions with other
anions.

2RH + Ca(HCO3)2 → R2Ca + H2CO3

2RH + Mg(HCO3)2 → R2Mg + H2CO3
2RH + CaCl2 → R2Ca + 2HCl
2RH + MgCl2 → R2Mg+ 2HCl
2RH + MgSO4 → R2Mg + H2SO4
2RH + CaSO4 → R2Ca + H2SO4 (RH = Cation exchange resin)
Advantages:

(i) Process used to soften highly acidic or alkaline water (ii) It produces water of very low hardness

Disadvantages:

(i) The equipment is costly

(ii) If water contains turbidity out-out of the process is reduced

Potable Water or Drinking Water

Water free from contaminants or water that is safe for human consumption is called potable water. The
following are the specifications of water drinking purpose.

1. The water should be clear (colourless), odourless and pleasant taste.

2. The optimum hardness of water must be 125 ppm.

3. The pH of potable water should be 7.0 to 8.5.

4. The recommended maximum concentration of total dissolved solids (TDS) in potable water must
not exceed 500 ppm.

5. The turbidity in drinking water should not exceed 25 ppm.

6. The water must be free from heavy metals like Lead, Arsenic, Chromium and Manganese.

7. The water must be free from pathogenic bacteria

8. The water must be free from dissolved gases like H2S, CO2 and NH3.
 Treatment of Potable water for drinking purpose

Treatment of water for drinking purposes mainly includes the removal of suspended impurities,
colloidal impurities and harmful pathogenic bacteria. The following stages are involved in purification.

1. Screening: The water is passed through screens having larger number of holes; it retains floating

impurities like wood pieces, leaves, heaver objectives etc.

2. Aeration: The water is then subjected to aeration (reacting with air) which helps in exchange of
gases between water and air, increases the oxygen content and removes the impurities like iron,
manganese and dissolved gases like H2S, CO2 and NH3.

3. Coagulation: Coagulants like alum, sodium aluminates and Aluminum sulphate are added which
produce gelatinous precipitates called flock. Flock attracts and helps accumulation of the colloidal
particles resulting in setting of the colloidal particles.

4. Filtration: Filtration may be defined as the process of passing a liquid containing suspended matter
through a suitable porous material in such manner as to effectively remove the suspended matter from
the liquid. Filters are of two types:

a) Gravity filters which again classified as slow sand filters & rapid sand filters

b) Pressure filters

SLOW SAND FILTERS:

• The filters are like large shallow tanks made of

concrete.

• At the bottom there is an under –drain system through

which the filtered water goes to the storage tank.

• Gravel is placed is the tank above the under –drain

system

• It consists of several layers of stone of sites 0.5 cm to

6cm

• In the gravel is placed a bed of course sand and above it a

layer of fine sound is placed.

• When the suspended matter has been deposited to such an extent that the rate of filtration

becomes very slow the portion of the top layer is scraped and the bed is used again.

RAPID SAND FILTERS: They need much less place. The general arrangement of the sand bed is
similar to that of slow sand filters, the distinguishing feature being the back wash system.

PRESSURE FILTERS: They have essentially the same

arrangement of the filter media as gravity filters. The filter is
kept in a closed cylinder and water is forced through the
filter bed under pressure. These are suitable for filtering hot
water and industrial purpose. After filtration it becomes
necessary to destroy or make inactive the residual bacteria
and to prevent their growth. This is achieved by sterilization
and disinfection.

5. Sterilization and disinfection

Sterilization: It is a term referring to any process that eliminates or kills all forms of microbial life,
including fungi, viruses and bacteria spore present on a surface or contained in a fluid. Sterilization can
be achieved by applying heat, chemicals, radiation, high pressure and filtration.

Disinfection: It is the process of elimination of most pathogenic micro-organisms (excluding bacterial

spores on inanimate objects. Disinfection can be achieved by physical (boiling, UV Treatment)
/chemical methods (Ozone, Chlorine etc) and the Chemicals used in disinfection are called
disinfectants.

Disinfection of potable water:

1. By Ozonization: Ozone is a powerful disinfectant and is readily absorbed by water. Ozone is

highly unstable and breaks down to give nascent oxygen.

O3 → O2 + [O] nascent oxygen

The nascent oxygen is a powerful oxidizing agent and kills the bacteria.

Disadvantages: This process is costly and cannot be used in large scale, due to unstable of ozone
cannot be stored for long time.

2. By adding Chlorine gas: Chlorine gas is a very good disinfectant, which can be bubbled in the
water. In this process calculated amount of chlorine gas is passed in order to destroy the pathogenic
bacteria is called chlorination. Chlorine also reacts with water and generates hypochlorous acid and
nascent oxygen, which acts a powerful oxidizing agent and kills the bacteria.

Cl2 + H2O → HOCl (Hypochlorous acid) + HCl

HOCl → HCl + [O] nascent oxygen

3. By adding Chloramine: When chlorine and ammonia are mixed in the ratio 2:1 a compound
chloramine is formed. Chloramine compounds decompose slowly to give nascent oxygen which will
be act as good disinfectant than the Chlorine. Chloramine gives good taste to the treated water.

Break-point chlorination: The amount of chlorine required to kill bacteria and to remove organic
matter is called break-point chlorination. When chlorine is added to water, it reacts with different
impurities. If we plot a graph of chlorine dose (x-axis) vs. residual chlorine left in water (y-axis), we
get the breakpoint chlorination curve.

Steps in the Curve:

1. Initial Stage (No Residual Chlorine)

1. At first, added chlorine reacts with reducing agents in water (iron, manganese,
hydrogen sulfide, organic matter).

2. No free chlorine remains → residual is nearly zero.

 2. Formation of Chloramines (Combined Chlorine)

1. As more chlorine is added, it reacts with ammonia (NH₃) present in water.

2. This forms chloramines.

3. Residual chlorine starts to appear, but it is in the form of combined chlorine (not free
chlorine).

3. Destruction of Chloramines

1. With further chlorine addition, chloramines themselves get destroyed (oxidized).

2. This causes a drop in residual chlorine level.

4. Break Point

1. After all ammonia and chloramines are oxidized, any further chlorine addition starts
appearing as free residual chlorine.

2. The point where the curve rises again sharply is called the Break Point.

5. Free Chlorine Residual Zone

1. Beyond the breakpoint, chlorine exists as free chlorine residual, which is highly
effective for disinfection.

Advantages of Break Point Chlorination: It oxidizes completely organic compounds, ammonia

and other reducing compounds.

• It removes color in water, due to the presence of organic matters.

• It destroys completely (100%) all the disease –producing bacteria.

 • It prevents the growth of any weeds in water.

• Usually all tastes, odours disappear at breakpoint, resulting is appearance of water free from
bad tastes and odours.

Brackish water

It is a mixture of freshwater and seawater. It has more salt than freshwater but less salt than
seawater.

• Its salinity usually ranges between 0.5 to 30 parts per thousand (ppt).

• Found in places where freshwater mixes with seawater, such as estuaries, mangrove etc..

• Not suitable for direct drinking, but some fish and plants adapt to it.

• Often used in aquaculture (shrimp, tilapia) and can be treated for desalination to make it
potable.

Desalination: The process of removal of dissolved salts like NaCl from saline water is known as
desalination of water. The methods used for desalination of brackish water are: Reverse Osmosis
and Electro dialysis.

Reverse osmosis

Principle

• Osmosis: Normally, water moves from low salt concentration (freshwater) to high salt
concentration (saline water) through a semi-permeable membrane.

• Reverse Osmosis: By applying external pressure greater than the osmotic pressure on the
saline side, water is forced to move in the opposite direction → from saline/brackish water to
freshwater side.

• The semi-permeable membrane allows only water molecules to pass, rejecting salts, ions, and
other impurities. Examples of Semi permeable membranes are Cellulose Acetate (CA)
Membranes, Cellulose Triacetate (CTA) Membranes, Polyamide (PA) Membranes, Thin Film
Composite (TFC or TFM) Membranes.

Process:

1. High-Pressure Pumping

1. A high-pressure pump applies pressure

(typically 10–30 bar for brackish water;
higher for seawater).

2. This pressure must exceed the natural

osmotic pressure of the saline solution.

2. Reverse Osmosis Membrane Separation

 1. Water is pushed through a semi-permeable RO membrane.

2. The membrane allows pure water molecules to pass but rejects salts, dissolved solids,
heavy metals, and microbes.

3. Collection of Permeate & Brine

1. Permeate (Product water): Freshwater obtained, safe for drinking after

remineralization.

2. Brine (Reject water): Concentrated salt water, discharged carefully to avoid

environmental harm.

4. Post-treatment

1. Sometimes remineralization is done (adding back small amounts of Ca²⁺, Mg²⁺) for
taste and health.

2. Disinfection (like UV or chlorination) ensures microbiological safety.

Advantages of RO for Brackish Water

• Produces high-quality potable water

• Removes dissolved salts, heavy metals, pesticides, and microorganisms

Limitations

• Requires significant energy for pumping

• Membrane fouling/scaling requires maintenance

• Brine disposal can cause environmental issues if not managed properly

Electrodialysis of Brackish Water

Principle: It is based on the principle that when direct current is passed through saline water
using electrodes, salt ions present in saline water migrate towards their respective electrodes through
ion selective membrane.

Apparatus: The electro dialysis unit consists of a chamber, two electrodes a cathode and an anode.
The chamber is divided into three compartments with the help of thin, ion – selective membranes
which are permeable to either cation or anion.
Process:

• Under the influence of applied EMF across the electrodes, the cations move towards cathode
and the anions move towards anode through the membrane.

• The net result is depletion of ions in the central compartment while it increases in the
Cathodic and anodic compartments.

• Desalinated water is periodically drawn from the central compartment while concentrated
brackish water is replaced with fresh water.

Advantages:

• All the contaminant ions are removed.

• It is not sensitive to flow and TDS levels of water.

• The equipment occupies less space as it is compact.

• Capital cost and operational expenses low.

• Low effluent concentrations are released.

Estimation of Dissolved Oxygen (DO) by Winkler’s Method

Principle:

Winkler’s method is used to determine the dissolved oxygen present in water.

• Dissolved oxygen in the sample oxidizes divalent manganese (Mn²⁺) to higher valence
manganese oxides under alkaline conditions.

• Upon acidification, the oxidized manganese releases iodine from potassium iodide (KI).

• The liberated iodine is equivalent to the dissolved oxygen and is titrated against a standard
sodium thiosulfate (Na₂S₂O₃) solution using starch as an indicator.

Overall reaction sequence:

1. Addition of manganous sulfate and alkali-iodide (MnSO₄ + NaOH + KI):

𝑀𝑛2+ + 2𝑂𝐻 − → 𝑀𝑛(𝑂𝐻)2 (𝑤ℎ𝑖𝑡𝑒𝑝𝑝𝑡. )

2. Oxidation by dissolved oxygen (in alkaline medium):

2𝑀𝑛(𝑂𝐻)2 + 𝑂2 → 2𝑀𝑛𝑂(𝑂𝐻)2 (𝑏𝑟𝑜𝑤𝑛𝑝𝑝𝑡. )

3. Acidification with H₂SO₄ (or HCl):

𝑀𝑛𝑂(𝑂𝐻)2 + 2𝐼 − + 4𝐻 + → 𝑀𝑛2+ + 𝐼2 + 3𝐻2 𝑂

4. Liberated Iodine titrated with Na₂S₂O₃:

𝐼2 + 2𝑁𝑎2 𝑆2 𝑂3 → 2𝑁𝑎𝐼 + 𝑁𝑎2 𝑆4 𝑂6

Procedure:

1. Take a BOD bottle (300 mL) filled with the water sample without any air bubbles.

2. Add 2 mL manganous sulfate solution and then 2 mL alkaline potassium iodide (alkali-
iodide-azide) reagent carefully (pipette tip under liquid).

