Chemistry Handout

Matrusri Engineering College B.E.
- Chemistry 1
CHEMISTRY HANDOUT
FOR STUDENTS OF B.E. FIRST YEAR
(AICTE MODEL CURRICULUM)
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Matrusri Engineering College B.E. - Chemistry 2
UNIT-I: ELECTROCHEMISTRY
1. Differentiate single electrode potential and standard electrode potential.

Single electrode potential is the potential of a half-cell in galvanic cell at non-standard
conditions. Standard electrode potential is the potential of an electrode at 25 0C
temperature, 1 atm pressure acting at 1M electrolyte solution.
2. Explain the relation between EMF and change in free energy?
The Gibbs free energy change is related to cell EMF by ΔG = -nFE. When EMF of the
cell is +Ve, ΔG is -Ve, the electrochemical reaction is spontaneous and feasible.
3. What is salt bridge? What is its role in Galvanic cell?
Salt Bridge: It is an inverted ‘U’ shape tube open at both the ends, it contains inert
electrolytes such as KCl, KNO3, NH4NO3 etc., mixed with agar-agar gel to make it as semi
solid paste.
Role of salt bridge:

i) It connects the two solutions and prevents their intermixing.
ii) It prevents the accumulation of charges around the electrode.
iii) It allows the movement of anions from cathodic solution to anodic solution.
iv) It maintains electrical neutrality of solution and this completes the circuit.
4. Derive Nernst equation? Give its applications.

NERNST EQUATION: The electrode potentials and emf of the cell depends on the nature of
the electrodes, temperature and activities (concentrations) of ions in solution. It
establishes the relationship between the concentrations of electrolyte solutions and emf .
Let us consider a galvanic cell whose cell reaction is written as
aA + bB → cC + dD
Where lower case letters a, b, c, d represent the number of moles of A, B, C, D
[C]c [D]d
respectively at equilibrium. The equilibrium constant for above equation K = [A]a [B]b =
activity coefficient = Q
Nernst equation can be derived from Vant Hoff’s isotherm
∆G = ∆G0 + RTlnQ --------------(1)
From the thermodynamics ∆G = - nFE and ∆G0 = -nFE0
By substituting the above values in equation (i)
-nFE = -nFE0 + RTlnQ
By dividing the equation with -nF on both sides,
𝑅𝑇
𝐸 = 𝐸0 − 𝑙𝑛𝑄
𝑛𝐹
2.303𝑅𝑇 [𝐶]𝑐 [𝐷]𝑑
𝐸 = 𝐸0 − 𝑙𝑜𝑔 𝑎 𝑏 𝑜𝑟
𝑛𝐹 [𝐴] [𝐵]
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2.303𝑅𝑇 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
𝐸 = 𝐸0 − 𝑙𝑜𝑔
𝑛𝐹 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠]
Where E denotes the emf of the cell, R the gas constant, T the temperature, n
number of faradays of current F passed, K the equilibrium constant and the quantities in
the square brackets refer the respective concentration.
At room temperature T= 298 K, taking = 8.314 J K-1, F=96500 C. the above equation
simplifies to
0.0592 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
𝐸 = 𝐸0 − 𝑛
𝑙𝑜𝑔 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠] at 250C
From the above equation we notice that the standard cell emf is equal to the cell
emf when the activities of both reactants and products are equal to unity.
For a Redox reaction: Zn + Cu2+ → Zn2+ + Cu
0
2.303𝑅𝑇 [𝑍𝑛2+ ][𝐶𝑢]
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙
− 𝑙𝑜𝑔
𝑛𝐹 [𝑍𝑛][𝐶𝑢2+ ]
Since, [Zn] and [Cu] are unity
For a reduction reaction: Mn+ → M + ne-
0 0.0592 [𝑀]
At 250C, 𝐸𝑀𝑛+/𝑀 = 𝐸𝑀 𝑛+ /𝑀 −
𝑛
𝑙𝑜𝑔 [𝑀𝑛+ ]
Since, [M] = 1
0 0.0592
Above equation become, 𝐸𝑀𝑛+/𝑀 = 𝐸𝑀 𝑛+ /𝑀 +
𝑛
𝑙𝑜𝑔𝑀𝑛+
Applications of Nernst Equation:

i. It is used to study the effect of electrolyte concentration on electrode potential.
ii. To calculate single electrode potential of a half cell.
iii. Used for calculation of cell potential under non-standard conditions.
0
iv. pH of solution can be calculated. Ecell = Ecell − 0.0591pH
v. It is helpful to determine the unknown concentration of one of the ionic species of cell
if E0 cell and concentration of other species is known.
vi. Used for finding the valence of number of e- involved in a reaction.
5. Calculate the Ecell of the following cell at 250C by using Nernst Equation.
Zn|Zn2+ (0.01M) || Ag+ (0.01M) | Ag (𝑬𝟎𝑨𝒈+ = 𝟎. 𝟖𝟎𝟏 𝑽 𝒂𝒏𝒅 𝑬𝟎𝒁𝒏𝟐+ = −𝟎. 𝟕𝟔𝟒 𝑽)
⁄𝑨𝒈 ⁄𝒁𝒏
Solution:
Cell Reactions: Anode: Zn → Zn2+ + 2e-
Cathode: 2(Ag+ + 2 e- → Ag)
Overall cell reaction: Zn + 2Ag+ → Zn2+ + 2Ag
Applying Nernst equation to Cell reaction:
0 0.0592 [𝑍𝑛2+ ]
At 250C, 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔
𝑛 [𝐴𝑔+ ]2
0 0 0
Now, 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 = 0.801 – (-0.764) = 1.565 V
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0.0592 10−2
Then, 𝐸𝑐𝑒𝑙𝑙 = 1.565 − 𝑙𝑜𝑔
2 (10−2 )2
= 1.565 – 0.0592 = 1.5058 V

6. Describe the construction of calomel electrode with its electrode reaction,
potential with well labeled diagram?
It is a secondary reference electrode consisting of mercury-mercurous chloride (Hg-Hg2Cl2)

paste in contact with KCl solution.
Construction: It consists of a plug at the bottom of which a small amount of Hg is placed.

This is covered with a paste of solid mercury-mercurous chloride (calomel paste). The
solution of KCl is placed over the paste and a platinum wire is employed for electrical
contact. The potential of calomel electrode depends on KCl solution.
It is represented as: Pt Hg, Hg2Cl2 KCl
Electrode reaction: Hg2Cl2 + 2e- 2Hg + 2Cl-
Electrode potential:
0
0.0592 [𝐻𝑔]2 [𝐶𝑙 − ]2
𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 − 𝑙𝑜𝑔
𝑛 [𝐻𝑔2 𝐶𝑙2 ]
𝑆𝑖𝑛𝑐𝑒, [𝐻𝑔] = [𝐻𝑔2 𝐶𝑙2 ] = 1
0
0.0592
𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 − 𝑙𝑜𝑔[𝐶𝑙 − ]2
2
0
𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 − 0.0592log [𝐶𝑙 − ]
The calomel electrode is reversible to Cl- ion concentration.
The standard reduction potential of calomel electrode at 250C is
0.1M KCl | Hg2Cl2(s) | Hg, Pt 0.3338V Decinormal Calomel Electrode(DNCE)
1.0M KCl | Hg2Cl2(s) | Hg, Pt 0.2800V Normal Calomel Electrode (NCE)
Sat. KCl | Hg2Cl2(s) | Hg, Pt 0.2415V Saturated Calomel Electrode (SCE)
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7. What is Quinhydrone? Explain the determination of pH of a solution using

Quinhydrone electrode?
Quinhydrone electrode: Quinhydrone is a 1:1 equimolar mixture of quinone and
hydroquinone which exist in equilibrium in presence of H + ions.
Quinhydrone electrode is setup by adding a pinch of Quinhydrone to the solution

whose pH is to be measured. A Pt electrode is placed in it to acquire potential. The
potential developed on a Pt electrode immersed in this system is given by Nernst equation
as:
2.303RT [QH ]
EQHE = E0QHE – log[Q][H2+ 2
2F ]
at 250C the equation may written as

0.0591 [Q][H+ ]2
EQHE = E0QHE + 2
log [QH2 ]
Since Quinhydrone is sparingly soluble salt, concentration terms [Q] and [QH 2] are
termed as unity.
Hence, EQHE = E0QHE + 0.0591 log [H+]
Since, pH = - log [H+]
EQHE = E0QHE – 0.0591pH

OR
EQHE = 0.6996 – 0.0591pH
Thus, the potential of Quinhydrone electrode depends on the pH of the solution
with which it is in contact. Therefore, it can be used for the measurement of pH.
Determination of pH using Quinhydrone electrode: The potential of Quinhydrone

electrode (QHE) is determined by connecting it with a saturated calomel electrode (SCE).
The combination may be represented as:
Pt | Hg, Hg2Cl2(s) | KCl(saturated) || H+ (unknown) | Q, QH2 | Pt
The emf of the cell Ecell = EQHE - ESCE
Ecell = (0.6996 – 0.0591pH) – 0.242 V