3. Stopper and mix thoroughly by inverting the bottle; a brown precipitate forms if DO is
present.

4. Add 2 mL concentrated sulfuric acid (H₂SO₄). Shake until the precipitate dissolves →
solution becomes yellow or brown due to iodine release.

5. Take 10 ml of this solution into a clean conical flask.

6. Titrate against standard hypo solution taken in the burettle until pale yellow color appears.

7. Add a few drops of starch indicator → solution turns blue.

8. Continue titration till the blue color disappears → endpoint.

Calculations:

If,

• V₁ = volume of sodium thiosulfate used (mL)

• N = normality of sodium thiosulfate

• V₂ = volume of sample taken for titration (mL)

Then, Dissolved Oxygen (mg/L or ppm):

𝑉1 × 𝑁 × 8 × 1000
𝐷𝑂 =
𝑉2

Where 1 mL of 0.025 N Na₂S₂O₃ = 0.2 mg O₂.

Unit-2 Electrochemistry and Applications
1. Electrochemical cell, 2. Nernst equation,
3. Cell potential calculations
4. Primary cells – Zinc-air battery, Secondary cells – Nickel-Cadmium (NiCad), and
lithium-ion batteries- working principle of the batteries including cell reactions;
Fuel cells: Basic Concepts, the principle and working of hydrogen-oxygen Fuel Cell.
==========================================================================

1. What is a galvanic cell and how does it differ from electrolytic cell? Describe the construction and working of
Daniel cell.

Electrolysis:
● In this, electric current is passed through a substance in order to produce chemical changes in the
substance.
Electrolytic cell:
1. It is a device that changes electric energy into chemical energy.
2. In this, electrolysis of a substance takes place to get chemical energy by breaking it.
3. For example: when electric current is passed through water, it breaks water into H2 and O2.
4. It has cathode as the -ve electrode and anode as the +ve electrode. Oxidation takes place at anode
and reduction takes place at cathode.

Electrochemical cell (or voltaic cell or galvanic cell):

1. It is a device that changes chemical energy into electric energy.
2. In this, electric energy is produced from a redox reaction that takes place inside the cell.
3. It has cathode as the +ve electrode and anode as the -ve electrode. Oxidation takes place at anode
and reduction takes place at cathode.
4. The best example for a galvanic cell is Daniel cell.
5. It has two half cells, one Zinc electrode put in ZnSO4 solution (anode) and the other a copper
electrode, put in CuSO4 solution (cathode).
6. The two solutions are separated by a salt bridge so that the solutions can flow out through it to
touch each other.
7. The EMF of the cell is 1.1 V and
8. The electrode reactions in Daniel cell are:
𝐴𝑡 𝑎𝑛𝑜𝑑𝑒 (−𝑣𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒): 𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛)

𝐴𝑡 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 ( +𝑣𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒): 𝐶𝑢2+ + 2𝑒 𝐶𝑢 (𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛)

2+ 2+
Cell reaction: 𝑍𝑛 + 𝐶𝑢 → 𝑍𝑛 + 𝐶𝑢

9. The cell shown as

10.
 EMF measurement of Daniel cell:
1. The EMF of Daniel cell can be calculated from the reduction half cell potentials as:
i. Ecell = E right - E left
2. Where Eright = right hand side’s electrode reduction potential
i. Eleft = reduction potential of left hand side electrode.
3. We know that a +ve value of Ecell shows that the cell reaction is feasible or possible. If Ecell is -ve
for particular cell then the electrodes must be reversed to bring about a cell reaction.

4.
5. Nernst’s equation for a cell and having cell reaction Zn + Cu2+ → Zn2+ + Cu
2.303 𝑅𝑇 [𝑧𝑛2+ ]
i. 𝐸 𝑐𝑒𝑙𝑙 = 𝐸0 − 𝑙𝑜𝑔 𝑙𝑜𝑔 [𝐶𝑢2+ ]
Where n = 2
𝑛𝐹
6. At 298K, the Nernst’s equation for the Daniel cell can be written as

2. Derive Nernst’s equation for single electrode potential and write its applications.

Nernst equation:
● Consider a general redox reaction 𝑀𝑛+ (𝑎𝑞) + 𝑛𝑒 ⇌ 𝑀 (𝑠)
● Now for a reversible reaction, the free energy change (∆𝐺) and it’s equilibrium constant (K) are inter
related as
[𝑃𝑟𝑜𝑑𝑢𝑐𝑡]
∆𝐺 = 𝑅𝑇 𝑙𝑛 𝑙𝑛 𝐾 + 𝑅𝑇 𝑙𝑛 𝑙𝑛
[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡]
 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡]
∆𝐺 = ∆𝐺 0 + 𝑅𝑇 𝑙𝑛 𝑙𝑛 − − − − − − − (1)
[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡]

Where, ∆𝐺 0 is the standard free energy change.

● In a reversible reaction, the electrical energy is produced at the expense of the free energy decrease,
i.e.
− ∆𝐺 = 𝑛𝐹𝐸 𝑎𝑛𝑑 ∆𝐺 0 = −𝑛𝐹𝐸 0 − − − − − − − (2)
Where, E is the electrode potential, E0 is the standard electrode potential,
F is Farady (or 96,500 coulombs).
● From 1&2 ⇒
[𝑀]
−𝑛𝐹𝐸 = −𝑛𝐹𝐸 0 + 𝑅𝑇𝑙𝑛 ( 𝑛+ )
[𝑀 ]

1
= −𝑛𝐹𝐸 0 + 𝑅𝑇𝑙𝑛 ( 𝑛+ ) (∵ [𝑀] = 1)
[𝑀 ]

⇒ −𝑛𝐹𝐸 = −𝑛𝐹𝐸 0 − 𝑅𝑇𝑙𝑛 [𝑀𝑛+ ]

𝑅𝑇
⇒ 𝐸 = 𝐸0 + 𝑙𝑛[𝑀𝑛+ ] (dividing on both side by -nF)
𝑛𝐹
The equation is known as Nernst’s equation for electrode potential.

Terms and What They Stand for in the

Ecell = cell potential of the cell E0 = cell potential under standard conditions
R = universal gas constant T = temperature
n = number of electrons transferred in the redox reaction
F = Faraday constant Q = reaction quotient

Nernst Equation -Applications:

1. The Nernst equation can be used to calculate the following:
2. Single electrode reduction or oxidation potential at any conditions
3. Standard electrode potentials: The electrode potential can be calculated at 250C from Nernst’s
equation as

4. Comparing the relative ability as a reductive or oxidative agent

5. Finding the feasibility of combining such single electrodes to produce an electric potential
6. Emf of an electrochemical cell
7. Unknown ionic concentrations
8. The pH of solutions and solubility of sparingly soluble salts can be measured with the help of the
Nernst equation.
9. Calculation of Equilibrium constant (Keq):
o At equilibrium, E = 0 or ∆𝐺 = 0
o For a chemical reaction 𝑎 𝐴 + 𝑏 𝐵 ⇌ 𝑐 𝐶 + 𝑑 𝐷, the Nernst’s equation can be written
as
 2.303 𝑅𝑇 [𝐶]𝑐 [𝐷]𝑑
0 = 𝐸0 − 𝑙𝑜𝑔 𝑙𝑜𝑔 [𝐴]𝑎 [𝐵]𝑏
(∵ 𝐸 = 0)
𝑛𝐹
2.303 𝑅𝑇 [𝐶]𝑐 [𝐷]𝑑
⇒ 𝐸0 = 𝑙𝑜𝑔 𝑙𝑜𝑔 𝐾𝑒𝑞 (∵ [𝐴]𝑎 [𝐵]𝑏
= 𝐾𝑒𝑞 )
𝑛𝐹

5. How do fuel cells differ from electrochemical cells?

Write informative note on Zn-air cell with special reference to cell reactions and applications

● Battery is a device that has one or more galvanic cells and it changes chemical energy into electric
energy.
● Batteries are used to get direct electric current (DC)
● Batteries are three types
1. Primary cells 2. Secondary cells 3. Fuel cells

Primary cell Secondary cell Fuel cell

1. Cell reaction can not be 1. Cell reaction can be reversed 1. Cannot be reversed.
reversed by passing direct electric
current in opposite direction.
2. Can’t be recharged. 2. Can be recharged. 2. Do not store energy.
[Link] be used as long as the 2. Can be used for a long time by It can be used as long as fuel is
materials are available recharging. supplied.

Zinc – air cell:

1. It contains a Zn electrode and air cathode.

2. Air cathode contains electrolyte (6M KOH), Catalyst (MnO2) and porous carbon electrode.
3. Atmospheric O2 diffuses into the porous carbon electrode.
4. The catalyst reduces O2 to OH- ions in electrolyte by using electrons generated at the anode.
5. The OH- ions move from air cathode to Zn anode to complete cell reaction.
6. The cell voltage is 1.65 V
7. The reactions at the Electrodes are:
o At anode: 𝑍𝑛 → 𝑍𝑛2+ + 2𝑒
𝑍𝑛2+ + 4𝑂𝐻 − → 𝑍𝑛(𝑂𝐻)2− 4 (𝑍𝑖𝑛𝑐𝑎𝑡𝑒)
 𝑍𝑛(𝑂𝐻)2−
4 → 𝑍𝑛𝑂 + 𝐻2 𝑂 + 2𝑂𝐻 −

At cathode: 𝑂2 + 2𝐻2 𝑂 + 4𝑒 → 4𝑂𝐻 −

Net reaction: 2𝑍𝑛 + 𝑂2 → 2𝑍𝑛𝑂 (𝐸 0 = +1.65 𝑉)

Uses:
● These are used in watches, hearing aids, telecoms, railway remote signaling, safety lamps and
electric fences.

Nickel-cadmium Battery
Nickel cadmium battery It is a secondary alkaline storage battery that consists of anode
grid consisting of spongy cadmium with cadmium hydroxide
The cathode is composed of a paste of nickeloxyhydroxide NiO(OH) (s) and small amount of graphite
to increase electrical conductivity.
The electrolyte used is 5 M KOH solution. The cell may be represented as
Cd(s)/Cd(OH)2 /KOH(5M)/NiO(OH)(s)/Ni(OH)2 (s)

Its voltage is ~ 1.35 V. However, its voltage is fairly constant. The reaction products adhere
to the electrode surface and the reaction can be easily reversed. This type of battery does not
undergo deterioration as no gases are produced. It is light, portable and rechargeable.
Applications It is used in calculators, electronic flash units, cordless shavers, transistors, etc.

[Link] informative note on Li-ion battery with special reference to cell reactions and applications

Lithium ion battery:

● It has graphite anode and lithium cobalt oxide cathode and diethyl carbonate having Li+ ions acts as
electrolyte.
● Lithium ion batteries are more costly than Ni-Cd batteries
● When a lithium-based cell is discharging, the positive lithium ion is removed from the anode and
inserted into the cathode.
 ● The cell reactions that take place during discharge are
At anode: 𝐿𝑖𝑦 𝐶 → 𝑛 𝐿𝑖 + + 𝑛 𝑒 + 𝐶
At cathode: 𝐿𝑖1−𝑛 𝐶𝑜𝑂2 + 𝑛 𝐿𝑖 + + 𝑛 𝑒 → 𝐿𝑖𝐶𝑜𝑂2
Net reaction: 𝐿𝑖𝑦 𝐶 + 𝐿𝑖1−𝑛 𝐶𝑜𝑂2 → 𝐿𝑖𝐶𝑜𝑂2 + 𝐶
● When the cell is charging, the reverse takes place.
● The cell reactions that take place during charging are
At anode: 𝑛 𝐿𝑖 + + 𝑛 𝑒 + 𝐶 → 𝐿𝑖𝑦 𝐶
At cathode: 𝐿𝑖𝐶𝑜𝑂2 → 𝐿𝑖1−𝑛 𝐶𝑜𝑂2 + 𝑛 𝐿𝑖 + + 𝑛 𝑒
Net reaction: 𝐿𝑖𝐶𝑜𝑂2 + 𝐶 → 𝐿𝑖𝑦 𝐶 + 𝐿𝑖1−𝑛 𝐶𝑜𝑂2
● Applications:
o Lithium cells are used in mobile phones, laptops etc.

What are fuel cells? Discuss the working of H2-O2 fuel cell

Fuel cell:
● A fuel cell changes the chemical energy of the fuel into electricity. Since the electrons exchange
takes place when a fuel gets oxidized.
● The essential process in fuel cell is
Fuel + oxygen → oxidation products + electricity
● Representation of fuel cell:
Fuel │electrode │ electrolyte │ electrode │ oxidizer
● In this cell the fuel and oxidizer are continuously supplied separately to the electrodes of the cell.
● Fuel cells are capable of supplying current as long as the fuel and oxidizer are supplied.
H2-O2 Fuel cell:
● It has as an electrolyte (25% KOH) and two inert electrodes having holes.
● H2 and O2 gases are passed through the anode and cathode rooms respectively.
● The electrodes made up of graphite are saturated with finely powdered platinum.
● A number of such fuel cells are joined together in series to make a battery.
● The following reactions take place in anode and cathode rooms are:
At anode: 2𝐻2 (𝑔) + 4 𝑂𝐻 − (𝑎𝑞) → 4𝐻2 𝑂 (𝑙) + 4 𝑒
At cathode: 𝑂2 (𝑔) + 2𝐻2 𝑂 (𝑙) + 4𝑒 → 4 𝑂𝐻 − (𝑎𝑞)
Net reaction: 2𝐻2 (𝑔) + 𝑂2 (𝑔) → 2𝐻2 𝑂 (𝑙)
0 0
o The standard EMF of the cell, 𝐸 0 = 𝐸𝑜𝑥𝑑 + 𝐸𝑟𝑒𝑑 = 0.83 + 0.40 = 1.23 𝑉
o Applications:
o These are used as auxiliary (extra or additional) energy sources in space vehicles, submarines &
military vehicles.
o The water formed from fuel cell is very useful to astronauts.
 1

Corrosion:
It is the gradual destruction of metals by chemical and/or electrochemical reaction with their environment.
Corrosion is a natural process Corrosion is a process which is the reverse of extraction of metals.

Ex: Rusting of iron, Tarnish of silver when placed in air for few days

Reason for corrosion: Except Gold and Platinum, all metals generally occur in compound state as oxides,

sulphides, carbonates etc., in nature. Metals are extracted from their ores in a metallurgical process.

Metals are more energetic and less stable than their compounds. Hence metals actively undergo

chemical and/or electrochemical reactions with the environment to again form metal compounds.

Ore + Energy → pure metal

(Stable form) (Unstable form)

Theories of corrosion (or) Mechanism of Corrosion

Based on the nature of the corroding environment, corrosion can be explained by the following two theories.

They are A. Chemical or dry corrosion B. Electrochemical or wet corrosion

A) Dry or Chemical corrosion Theories/ Mechanism: It occurs because of direct chemical action of the
environment on metal
surface in absence of moisture or liquid electrolyte. It generally occurs at a temperature higher than 100 °C
when it is not possible to develop a surface water layer. It is generally of three types

I. Oxidation corrosion: In absence of moisture, at elevated temperatures, metals (except Au, Pt and
Ag) will react directly with oxygen forming an oxide layer.
Chemical reactions: M → M n+ + ne- loss of electrons

O2 + 2e- → O2- gain of electrons

Mn+ + O2 - → Metal oxide.

The nature of the oxide layer is different from metal to metal. There are four types of oxide layers. They are

1. Stable oxide film

2. Unstable oxide film
3. Volatile oxide film
4. Porous oxide film

Engineering Chemistry
 2

1. Stable oxide film:

Metals like Cu, Al, Sn and Pb undergo this type of corrosion. The metal oxide layer formed will
stick to the metal surface tightly. It acts as a protective layer. It prevents further corrosion.

2. Unstable oxide film:

In metals like Ag, Au and Pt, the oxide film formed decomposes back to metal and oxygen.
Hence the film is unstable.

Fresh metal surface is exposed for further attack.

3. Volatile oxide film:
In metals like Molybdenum, the oxide layer formed will be evaporated as soon as it is
formed.
Fresh metal surface is exposed for further attack.

4. Porous oxide film:

In metals like Na, K and Fe etc., the oxide film formed has porous nature. The oxide film
has pores
and cracks. Here O2 will be passed through these pores and further corrosion occurs at interior
layers.

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 3

II. Corrosion by other gases:

In this, dry gases like H2, Cl2, F2, SO2 and CO2 directly attack the metal surface. Rate of corrosion depends
upon the chemical affinity between the metal and gas and also on the nature of the film formed.
Ex:

1. H2S attacks steel forming FeS layer, which is porous in nature.

2. 2Ag + Cl2→2AgCl.
The AgCl film is nonporous and protective and thus it protects the metal from further attack.
3. Sn + 2Cl2→SnCl4
SnCl4 being volatile, Sn undergoes excessive corrosion.

III. Liquid metal corrosion:

It occurs when an anhydrous liquid attacks the metal surface.
When a liquid metal flows over a solid metal at high temperature it weakens the solid metal
because of
• Its dissolution in liquid metal.
• Penetration of liquid metal into solid metal. For example, sodium metal (coolant)
leads to the corrosion of cadmium in a nuclear reactor.
Pilling –Bed worth Rule:
The protective or non-protective nature of oxide layer is determined by
[Link] metal oxide formed
Pilling-Bed worth ratio =
[Link] metal consumed
According to this, an oxide layer is protective if it is non-porous. The volume of the oxide
layer is at least as great as the volume of the metal from which it is formed. An extremely tightly
adhering non-porous layer is formed.
For e.g., 4 Al + 3O2 → 2 Al2O3
An oxide layer is non-protective if it is porous. The volume of the oxide layer is less than
the volume of metal from which it is formed. So O2 reacts with the metal and rapid continuous
corrosion takes place.
E.g., Alkali and Alkaline earth metals Li, Na, K, and Mg.
The oxide layer faces stress and strains thereby developing cracks in the structure.

Wet (or) Electrochemical Corrosion

This type of corrosion occurs under wet or moist conditions, and is more common than dry
corrosion. It occurs when a metal is in contact with conducting liquid or when different metal are in
contact with a solution
Ex: Rusting of iron in water
Let us consider that an iron rod is placed in water or conducting liquid. Upon the surface of
the iron rod, many numbers of anodic and cathodic areas are formed. This is called formation of
corrosion cells.

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 4

At anode, oxidation occurs. Electrons are passed from anodic area to cathodic area due to demand of
electrons. Therefore, corrosion occurs at anode.
Wet corrosion can happen in the following ways.

Oxygen absorption corrosion: Oxygen absorption corrosion takes in the presence of dissolved
oxygen in the medium. This type of reaction takes place in a neutral or weakly alkaline medium.
At Anode: Fe → Fe2+ + 2e- (Oxidation)
Metal dissolves and electrons are released.
The released e- flow from anode to the cathode, through the iron metal.
At cathode: 1⁄2 O2 + H2O + 2e- → 2 OH- (Reduction)
The Fe2+ ions and the OH- ions diffuse and form ferrous hydroxide.
Fe2++ 2 OH- → Fe (OH)2
If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide
4 Fe (OH)2 + O2 + 2 H2O → 4 Fe (OH)3 which is 2Fe2O3.6H2O
If the supply of oxygen is limited the corrosion product is black anhydrous magnetite Fe3O4.
Hydrogen Evolution corrosion: This corrosion occurs in acidic environment.
At Anode: Fe → Fe2+ + 2e- (Oxidation)
At cathode: 2 H++2 e → H2
-
(Reduction)
Net reaction: Fe + 2 H+ → Fe2+ + H2

Types of Electrochemical corrosion:

Galvanic corrosion:
It occurs when two dissimilar metals (like Zn & Cu) are electrically connected and exposed to an electrolyte.
Out of the combined metals, the metal with high oxidation potential goes into corrosion
For example, if zinc and copper are connected, Zn acts as anode and undergoes corrosion. Zinc
gives two electrons to copper. Copper acts as a cathode. However, the type of reaction at cathode
(at copper), depends on the nature of the environment around it.

At anode: Zn →Zn+2+2e-

At cathode: In acidic environment---- 2H + + 2e - → H2

In neutral or alkaline environment---- 1⁄2 O2 + H2O + 2e- → 2 OH-

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 5

Differential aeration corrosion: It occurs when one part of the metal has more aeration and the
other part has less aeration. Less aerated area becomes anodic and loses electrons
More aerated area becomes cathodic and gains electrons Ex: Waterline corrosion, Pitting corrosion
Waterline corrosion: If Water is taken in Iron vessal as shown in figure, the metal present in upper
part, i.e., above the surface of solution acts cathode and metal present in solution acts as anode.
That means metal present above the surface of solution is more aerated. So, there is more electron
demand at the upper part. Therefore, electrons were transported from the lower part (in solution)
to the upper part.
Electrons flow from less aerated area to more aerated area due to developed potential difference.
Waterline corrosion is mostly observed near the top layer of liquid.
At anode: Fe→ Fe+2 + 2e-
At cathode: 1⁄2 O2 + H2O + 2e- → 2OH-
Fe+2 + 2OH- →Fe (OH)2

Pitting corrosion: It is also an example of differential aeration corrosion. If metal like iron has small pits or
pin holes or cavities on the surface and if that area is less aerated then electrons pass from the cavity area to
other areas (where the metal is more aerated) of metal.

Pitting corrosion occurs when small particles like dust, mud etc get deposited on metal surfaces.
Here the area under the pit acts as anode and other areas on metal acts as cathode. In this corrosion
the pit further penetrates deep into metal.
This type of corrosion is generally observed in iron pipes buried in soil or stainless steel immersed in
sea water.
At anode: Fe→ Fe+2 + 2e-
At cathode: 1⁄2 O2 + H2O + 2e- → 2OH-
Fe+2 + 2OH- →Fe(OH)2

Factors influencing Corrosion:

The rate and extent of corrosion depend on the following
I. Nature of metal
II. Nature of the corroding environment
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 6

I. Nature of metal:
Corrosion rate depends on properties of the metal
1 .Position of metal in galvanic (or electrochemical) series:
The rate of corrosion depends on the position of metal in the galvanic series.
More the oxidation potential the more corrosion & act as anode.
2. Purity of metal:
The rate of corrosion depends on the purity of metal
More the purity less the corrosion of metal
3 Physical state:
The rate of corrosion is influenced by the physical state of a metal.
As size of crystal of metal decreases the rate of corrosion increases.
4. Passivity: Metals like Al, Ti, Cr, Ni etc show passivity due to more stable thin oxide film.
5. Nature of corrosion product: Greater the pilling-bedworth ratio, lesser will be corrosion rate..
6. Relative areas of anodic and cathodic areas: Rate of corrosion is high if anodic areas are small
and cathodic areas are large.
7. Volatility of the corrosion product: If the corrosion product has volatile nature, then rate
of corrosion is more.
II. Nature of corroding environment:
1. Temperature: At elevated temperature, the rate of corrosion is more.
2. Humidity of air: Corrosion increases in moist air. Here wet corrosion takes place.
3. Effect pH: In acidic pH, many metals corrode quickly due to electron demand by H+ ions.
4. Presence of impurities: Acidic gases like CO2, SO2, H2S etc., present in the atmosphere will
increase the rate of corrosion of metal.
5. Conductance of corroding medium: If metal pipe is buried in dry soil, corrosion is less. If it is
buried in wet clay containing minerals then corrosion is more.
6. Concentration of oxygen: Differential aeration corrosion affects rate of corrosion.
7. Effect of suspended particles in atmosphere: If suspended particles in air like NaCl, charcoal fall
on metal surface, they absorb moisture in air and start wet corrosion.

Corrosion controlling by cathodic protection method:

Cathodic protection of metal is of two types

● Sacrificial anodic protection to cathode

● Impressed current cathodic protection
Sacrificial anodic protection to cathode:
In this method the metal iron which is to be protected is connected to anode (ex: Mg). In this Mg-Fe
combination, Mg acts as anode and Fe acts as cathode. Electrons which are to be lost by Fe are
immediately supplied by Mg (sacrificial anode)

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 7
Using this technique corrosion of buried pipes can be stopped. Corrosion of ships and water heaters can be
stopped.
Advantages:
1. Minimum maintenance
2. External power supply is not needed.
3. Replacement of anode is easy.
4. Installation is easy.

Disadvantages:
1. Supply of electrons from anode is limited.
2. Regular replacement of anode is needed.
3. In a highly resistive environment, this technique will not work properly.

Impressed current cathodic protection:

In this method the metallic pipe (ex: iron) which is to be protected is connected to negative
terminal of a battery and positive terminal is connected to inert anode (graphite).
In this battery-Fe combination, battery supplies electrons (so acts as anode) and iron pipe take
those electrons (so acts as cathode). Hence, electrons which are going to be lost by Fe are supplied by a
battery (impressed current).

Advantages:
1. This technique can be applied in highly resistive environment also.
2. Voltage can be adjusted according to the demand of electrons

----------------------------------------------------------------------------------------------------------------------------- -------
Electroplating:

1. The process of depositing the coating metal on the surface of base metal by electrolysis is called electroplating.
2. A pure metal (Au) which gives protective coating is connected to positive terminal of battery. It acts as anode.
3. The base metal ornament (ex: copper bangle) is connected to negative terminal of the battery. It acts as cathode.
4. The anodic metal salt solution, i.e., gold (III) chloride (AuCl3) solution is taken as electrolyte.
5. Upon passing direct current from battery, electrolysis occurs.
6. During electrolytic process, anodic metal dissolves in electrolyte and deposits on the surface of base metal as
coating.
7. Since the coated metal has noble character, it doesn’t undergo corrosion
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 8
Factors effecting electroplating:

1. Base metal must be perfectly cleaned.

2. Concentration of electrolyte must be low.
3. For smooth coating, some additives like boric acid must be added to electrolyte.
4. pH of the solution must be maintained constant

Electroless plating or Immersion plating or displacement plating:

1. In electroless plating, a noble metal is deposited on a reactive metal without the passage of
electric current.
[Link] alloy of the noble metal is taken. In the presence of a reducing agent, the alloy is subjected to
reduction.
Finally, the noble metal (which comes from its alloy) will stick to the reactive metal.
[Link] method is also called autocatalytic coating.
[Link]: Reactive metal is Iron. Alloy is Nickel phosphate Reducing agent is Sodium hypo phosphite.
a) The base metal (ex: iron) is immersed in hot solution of nickel phosphate and
Sodium hypo phosphite at 100oC at pH 4.5.
b) Ni+2 ion is reduced to metallic nickel.
c) An alloy of nickel and nickel phosphide sticks to base metal surface.
d) This coating protects the base metal from corrosion. Since no external electrical energy is used, it is
called Electroless plating.

Engineering Chemistry
 9

Engineering Chemistry
 UNIT III Polymers and Fuel Chemistry
Syllabus:
Introduction to polymers, functionality of monomers, Mechanism of chain growth, step growth
polymerization.
Thermoplastics and Thermo-setting plastics(page-4): Preparation, properties and applications of
polystyrene. PVC, Nylon 6,6 and Bakelite.
Elastomers – Preparation, properties and applications of Buna S, Buna N, Thiokol rubbers.
Fuels: Types, calorific value of fuels, numerical problems based on calorific value; Analysis of
coal (Proximate and Ultimate analysis)
Liquid Fuels, refining of petroleum, Octane and Cetane number alternative - fuels- propane,
methanol, ethanol, and biofuel-biodiesel.
===============================================================
INTRODUCTION TO POLYMERS: Polymers form very important components in our daily
life. The polymers are highly useful in domestic, industrial & medical fields. The following are
the reasons for the extensive use of polymers.
1) Most of the polymers are non-toxic & safe to use
2) They have low densities (light in weight) so transportation polymers will be easy.
3) They possess good mechanical strength.
4) These are resistant to corrosion and will not absorb moisture when exposed to the
atmosphere.
5) These can function as good thermal & electrical insulators.
6) These can be moulded and fabricate easily.
7) They possess aesthetic colours
Q. Define Polymer and give examples?
The word Polymer is derived from Greek. Poly means Many; Meros means Units/ Parts
Definition: Polymers are macro molecules of high molecular weight, built up by the linking
together of a large number of small, repeated units by covalent bond. The repeating units are
known as Monomer. Polymers are formed by joining large number of small molecules (units)
called monomers.
Example: Polyethylene, Poly vinyl chloride (PVC), Polystyrene (PS), Nylon 6,6, Bakelite

Q. What is meant by polymerisation. Give an example?

Polymerization: “The process of formation of polymers by the addition of large number
monomer units” is called polymerisation.

Examples:

Q. What is the functionality of a monomer? Discuss with examples.

FUNCTIONALITY: “The number of reactive sites (bonding sites) in a monomer
molecule is termed" as its functionality.
Polymers can be classified on the basis of functionality into the bifunctional polymers,
tri functional polymers and poly functional polymers, etc.
For example, ethylene can add two molecules of hydrogen or halogen. Hence, it is bifunctional

1|Page
(functionality two) and which give linear polymers.
Phenol has three reaction sites (2-ortho and one para). It undergoes substitution reaction at
these sites. Hence, it is trifunctional and which give branched or cross-linked polymers.
Similarly, acetylene has a functionality of four (tetra functional), as it can react with four
atoms of hydrogen or halogen. And which give branched or cross-linked polymers.
If a monomer contains more than three reactive sites, it is called as poly functional monomer.
Hence three-dimensional network of polymer is produced and which give branched or cross-
linked polymers.
No. of Bonding sites Functionality Structure of polymer

Ethylene 2 Bifunctional Linear and straight chain

Phenol 3 Tri functional Branched or 3-D network

Acetylene 4 Tri functional Branched or 3-D network

=================================================================
Q. Write the Mechanism for free radical addition polymerisation Mechanisms?
Mechanism of chain growth:
Addition or chain growth polymerization: “The process of formation of a polymer without
any by-product such as H2O, CO2, NH3, etc. by addition of large number of monomer units”
Ex:

Free radical mechanism: In this, free radicals are involved in the mechanism of
addition polymerization. The mechanism consists of the following three steps
Step-I: Chain initiation step
Step-II: Chain propagation step
Step-III: Chain termination step

2|Page
Q. Write a note on mechanism or Step growth polymerization (Condensation
polymerisation)
Q. Explain the Preparation, properties and applications of Nylon 6, 6?
Nylon 6,6 is a type of synthetic polymers known as polyamides.
Preparation: It is prepared by condensation polymerization of Hexamethylenediamine
and Adipic acid.

Properties
1. Nylons are generally tough, strong, durable fibres
2. Nylon is a high-performance plastic. It has great wear properties, impact
properties, abrasion resistant and very durable. +
3. High mechanical strength and rigidity
3|Page
4. Good stability under heat and /or chemical resistance
5. Dries quickly, it retains its shape.
Uses/Applications
1. Used as thread in bristles for tooth brushes.
2. As gears, fittings and bearings, automotive industry.
3. Surgical sutures, strings for musical instruments
4. In hosiery and knitted garments
5. The items made with nylon are Footwear, fishing line, Tents, hoses,
parachutes, gloves, Gun frames, Threads, ropes, filaments, nets.
6. Used in fibers for textiles and carpets and moulded parts.
7. Luggage bags, airbags, and for carpet fibres.
8. Use for Kitchen tools, automotive parts, medical tools, reels and gears, bearings,
clothing fabric, computer parts, etc.

PLASTICS: Plastic is a polymer which possesses plasticity properties and moulded in to our
desire shape, size, strength, structure and colour by subjected apply pressure and heat on it.
Q. Differentiate Thermoplastics and Thermosetting plastics.
Thermoplastics plastics Thermosetting plastics

These are become soft when heated and become solid These are permanent change on heating. That means once
(hard) when cooled. they solidified, they cannot be softened.

These polymers have linear and branched structures. These polymers have cross linked, 3D- structure

These are soft, weak and less hard. These are hard, strong, tough and brittle.

They can be amorphous (or) semi crystalline materials. These are crystalline in structure

Neighboring polymer chains held together by the weak The polymer chains are held together by cross links (covalent
Vanderwaal forces of attraction (or) Dipole Dipole bonds).
interaction (or) Hydrogen bonding.
Structure:

Structure:

These are prepared by addition polymerization. These are prepared by condensation polymerization.

These are soluble in organic solvents. These are not easily soluble in organic solvents.

They can be reuse and changed into forms They cannot be reused.

Examples: Polyethylene (PE), Poly vinyl chloride (PVC), Examples: Bakelite, Urea-formaldehyde, Polyesters like
Poly styrene (PS) Nylon-6,6 and Nylon-6, Rubbers and poly urethanes

4|Page
 Poly Vinyl Chloride (PVC)
Preparation: The process of formation a PVC by the addition (chain growth) polymerisation
of Vinyl chloride in the presence of pressure.

Vinyl chloride Poly Vinyl Chloride (PVC)

Properties of PVC
1. PVC is a lightweight, durable, low-cost, and long-life is assured.
2. Polyvinyl Chloride is a white, brittle solid material
3. It has high tensile strength and is naturally stiff.
4. It requires less maintenance and is resistant to grease and oil.
5. This polymer has chemical resistant to all inorganic chemicals.
6. It is an excellent material for electrical resistance.
7. It has good corrosion resistance.
8. It is an intrinsic flame retardant (thermal resistance).
9. It is an Abrasion-resistant material.
Applications: (Uses):
1. Plasticized PVC is used in flooring.
2. (PVC-U) unplasticized PVC is used in making window frames.
3. It is used in making sewage pipes.
4. Used in construction fields for insulation on electrical wires or in flooring for
hospitals, schools and homes.
5. It is used in various industries like building, electronics, electrical, automotive,
medical and packaging.
6. PVC fabric is used in the manufacture of aprons shower curtains,
raincoats, jackets and sports bags.
7. It is used in the garden hose and imitation leather upholstery.
======================================================
Preparation of Polystyrene
The process of formation of polystyrene by the addition of large number of styrene units in
the presence of benzoyl peroxide.

Polystyrene Properties
1. It is rigid, brittle, and quite strong.
2. The heat resistance of Polystyrene is relatively low.
3. It has a low thermal conductivity and is an insulator. (good electrical resistance)
4. It is non-polar so it is not soluble in water and has poor oxygen and UV
resistance.
5. It has good resistance to bases and diluted acids. (good chemical resistance).
6. The melting point and boiling point of Polystyrene are 513 K and 703 K, respectively.
7. It is non-polar and has average oil resistance.

5|Page
 8. It gets easily coloured and has a low-impact strength.
9. It is soluble in benzene, ethyl acetate, chloroform, etc.
Polystyrene Uses
1. Medically it is used for sterilizing test tubes, diagnostic components, and other
medical devices.
2. It is used to manufacture car parts which include knobs, instrument panels, sound
dampening foam, etc.
3. Polystyrene foodservice packaging keeps the food fresh for a longer period of time
and is less expensive than alternatives.
4. It is used in packaging consumer goods such as DVD cases, and egg cartons, to
protect against spoilage or damage.
5. It provides thermal insulation and is used in refrigerators, freezers, etc.
6. Used in housing in all IT equipment such as Television, computer, etc.
----------------------------------------------------------------------------------------------------
Write a note on Step growth polymerization (Condensation polymerisation)
mechanism
Preparation properties and applications of of phenol formaldehyde resin of Bekalite?

Properties
1. Bakelite plastic resins are hard, rigid and strong.
2. Bakelite is an excellent electrical insulator.
3. It is a very good adhesive.
4. Bakelite has very good corrosion resistance, resistant to atmospheric
conditions like light, moisture, O2, CO2, etc.
5. Bakelite has good chemical resistance, resistant to acids, salts and organic solvents.
6. It is a scratch resistant and water-resistant polymer.

6|Page
Uses/Applications Bakelite is used
1. For making electrical insulator parts like switches, switch boards, Plugs, Panels, etc.
2. Used for making heater handles, handles for pressure cookers, frypans, etc.
3. For making moulded articles like telephone parts, cabinets for radio and television.
4. Used as an anion exchanger in water purification by ion exchange
method. 5. Used as an adhesive (binder) for grinding wheels and brake
linings, etc.
6. Used in paints and varnishes (protective coatings)
7. Used in kitchen wares, jewelry and children’s toys
8. It is used to fix metal samples in a frame to study the properties of
metals.
============================================================
BUNA-N (NBR OR NITRILE RUBBER) It is copolymer of Acrylonitrile and Butadiene
Preparation: The process of formation of BUNA-N rubber by the addition of large
number of 1,3-butadiene and acrylonitrile in the presence of peroxide.
This copolymer contains about 75% 1,3-butadiene and 25% styrene.

Properties
1. It can withstand scratching, Abrasion Resistance.
2. It has good tensile (extension) strength.
3. Possesses excellent heat resistance, sunlight, fuels, oils, acids, and salts but it is less
resistant to alkali because of the CN group. (So it may be exposed to high temperature).

Engineering applications: They are used to

1. Make Fuel tanks, gasoline hoses, petrol carrying pipes,
2. Rubber sealing joints between metal parts and air craft parts.
3. Used in textiles, leather manufacturing, paper, etc.
4. Used as adhesive
5. Used in making of automobile parts, hoses,
6. Gaskets, Conveyor belts, Printing rollers.
Used as blend component in tyre manufacture
===========================================================
Styrene Butadiene, Buna S, SBR, GRS
The process of formation of BUNA-S rubber by the addition of large number of 1,3-
butadiene (75%) and styrene (25%) in the presence of sodium metal as catalyst.

Properties:

7|Page
They have a high load-bearing capacity.
Buna-S is a polymer, that has high resistance to abrasion.
It swells in oil and solvents.
Uses
It is used for making motor tyres, and conveyor belts.
They are also useful in making shoe soles, footwear, electrical insulations, etc.
It is also used in building applications, as a sealing and binding agent.
FUELS: Any combustible substance which during combustion give large amount of heat
which can be used economically for domestic and industrial purposes.
FUEL + O2 → PRODUCT + HEAT
--------------------------------------------------------------------------------------------------------------
Fuels Classification: Fuels are classified based on their Occurrence
A. Natural or Primary fuels: Fuels found in nature. E.g., wood, peat, coal, petroleum,
natural gas etc.
B. Artificial or Secondary fuels: Fuels prepared artificially (from the primary fuels).
E.g. charcoal, coke, kerosene, diesel, petrol, coal gas, oil gas, producer gas, etc.
Fuels Classification On the basis of Physical State:
a) Solid, b) Liquid and, c) Gaseous fuels.

Calorific value: The amount of heat liberated by the complete combustion of a unit weight
of the fuel ‘’ and in usually expressed as cal gm-1 or kcal gm-1 or [Link].U.
Gross calorific value is the heat liberated when a unit quantity of fuel is completely burnt
and the products of combustion are cooled to room temperature.
Higher calorific value or gross calorific value is defined as the total amount of heat
liberated, when unit mass or unit volume of the fuel has been burnt completely and the
products of combustion are cooled down to 150C.
Net calorific value or lower calorific value: lower calorific value is defined as “the net heat
produced, when unit mass or unit volume of the fuel is burnt completely and the combustion
products are allowed to escape.
LCV or NCV = HCV – Latent heat of water vapour formed
----------------------------------------------------------------------------------------------------------
Analysis of coal:
The composition of coal varies widely and hence it is necessary to analyze the coal samples
so that types of coal can be selected for a particular industrial use. The following methods of
analysis can be utilized for the selection of coal.
Proximate analysis: This analysis records moisture, volatile matter, ash and fixed carbon
as percentages of the original weight of the coal sample. Proximate analysis is of
significance in commercial classification and industrial utilization of coal.
Ultimate analysis: This consists of determination of C, H, S, N and O. The ultimate
analysis is essential for calculating heat balances in any process for which coal is employed
as a fuel.
--------------------------------------------------------------------------------------------------------

8|Page
Explain in detail an account of proximate analysis of coal.
1. Proximate analysis: It is a quantitative analysis of the following parameters.
1. Moisture 2. Volatile matter 3. Ash 4. Fixed carbon
1. Moisture: About 1 gram of finely powdered air-dried
coal sample is weighed in a crucible. The crucible is
placed inside an electric hot air-oven, maintained at 105
to 1100C. The crucible is allowed to remain in oven for 1 hour and then taken out, cooled in
desiccators and weighed. Loss in weight is reported as moisture.
Significance: Lesser, the moisture content; better the quality of coal as a fuel. However,
presence of moisture, up to 10%, produces a more uniform fuel-bed and less of “fly-ash”.
2. Volatile Matter: The dried sample taken in a crucible in and then covered with a lid and
placed in an electric furnace or muffle furnace, maintained at 925 + 20 oC. The crucible is
taken out of the oven after 7 minutes of heating. The crucible is cooled first in air, then
inside desiccators and weighed again. Loss in weight is reported as volatile matter on
percentage-basis.

significance: a high volatile matter content means that a high proportion of fuel will distil
over as gas or vapour, a large proportion of which escapes un-burnt, So, higher volatile
content in coals undesirable. A high volatile matter containing coal burns with a long flame,
high smoke and has low calorific value. Hence, lesser the volatile matter, better the rank of
the coal.
3. Ash: The residual coal sample taken in a crucible and then heated without lid in a muffle
furnace at 700 +50 C for ½ hour. The crucible is then taken out, cooled first in air, then in
desiccators and weighed. Hearing, cooling and weighing is repeated, till a constant weight is
obtained. The residue is reported as ash on percentage-basis. Thus,

Significance: Ash is a useless, non-combustible matter, which reduces the calorific value
of coal. Moreover, ash causes the hindrance to the flow of air and heat, thereby lowering
the temperature. Also, it often causes trouble during firing by forming clinkers, which
block the interspaces of the grate, on which coal is being burnt. This in turn causes
obstruction to air supply; thereby the burning of coal becomes irregular. Hence, lower the
ash content, better the quality of coal. The presence of ash also increases transporting,
handling and storage costs. It also involves additional cost in ash disposal. The presence of
ash also causes early wear of furnacewalls, burning of apparatus and feeding mechanism.
4. Fixed carbon:
Significance:: Higher the percentage of fixed carbon, greater is it’s calorific and betters the
quality coal. Greater the percentage of fixed carbon, smaller is the percentage of volatile
matter. This also represents the quantity of carbon that can be burnt by a primary current of
air drawn through the hot bed of a fuel. Hence, high percentage of fixed carbon is desirable.
The percentage of fixed carbon helps in designing the furnace and the shape of the
fire-box, because it is the fixed carbon that burns in the solid state.
--------------------------------------------------------------------------------------------------------

9|Page
Explain the determination & significance of the following constituents present in coal.
i. Total carbon ii. Hydrogen iii. Nitrogen iv. Sulphur and v. Oxygen. OR
Give an account of the analysis of coal by ultimate analysis and its significance.
[JUNE-2010]
Ultimate analysis: This is the elemental analysis and often called as qualitative
analysis of coal. This analysis involves the determination of carbon and hydrogen, nitrogen,
sulphur and oxygen.
Carbon and Hydrogen: About 1 to 2 gram of accurately weighed coal sample is burnt in a
current of oxygen in a combustion apparatus. C and H of the coal are converted into CO2
and H2O respectively. The gaseous products of combustion are absorbed respectively in
KOH and CaCl2 tubes of known weights. The increase in weights of these are then
determined.
C + O2 → CO2 2KOH + CO2 → K2CO3 + H2O 12g →44g
H2 + ½ O2 → H2O CaCl2 + 7 H2O → CaCl2.7H2O 2g → 18g

Significance: Greater the percentage of carbon and hydrogen better is the coal in quality and
calorific value. However, hydrogen is mostly associated with the volatile mater and hence, it
affects the use to which the coal is put.
Nitrogen: About 1 gram of accurately weighed powdered coal is heated with concentrated
H2SO4 along with K2SO4 (catalyst) in a long-necked Kjeldahl’s flask. After the solution
becomes clear, it is treated with excess of KOH and theliberated ammonia is distilled over
and absorbed in a known volume of standard acid solution. The unused acid is then
determined by back titration with standard NaOH solution. From the volume of acid used
by ammonia liberated, the percentage of N in coal is calculated as follows:

Significance: Nitrogen has no calorific value and hence, its presence in coal is underirable.
Thus, a good qualitycoal should have very little Nitrogen content.
Sulphur: Sulphur is determined from the washings obtained from the known mass of coal,
used in bomb calorimeter for determination of a calorific value. During this determination, S
is converted in to Sulphate. The washings are treated with Barium chloride solution, when
Barium-sulphate is precipitated. This precipitate is filtered, washed and heated to constant
weight.

Significance:: Sulphur, although contributes to the heating value of coal, yet on combustion
produces acids like SO2, SO3, which have harmful effects of corroding the equipments and
also cause atmospheric pollution. Sulphur is, usually, present to the extent of 0.5 to 0.3% and
derived from ores like iron, pyrites, gypsum, etc., mines along withthe coal. Presence of
sulphur is highly undesirable in coal to be used for making coke for iron industry. Since it is
transferred to the iron metal and badly affects the quality and properties of steel. Moveover,
oxides of sulphur
pollute the atmosphere and leads to corrosion.
Ash: The residual coal taken in the crucible and then heated without lid in a muffle furnace
at 700 + 50 C for ½ hour. The crucible is then taken out, cooled first in air, then in
desiccators and weighed. Hearing, cooling and weighing is repeated, till a constant weight is

10 | P a g e
obtained. The residue is reported as ash on percentage-basis. Thus,

Significance: Ash is a useless, non-combustible matter, which reduces the calorific value of
coal. Moreover, ash causes the hindrance to the flow of air and heat, thereby lowering the
temperature. Hence, lower the ash content, better the quality of coal. The presence of ash
also increases transporting, handling and storage costs. It also involves additional cost in
ash disposal. The presence of ash also causes early wear of furnace walls, burning of
apparatus and feeding mechanism.
Oxygen: It is determined indirectly by deducting the combined percentage of carbon,
hydrogen, nitrogen, sulphur and ash from 100.

Significance: Oxygen content decreases the calorific value of coal. High oxygen-content
coals are characterized by high inherent moisture, low calorific value, and low coking power.
Moreover, oxygen is a combined form with hydrogen in coal and thus, hydrogen available
for combustion is lesser than actual one. An increase in 1% oxygen content decreases the
calorific value by about 1.7% and hence, oxygen is undesirable. Thus, a good quality coal
should have low percentage of oxygen.
Liquid Fuels, Refining of petroleum:
Crude oil obtained from the mine is not fit to be marked. It contains a lot of soluble and
insoluble impurities which must be removed. Previously the purification of crude oil is done
by simple fractional distillation. Further treatment of the products is done by refining.
Refining can be defined as the process by which petroleum is made free of impurities, division
of petroleum into different fractions having different boiling points and their further treatment
to impart specific properties.
Refining of petroleum is done in different stages:
a. Removal of solid impurities: The crude oil is a mixture of solid, liquid and gaseous
substances. This is
allowedto stand undisturbed for some time, when the heavy solid particles settle down and
gases evaporate. The
supernant liquid is then centrifuged where in the solids get removed.
b. Removal of water (Cottrell’s process): The crude oil obtained from the earth’s crust is
in the form of stable
emulsion of oil and brine. This mixture when passed between two highly charged electrodes
will destroy the
emulsion films and the colloidal water droplets coalesce into bigger drops and get separated
out from the oil.
c. Removal of harmful impurities: In order to remove sulphur compounds in the crude oil.
It is treated with
copper oxide. The sulphur compounds get converted to insoluble copper sulphide, which can
be removed by
filtration. Substances like NaCl and MgCl2 it present will corrode the refining equipment and
result in scale
formation. These can be removed by techniques like electrical desalting and dehydration.
Fractional distillation: Heating of crude oil around 4000C in an iron retort, produces
hot vapor which is allowed to pass through fractionating column. It is a tall cylindrical tower
containing a number of horizontal stainless trays at short distances and is provided with small
chimney covered with loose cap. As the vapors go up they get cooled gradually and fractional
condensation takes place. Higher boiling fraction condenses first later the lower boiling
fractions.

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 OCTANE NUMBER:
Definition: The octane number of a petrol sample is defined as the
percentage of isooctane in a mixture of isooctane and n-heptane
which matches the fuel under test in knocking characteristics.

Definition: Cetane number is defined as

the percentage of hexadecane (n-cetane)
present in a mixture of hexadecane and
2-methyl naphthalene, which has the
same ignition characteristic of diesel
fuel in test.

Q. Difference between Octane and Cetane Number?

Octane number Cetane number

It is the percentage of iso-octane in a mixture It is the percentage of hexadecane in a mixture

of isooctane and n-heptane that matches the of hexadecane and α-methyl naphthalene which
fuel under test in knocking characteristics. have the same knocking characteristics as the
diesel fuel.

It is used to find the suitability of gasoline or It is used to find the suitability of a diesel fuel.
any other internal combustion engine fuel.

12 | P a g e
 The octane number of internal combustion The cetane number of diesel fuel can be increased
fuels can be increased by the addition of by the addition of‘pre ignition dopes’ such as
tetraethyl lead (TEL), (C2H5)4Pb and diethyl ethyl nitrite, isoamyl nitrite, acetone
telluride, (C2H5)2Te.

Hydrocarbons which are poor diesel fuels are The order of ignition quality among hydrocarbon
quite good gasoline fuels. constituent of a diesel fuel is n- alkanes >
naphthalenes > alkenes > branched alkanes >

Straight chain hydrocarbons are worst Straight chain hydrocarbons are best fuels as they
fuels as they have low octane number have high cetane number.

Propane: Also known as liquefied petroleum gas (LPG), propane is a clean-burning fuel
with lower emissions compared to gasoline or diesel.
It's commonly used for heating, cooking, and as a transportation fuel for vehicles like
forklifts, buses, and fleet vehicles.
The main constituent of LPG is propane and Butane..
The chemical formula for propane is 𝐶3𝐻8
------------------------------------------------------------------------------------------
Methanol:
Methanol (CH3OH), also known as wood alcohol.
Methanol is a liquid fuel that can be produced from natural gas, coal, biomass.
It's used as a fuel additive, in fuel cells, and as a gasoline substitute in some vehicles.
Methanol has lower carbon emissions compared to gasoline and diesel and can be produced
sustainably from renewable sources.
Benefits: The benefits of methanol include:
Lower production costs—Methanol is cheap to produce relative to other alternative fuels.
Improved safety—Methanol has a lower risk of flammability compared to gasoline.
-------------------------------------------------------------------------------------------------------
Ethanol:
Ethanol is a renewable fuel made from various plant materials collectively known as
"biomass." More than 98% of U.S. gasoline contains ethanol to oxygenate the fuel.
Ethanol is a renewable fuel made from plant materials such as corn, sugarcane, or
switchgrass.
It's commonly blended with gasoline to reduce emissions and enhance octane levels.
Ethanol production also helps reduce greenhouse gas emissions by offsetting fossil fuel use.
-------------------------------------------------------------------------------------------------------
Biodiesel: Biodiesel is a renewable fuel made from vegetable oils, animal fats, or recycled
cooking grease.
It can be used in diesel engines without modifications and is often blended with petroleum
diesel in various proportions (e.g., B20 contains 20% biodiesel).
Biodiesel reduces emissions of carbon monoxide, particulate matter, and hydrocarbons
compared to conventional diesel.

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 Modern Engineering Materials

Composite materials
Definition
A composite material is a solid material that's made by combining two or more substances with
different properties. The new material has properties that are better than the original components for
a specific application.

Constituents of Composites

Two essential constituents of composites are

1. Matrix:
The matrix is the continuous phase that surrounds and
binds together the reinforcement materials.
It provides support to the reinforcement and helps distribute loads and stress throughout the material.
Common matrix materials include polymers (polymer matrix composites or PMCs), metals (metal
matrix composites or MMCs), and ceramics (ceramic matrix composites or CMCs).
[Link]: (Dispersed Phase)
The reinforcement phase is composed of materials with high strength and stiffness, and it is
embedded in the matrix to enhance the overall performance of the composite.
Reinforcements can be in the form of Fibers, particles, or other geometrical shapes.
The choice of reinforcement material depends on the desired properties of the composite.

Classification of composites:
1. Fibre Reinforced Composites
Fiber-reinforced composites: In these composites, the dispersed phase is in the form of fibers. These
are subdivided into (a) continuous aligned (b) discontinuous.
Discontinuous composites are further divided into (a) aligned (b) randomly oriented
Fiber-reinforced Composites are made of metals, ceramics, glasses, carbon Fibers.

Some important types of Fiber reinforced composites are

[Link] fiber reinforced polymer composite
[Link] fiber reinforced polymer composites
[Link] oxide/ carbon fiber reinforced metal composites

[Link] Composites
Particle-reinforced composites: In these composites, the dispersed phase is equi-axed, i.e., the
dimensions of the particles are nearly the same in all directions.
They are subdivided into the following:
(a) Large-particle composites

(b) Dispersion-strengthened composites

Example: concrete which is composed of
cement matrix and particulates of sand and gravel.

3. Structural composites
Structural composites: In these composites, the
properties depend not only on the constituent
material but also on this geometrical design.

These are of two types

1. Laminated composites
2. Sandwich composites
A laminated composite is a composite material made up of multiple layers of fibrous materials
Example: Plywood, Copper bottom steel articles

A sandwich composite, often referred to as a sandwich structure, is a type of material construction

that consists of three layers: two outer layers (called face sheets or skins) and a core material placed
between them.
Example: Synthetic rubber, Foamed polymer

Properties:
[Link] Strength-to-Weight Ratio: One of the main advantages of composite materials is their
exceptional strength-to-weight ratio.
2. Tailorable qualities: By changing the type, orientation, and volume of a composite, its qualities
can be made to match certain needs.
3. Anisotropy: A fraction of the constituent materials can be displayed differently in different
directions by composite materials.
4. Corrosion Resistance: Composites, as opposed to metals, frequently exhibit corrosion resistance,
which can be a big benefit in difficult situations.
[Link] Insulation: Electrical and electronic applications benefit from the electrical insulation
found in many composite materials.
6. Fire Resistance: Certain composites can be made to be fire-resistant, depending on their
composition, which qualifies them for uses where fire safety is an issue.
7. Design versatility: When it comes to shaping and mouldings components, composites give
designers a great deal of versatility.

Applications:
Composite materials have found widespread applications in various engineering fields due to their
unique combination of properties
1. Aerospace Industry: Composites, such as carbon Fiber-reinforced polymers (CFRP), are
extensively used in the aerospace industry for components like wings, fuselage sections, and tail
structures. These materials provide high strength-to-weight ratios, which are crucial for aircraft
performance.
[Link] Industry: Components like dashboards, seat frames, and door panels often
incorporate composite materials for their lightweight and durable properties.
[Link] Engineering: Composite materials, particularly Fiber-reinforced polymers (FRP), are used in
the construction of bridges and other infrastructure components. These materials offer high strength,
corrosion resistance, and durability.
[Link] and Recreation: Composite materials are commonly used in the production of sporting
goods such as tennis rackets, golf clubs, and bicycle frames.
[Link] Devices: Some medical implants, such as bone plates and screws, are made from
composite materials.
[Link]: used in the manufacturing of Printed Circuit Boards due to their excellent electrical
insulating properties and mechanical strength.

REFRACTORIES
REFRACTORIES: Refractories are inorganic materials that can withstand high temperatures without
softening, melting or deformation.
CHARACTERISTICS (OR) REQUISITES OF A GOOD REFRACTORY:
• It must be able to withstand high temperature generated in the furnace.
• It should be chemically inert towards the corrosive gases, metallic slag and liquids.
• It should resist the abrasive action of flue gases, flames, etc.

Classification of Refractories:
[Link] Based on fusion temperature:

On the basis of fusion temperature ranges, they are classified as:

a) Normal refractory: fusion temperature = 1580 - 1780 °C (e.g: fire clay)

b) High refractory: fusion temperature = 1780 - 2000 °C (e.g: chromite)

c) Super refractory: On the basis of fusion temperature => 2000 °C (e.g: zircon)

2. Classification Based on Chemical Composition:

(i) Acidic Refractories: Refractories which consist of acidic materials are known as acidic refrac-
tories. These are easily attacked by basic materials and not by acidic materials.
Eg.: Alumina, silica
Neutral Refractories: Refractories which consist of weakly acidic/basic materials are known as
neutral refractories.
Eg.: Zirconia, graphite, chromite
Basic Refractories: Refractories which consist of basic materials are known as basic refractories.
There are easily attacked by acidic materials and not by basic materials.
Eg.: Magnesite and dolomite.
3. Classification Based on oxide content:
On the basis of the oxide content the refractories are further classified into :

a) Single oxide refractories eg: alumina, magnesia and zirconia.

b) Mixed oxide refractories eg: zircon, spinel, mullite
c) Non-oxide refractories eg: borides, carbides, silicide’s and nitrides

4. Classification Based on Physical Form:

Refractories are classified according to their physical form. These are the shaped and unshaped
refractories.
Shaped Refractories:
Shaped refractories are those which have fixed shaped when delivered to the user. These are what we
call bricks. Brick shapes maybe divided into two: standard shapes and special shapes.
Unshaped Refractories:
Unshaped refractories are without definite form and are only given shape upon application
Properties of Refractories:
Refractories are characterized by a certain set of properties. These are outlined below :
1. Refractoriness:
It is the ability of a material to withstand high temperature
without appreciable deformation or softening under given
working conditions. As the temperature increases normally a
material softens and deforms, but a refractory should resist
such a tendency. Higher the softening temperature, more
valuable is the refractory.
Measurement of refractoriness is done by using pyrometric
cones. Each cone is a mixture of oxides that melts at specific temperatures.
2. Porosity: It is the ratio of pore volume to the bulk volume. Refractories usually contain pores
which result from their manufacturing methods, these pores may be open or closed.
𝑊−𝐷
P = 𝑊−𝐴 × 100

where, P= Porosity
W = saturated weight of specimen
D=dry weight of the specimen
A= saturated weight + moisture content of specimen

[Link] Melting Point: Refractories are designed to withstand extremely high temperatures without
undergoing significant physical or chemical changes. This property allows them to maintain their
structural integrity in applications involving intense heat.
[Link] Stability: Refractories must be chemically stable in the presence of various substances,
including acids, bases, and other reactive materials.
[Link] Shock Resistance: Refractories often experience rapid temperature changes, leading to
thermal shock. Good refractory materials are designed to withstand these sudden changes in
temperature without cracking
[Link] Mechanical Strength: Refractories need to have sufficient mechanical strength to withstand
the weight of the lining and any external loads.
[Link] of Installation: Some refractories come in pre-shaped forms or can be easily molded and
installed.
[Link] to Corrosion: Refractories must resist corrosion from chemical reactions with
substances present in the operating environment. This property is crucial for their long-term
performance and durability.
Factors affecting Refractory materials:
[Link]: Different materials have different temperature limits, and exposure to temperatures
beyond their capacity can lead to thermal degradation.
[Link] chemical environment in which refractory materials operate is crucial. Certain materials may
react with specific chemicals or slags present in the process, leading to corrosion or chemical attack.
[Link] Stress: Mechanical stress, including thermal shock and mechanical impact, can affect
the integrity of refractory materials.
[Link] and Permeability: The porosity and permeability of refractory materials can affect their
resistance to penetration by gases or liquids.
[Link] Attack: Alkali attack can lead to degradation and weakening of the refractory structure.
[Link] Conductivity: The ability of a refractory material to conduct heat can impact its
performance.
Applications of Refractories
[Link] materials are used to make furnaces, kilns, incinerators, and
reactors.
2. To make crucibles
3. Moulds for casting glass and metals
4. Surfacing flame deflector systems for rocket launch structures.
5. Used to make different parts of solid and liquid rockets, nuclear propulsion
devices and high-performance air breathing devices such as ramjet engines
6. Valves for missiles

LUBRICANTS

Lubricants: A lubricant is a substance introduced to reduce friction between moving surfaces.

The process by which friction between sliding surface is reduce, known as Lubrication.
Types of lubricants:
[Link] lubricants or oils
e.g., vegetable oils, mineral oils, blended oils, synthetic oils.
[Link]-solid lubricants
e.g., Lime/ Calcium soap base grease, sodium soap grease, barium soap grease etc.
3. Solid lubricants
e.g., Graphite, Soap, Refractories, Ceramics, chemically active lubricants etc.
[Link]
e.g., o/w emulsion and w/o emulsion.

Functions of lubricants
Lubrication – Provide a film between moving parts.
Cooling – Heat transfer media.
Sealing – Filling in uneven surfaces
Cleaning – Holding contaminants in suspension.
Dampening & Cushioning – Of components under high stress.
Protection – From oxidation & corrosion.
Mechanism of Lubrication
a) Thick Film or Fluid Film or Hydrodynamic
Lubrication: It is carried out with the help of liquid
lubricants. In this mechanism, two moving and sliding
surfaces are separated by thick film of lubricant fluid
of about 1000A°. Fluid film lubrication is useful in
delicate and light machines like watches, clocks, guns,
scientific equipment.
b) Thin Film or Boundary Lubrication: It is carried
out with semi-solid (grease) and solid (and graphite
molybdenum disulphide) lubricants. Boundary lubrication is
a condition in which the lubricant film becomes too thin to
provide total separation. Thin film lubrication is operating
at relatively low speed and heavy loading (pressure).
c) Extreme Pressure (or Temperature) Lubrication: In
this mechanism, moving or sliding surfaces are under high
pressure and speed, therefore this is known as extreme pressure lubrication. In such a case high
temperature generated due to friction, under these condition liquid lubricants are fail to stick and
decompose or vaporize. These problems are minimized by special additives are added to mineral
oils. Important additives are organic compound having group like chloride, sulphur, phosphorus etc.

Properties of Lubricants

a) Cloud Point: The temperature at which lubricating oil becomes cloudy in appearance is called
cloud point.
b) Pour Point: The lowest temperature at which the lubricant oil become semi-solid and ceases to
flow is called pour point. Good lubricant should possess low pour point.
c) Flash point: The flash point of a volatile material is the lowest temperature at which vapours of
the material will ignite for a moment when an ignition source brought near to it. The lubricating oil
should have flash point reasonably above its working temperature.
d) Fire point: The fire point of a fuel is the lowest temperature at which the vapour of that fuel will
continue to burn for at least 5 seconds when an ignition source brought near to it.
Fire point is around 10oC higher than flash point.
e) Viscosity: Viscosity is the property of a fluid that determines its resistance to flow. If temperature
increases viscosity of the lubricating oil decreases and pressure increases viscosity of lubricating oil
increases. In short, we can say that good lubricating oil is that whose viscosity does not change with
temperature.
f) Viscosity Index: The variation of viscosity of a liquid with temperature is called viscosity index. A
relatively small change in viscosity with temperature is indicated by high viscosity index whereas, a
low viscosity index shows, a relatively large change in viscosity with temperature.
g) Saponification: It is defined as the no. of mg of KOH required to saponify 1 gm of oil.
The determination of saponification value helps to know the presence of animal and vegetable oils in
a lubricant.
Functions of lubricants: 1. It avoids direct contact between the rubbing surfaces and reduces
surface deformation, wear, tear and seizure.
2. It acts as a coolant by reducing loss of energy in the form of heat.
[Link] enhances efficiency of a machine by reducing wastage of energy and expansion of metal by local
frictional heat.
4. It avoids seizure and relative motion of moving surfaces, such that running cost of the machine
will be reduced.
5. Lubricant used between piston and the cylinder wall of an internal combustion engine acts as a
seal and can prevent the leakage of gases from the cylinder under high pressure.

Application of Lubricants
i) Lubricants are primarily used to reduce the friction between two moving surface.
ii) Rust and corrosion inhibitors
iii) Used in the soap and paint industries.
iv) Liquid lubricants are used in medicines
v) Lubricants are also used as cutting fluid in cutting, grinding, drilling of metals.
vi) Used as anti-wear, antioxidants, and antifoaming agents
vii)Lubricants transfer heat and acts as coolants.

Building Materials

Cement: Concrete is most widely used non-metallic material in construction of buildings, dams,
bridges, high ways etc. In concrete, cement is the essential bonding material which binds sand and
rock when mixed with water.
Cement is a dirty greenish heavy powder and finds its importance as a building material. It can be
described as material possessing adhesive and cohesive properties and capable of bonding materials
like stones, bricks, building blocks etc. Cement has the property of setting and hardening in the
presence of water. So it is called as hydraulic cement. The essential constituents of cement used for
constructional purposes are compounds of calcium (calcareous) and Al +Si (argillaceous).
Portland cement: It is most widely used non-metallic material of construction. It is a mixture of
calcium silicates and calcium aluminates with small amount of gypsum. The name Portland cement
is used because this powder on mixing with water gives a hard, stone like mass which resembles
Portland rock. All Portland cements are hydraulic in nature.

Composition of Portland cement: -

 Calcium Oxide or lime (CaO) : 60-70%

 Silica (SiO2) : 20-24%
 Alumina (Al2O3) : 5-7.5%
 Magnesia (MgO) : 2-3%
 Ferric Oxide (Fe2O3) : 1-2.5%
 Sulphur trioxide (SO3) : 1-1.5%
 Sulphur Oxide (Na2O) : 1%
 Potassium Oxide (K2O) : 1%
Setting and Hardening of Cement

When water is added and mixed to cement to form cement

paste, start hydration, convert into gel and crystalline material.
Solidification, interlocking and binding of the aggregates into
a rock-like matter is two-step process, they are setting and
hardening.

Setting: It is the stiffening of the cement paste with the formation of gel setting that is divided into
initial setting and final setting.

Initial setting: It is hydration and gel formation from the different constituents of cement.

C3A+6H2O → C3A .6H2O + Heat

Tricalcium aluminate Crystalline hydrated
Tricalcium aluminate

C4AF+ 7H2O → C3A.6H₂O + CF.H2O + Heat

Tetra calcium Crystalline gel
alumina ferrite

During the hydration of dicalcium silicate gives tobermonite gel, which possesses very high surface
area and high adhesive property.

2C2S+4H2O → C3S₂ .3H2O + Ca (OH)2 + Heat

Dicalcium silicate Tobermonite gel crystalline

Final setting: It is the complete formation of tobermonite gel.

Hardening: Hardening is the development of strength with the crystallization of calcium hydroxide
and hydrated tricalcium aluminate.

2C3S+6H2O → C3S2 .3H2O + 3Ca (OH)2 + Heat

Tricalcium silicate Tobermonite gel Crystalline calcium hydroxide

3C3A+6H₂O → C3A .6H₂O + Heat

tricalcium aluminate Crystalline hydrated tricalcium aluminate
 Unit -5
Surface Chemistry and Nano Materials
INTRODUCTION: Surface Chemistry is closely related to interface and colloidal science.
Surface chemistry is important in many critical chemical processes, such as enzymatic
reactions at biological interfaces found in cell walls and membranes, in electronics at the
surfaces and interfaces of microchips used in computers, and the heterogeneous catalysts
found in the catalytic converter used for cleaning emissions in automobile exhausts.
Definition: It is defined as the study of chemical reactions at interfaces.
Important Terms:
Adsorption: The accumulation of molecular species at the surface rather than in the bulk of a
solid or liquid is termed adsorption
Example: Adsorption of gas by charcoal
Absorption: It is the phenomenon in which a substance is uniformly distributed throughout
the bulk. Example: Water vapours are absorbed by anhydrous CaCl2.
(i) Adsorbent: The solid substance on the surface of which adsorption occurs is known as
adsorbent.
(ii) Adsorbate: The substances that get adsorbed on the solid surface due to intermolecular
attraction are called adsorbate.
(iii) Sorption: In some cases, both absorption and adsorption occur together and are not
distinguishable. Such a phenomenon is called sorption.
(iv) Desorption: The process of removal of an adsorbed substance from a surface on which it
is absorbed is called desorption

Types of adsorptions:
Colloids:
Colloidal solutions are heterogenous in nature and always consist of at least two phases: the
dispersed phase and the dispersion medium.
Example: milk, smoke
Dispersed Phase: It is the substance present in small proportion and consists of particles of
colloids size (1 to 100 nm)
Dispersion Medium: It is the medium in which the colloids particles are dispersed.
For example, in a colloidal solution of sulphur in water, sulphur particles constitute the
‘dispersed phase’ and water is the ‘dispersion medium’

Micelle Formation:
1. Micelles are the cluster or aggregated particles formed by association of colloid in
solution.
[Link], a micelle is made up of at least 100 molecules of the constituent material.
3. The common examples of micelles are soaps and detergents.
4. The formation of micelles takes place above a particular
temperature called Kraft temperature (Tk) and above a particular
concentration called critical micellization concentration (CMC)
5. Micelles may contain as many as 100 molecules or more.
[Link] example, sodium stearate (C17 H35COONa) is a typical
example of such type of molecules.
7. When sodium stearate is dissolved in water, it gives
Na  and C17 H35COO ions.
8. When soap is dissolved in water, the carbon chain i.e., hydrophobic end gets attracted
towards the oil, dirt and grease.
[Link] hydrophilic end which is attracted by water molecules points outwards thus, the
micelle formation takes place.
Synthesis of Colloids:
1. Bredig's arc method or electrical disintegration is a method
of preparation of colloidal solution, of metals such
as gold, silver or platinum.
2. Metal electrodes are dipped in the dispersion medium and an
electric arc is struck between these electrodes.
3. By doing so, intense heat is generated that helps in the vaporization of metal.
4. Then, condensation of metal takes place and results in the formation of particles having
colloidal size.
Stabilization of colloids:
Colloids must be stabilised in order to keep the dispersed particles uniformly distributed
throughout the medium and avoid coagulating or precipitating.
This can be accomplished by using a variety of stabilising chemicals, also referred to as
protective colloids or colloidal stabilisers.
1. Surface-Active Agents:
Surface-Active Agents, or surfactants, are compounds that have both hydrophilic and
hydrophobic components. The addition of surfactants to a colloidal system result in the
formation of a monolayer around the colloidal particles, which acts as a barrier to prevent
particle fusion. Soap and detergents are common examples.
2. Peptization: The process of conversion of a precipitated substance into colloidal solution
by the addition of a small amount of electrolyte is called peptization.
The electrolyte used for peptization process is called peptizing agent.
Ex: Ferric hydroxide Fe (OH)3 is
peptized by ferric chloride giving
positive sol of [Fe (OH)3] Fe3+

During peptization the precipitate

adsorbs one of the ions of electrolyte on its surface. This cause of development of charge on
precipitate which ultimately breakup to colloidal particle.
[Link] Stabilisers: Colloids can be stabilised by using polymer like polyvinyl alcohol
(PVA) These polymers create steric barrier and repulsion between the particles by binding to
the surface of the colloidal particles. By doing this, they are kept from getting too close and
coagulating.
[Link] of Solvent: The stability of colloids can be affected by the solvent used. Some
colloids are more stable in specific solvents due to favourable interactions between the
solvent and the dispersed particles. Choosing the right solvent can help maintain the colloidal
stability.
Applications of colloids:
1. Colloids are used in the medicinal industry such as colloidal sulphur and calcium is used in
making medicines.
2. An antacid that is used to treat stomach problems is a colloid.

3.A colloid can also be used in the food industry such as milk, whipped cream, butter, and
curd.
[Link] are used in water treatment, soil remediation, and air purification.
[Link] are used in metallurgy during froth floatation
6. Colloids like copper colloids are used as anti-cancer medications.
7. These are used as fungicides and pesticides

Adsorption Isotherms:
The process of Adsorption is usually studied through graphs called as adsorption isotherm. It
is the graph between the amounts of adsorbate (x) adsorbed on the surface of adsorbent (m)
and pressure at constant temperature.
Freundlich adsorption isotherm:
Freundlich provided an empirical relationship between the amount of gas adsorbed by a unit
mass of solid adsorbent and pressure at a particular temperature. It is expressed using the
following equation –

x/m = k.P1/n (n > 1)

where ‘x’ = mass of the gas adsorbed

‘m’ = mass of the adsorbent
‘P’ = pressure
‘k’ and ‘n’ = constants of Freundlich adsorption
isotherms.

The mass of the gas adsorbed per gram of the adsorbent is

plotted against pressure in the form of a curve to show the
relationship. Here, at a fixed pressure, physical adsorption
decreases with increase in temperature. The curves reach
saturation at high pressure
Now, if you take the log of the above equation –

log x/m = log k + 1/n log P

To test the validity of Freundlich isotherm, we can plot log

x/m on the y-axis and log P on the x-axis. If the plot shows a
straight line, then the Freundlich isotherm is valid, otherwise,
it is not. The slope of the straight line gives the value of 1/n,
while the intercept on the y-axis gives the value of log k.

Limitations of Freundlich Isotherm

Freundlich isotherm only approximately explains the behaviour of adsorption. The value of 1/n
can be between 0 and 1, therefore the equation holds good only over a limited range of pressure.

 When 1/n = 0, x/m is constant, the adsorption is independent of pressure.

  When 1/n =1, x/m = k P, i.e. x/m 𝖺 P, adsorption is directly proportional to
pressure.
At high pressure, the experimental isotherms always seem to approach saturation. Freundlich
isotherm does not explain this observation and therefore, fails at high pressure.

Langmuir adsorption isotherm: Some of the major Langmuir adsorption isotherm

assumptions are
1. Adsorption is always monolayer.
2. The adsorbed layer is homogeneous across the adsorbent.
3. No interaction between the molecules that are adsorbed next to one another.
4. Each adsorbent has different energy sites, but the adsorption energy is the same for all of
them.
5. Adsorption is a reversible process.
Langmuir proposed that dynamic equilibrium exists between adsorbed gaseous molecules and
the free gaseous molecules.
Limitations:
 Describe only the formation of the monolayer.
 The effect of temperature on adsorption is not considered.

BET Equation:

1. BET adsorption isotherm proposed by Brunauer, Emmett, and Teller accounts for
multilayer adsorption.
2. According to the theory, adsorption takes place only on specific areas of the sample
surface (one per molecule), and doesn’t stop at monolayer formation
3. That is after the monolayer has formed, the adsorption process proceeds to the
formation of the multilayer forming second, third, and so forth layers.
4. BET theory also considers that adsorption sites on the solid surface are homogenous
and that adsorption at one site has no effect on adsorption at nearby sites.

Nano Materials: Nanomaterials are materials having at least one of their dimensions (length or
width or height) in the range of 1-100 nm.

1 nm = 10-9m = 10Å.

Examples of various Nano metal oxides are TiO2, ZnO

Preparation of Nanomaterials:
1. Preparation of nanomaterials by precipitation method (chemical method)

Synthesis involves mixing two or more solutions containing metal ions. When the solutions
are mixed, metal ions precipitate out of the solution and form nanoparticles.
𝐹𝑒𝐶𝑙3 + 3𝑁𝐻4𝑂𝐻 → 3𝑁𝐻4𝐶𝑙 + 𝐹𝑒(𝑂𝐻)3
𝐹𝑒𝑆𝑂4 + 3𝑁𝐻4𝑂𝐻 → 𝐹𝑒(𝑂𝐻)2 + (𝑁𝐻4)2𝑆𝑂4
2𝐹𝑒(𝑂𝐻)3 + 𝐹𝑒(𝑂𝐻)2 → 𝐹𝑒3𝑂4 (𝑛𝑎𝑛𝑜𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠)↓ + 4𝐻2𝑂
First, the beaker containing Iron (III) chloride and iron (II) sulphate solution is placed on a
hot plate at room temperature or 70 ℃ and keeps a magnetic stirrer bar inside the solution.
Then the solution is stirring continuously by adjusting the stirring speed around 1000 rpm for
10 min. Then ammonium hydroxide is added drop wise slowly to this mixture until the black
precipitate is formed at pH between 9-10. Then the precipitate is filtered through a filter
paper and dried in a furnace around 200 ℃ for 2 h. Finally, the iron (III) oxide nanoparticles
are formed. The magnetic properties of these particles are tested with the real magnets.

2. Sol-gel process: (chemical method)

1. The sol-gel method is one of the versatile chemical methods to
synthesize metal/metal oxide nanomaterials at low temperature
and low cost. This method is used for inorganic ceramics, glass
materials, and catalyst synthesis with high purity, fine-scale and
high homogeneity. Ex: TiO2, SnO2, Fe2O3-SiO2, NiO-SiO2

2. In this process, alkoxide and water are dissolved in a common

alcoholic solvent. The process involves the generation of a colloidal
suspension (sol) which is then converted to viscous gel by aging ( a
3-D continuous network, which encloses liquid phase). The
removal of solvents, appropriate drying and heat treatment
(calcination or annealing) produces the required nanoparticles.

3. The two main primary reactions involved in the sol-gel technique: (1) hydrolysis of the precursor in the
acidic or basic mediums and (2) polycondensation of the hydrolyzed products. This results in the
generation of a polymeric network that is retained with the metal nanoparticles.

Biological methods for synthesis of Nano Materials:

Biological methods of synthesizing nanoparticles involve the use of living organisms or their
components to produce nanoparticles. These methods are often considered environmentally
friendly and cost-effective compared to traditional chemical synthesis methods. Here are
some common biological methods for synthesizing nanoparticles.
A) Synthesis of Nanoparticles from Plants

Plants have biomolecules (like carbohydrates, proteins, and coenzyme) with exemplary
potential to reduce metal salt into nanoparticles. Various plants like aloe vera, Tulsi, Lemon,
Neem, Coriander, Mustard and lemon grass have been utilized to synthesize silver
 nanoparticles and gold nanoparticle
Synthesis of Silver Nanoparticles by Leaf Extract:
[Link] leaves of desired plant, wash & cut in small pieces
[Link] the magnetic stirrer
[Link] 25g of leaves in 100ml of De-ionised Water
[Link] Temperature to 80-90°C
[Link] the Green extract in Burette to use as Reducing and Capping agent
[Link] 10mg Silver Nitrate in 50ml De-ionised Water
7. Set Temperature to 60-70°C
8. Add Leaf extract dropwise very slowly until the light-yellow colour forms.
[Link] light-yellow colour indicates the formation of silver Nano particles.

B) Synthesis of Nanoparticles from Microbes

Microbial Synthesis: Microorganisms like bacteria, fungi, and algae are used to produce
nanomaterials. They act as natural factories, reducing metal ions into nanoparticles through
enzymatic processes. This method is eco-friendly and operates under mild conditions. This
approach is often referred to as "biosynthesis" or "biogenic synthesis"
Bacteria: Certain bacteria can reduce metal ions to form nanoparticles. For example,
Pseudomonas aeruginosa synthesizes silver nanoparticles, which are useful for their
antimicrobial properties. Also, E. coli, a bacterium that is commonly found in the lower
intestine of warm-blooded organisms havebeen used to synthesize silver nanoparticles.
Fungi: They act as better biological agents for the preparation of metal and metal oxide
nanoparticles, due to the presence of a variety of intracellular enzyme. For example,
Candida albicans was used to synthesize CdSe nanoparticles. Also, Different species of
Fusarium can produce nanoparticles such as silver, gold, platinum, silica, and
palladium.
.
Aplications of Nano Materials:
1. Nano materials provide a high surface area per unit mass or volume. This increased surface
area is beneficial for catalysis.
[Link] materials are widely used in heterogeneous catalysis
[Link] materials, including platinum and palladium nanoparticles, are used as catalysts in
fuel cells
[Link] are used as carriers for vaccine delivery, improving the stability and efficacy
of vaccines.
[Link] materials with antimicrobial properties are employed in the development of
antibacterial agents.
[Link] materials, including nanoparticles and nanofibers, are used in wound dressings to
promote faster healing.
[Link] materials enable targeted drug delivery to cancer cells, minimizing damage to healthy
tissues.
[Link] materials are employed in chemical sensors for the detection of specific chemical
compounds.
[Link] play a crucial role in biosensors for the detection of biological molecules
such as proteins, DNA, and enzymes.
Stabilization of Nano materials:

Nanomaterials, due to their high surface-to-volume ratio, exhibit unique properties that make
them valuable in various applications.

1. Surface Functionalization:
 Coating the surface of nanomaterials with inert materials or molecules to
minimize reactivity.
 Introduction of specific functional groups on the surface of nanomaterials
creates a protective layer and enhancing stability.
2. Polymer Coating:
 Aggregation is inhibited when nanomaterials are protected in a polymer
matrix, which acts as a barrier against outside influences.
3. Surfactant Stabilization:
 By lowering inter-particle forces, surface-active chemicals create a stabilising
layer surrounding nanomaterial to stop them from clustering together.
4. Inorganic Coatings:
 Coating nanomaterials with silica imparts stability and protects against
environmental factors.
 Nanoparticles coated with metal oxides, such as titanium dioxide, gain
stability and resistance to aggregation