0.4576−Ecell
pH = 0.0591
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8. What is ion selective electrode? Explain construction and working of glass

electrode.
Ion selective electrode is the electrode which possesses the ability to respond only to
certain specific ions there by developing a potential with respect to those ions and ignoring
the other ions totally.
Glass electrode: The typical glass electrode consists of thin-walled glass bulb containing Pt
wire of AgCl coated, dipped in 0.1N HCl solution. The glass membrane acts as an ion
exchange resin which is highly pH sensitive. Glass bulb, when in contact with acid test
solution furnishes a constant H+ ion concentration on both sides which is responsible for
potential difference. This potential difference is directly proportional to the pH difference
between solutions on both sides of glass.
It is represented as: Pt | Ag, AgCl | 0.1N HCl | Glass membrane
Electrode Reaction: AgCl + e- AgCl
Eglass = E0glass + 0.0592 pH
9. How do you relate the cell EMF with Enthalpy and Entropy?
Enthalpy and EMF:

From thermodynamics
∆G = ∆H - T∆S
According to Gibbs-Helmholtz equation
∂(∆G)
∆G = ∆H + T ( )
∂T P
Since, ∆G = -nFE
∂(−nFE)
−nFE = ∆H + T ( )
∂T P
∂E
−nFE = ∆H − nFT ( )
∂T P
𝛛𝐄
∆𝐇 = −𝐧𝐅𝐄 + 𝐧𝐅𝐓 ( )
𝛛𝐓 𝐩
∂E
Here, the (∂T) is called Temperature Coefficient of the cell.
P
∂E
If (∂T) = 0, then Electrical energy is equal to Enthalpy of the cell reaction. EMF of
P
the cell increases with temperature.
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Entropy and EMF:

From thermodynamics
∆G = ∆H - T∆S ----------(1)
Since,
∂E
∆H = −nFE + nFT ( )
∂T p
and
∆G = -nFE
Then equation (1) can be written as

∂E
−nFE = −nFE + nFT ( ) − T∆S
∂T p
Then,
∂E
T∆S = nFT ( )
∂T p
And
∂E
∆S = nF ( )
∂T p
10. Differentiate between primary and secondary batteries.
Primary cells: A primary cell is the one in which electrical energy can be obtained at the
expense of chemical energy only as long as the active materials are still present. Once
these have been consumed, the cell cannot be profitably or readily rejuvenated and must
discarded. Or in other words, they cannot be recharged and re-used.
Ex;- dry cell ( Leclanche cells)
Secondary cells: These cells are rechargeable and reusable. A combination of all
reversible electrochemical cells gives secondary batteries. The secondary cells can be used
through a large number of cycles of discharging and charging.
Ex:- Lead-acid cells, Nickel-Cadmium cell, Lithium cells
11. Describe the construction and working of Zn-C cell with relevant reactions.
Zinc – Carbon Battery (Dry cell): The dry cell is a primary cell. It consists of a cylindrical
zinc container, acting as the anode containing an electrolyte consisting of NH4Cl, ZnCl2
and MnO2 to which starch is added to make it thick paste-like so that it is less likely to
leak. A graphite rod serves as cathode, which is immersed in the electrolyte in the centre
of the cell.
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Electrode reactions:
At anode: Zn → Zn2+ + 2e-
At cathode: 2MnO2 + H2O + 2e- → Mn2O3 + 2OH-
The overall cell reaction: Zn + 2MnO2 + H2O → Zn2+ + Mn2O3 + 2OH-
The cathode reaction involves the reduction of Mn+4 to Mn+3 oxidation state.
Secondary reactions:
The hydroxyl ions generated during the cell reactions liberate ammonia from
ammonium chloride which disrupts the current flow.
2NH4Cl + 2OH- → 2NH3 + 2H2O + 2Cl-
This is prevented by a reaction of NH3 with Zn2+ ion to form the [Zn(NH3)2]Cl2
complex.
Zn2+ + 2NH3 + 2Cl- → [Zn(NH3)2]Cl2
The secondary reactions are not involved directly in the electrode reaction and so
they do not contribute to the emf of the cell. But these reactions are irreversible and
therefore, the cell cannot be recharged.
A fresh dry cell has a potential of 1.5V. The voltage of the cell decreases gradually
with usage and finally it has to be discarded.
Applications: Dry cell find extensive use in flash lights, portable radios, transistors, tape
recorders and similar electronic devices where small amount of current is required.
12. Describe the construction of Lead Acid battery with reactions occurring
during Discharging and Charging?
Lead-Acid Battery: This storage cell has the great advantage of working both as an
electrolytic cell and as a voltaic cell.
The electrodes are lead grids. The anode grid is filled with spongy lead and the
cathode grid is filled with lead dioxide (PbO2). A number of lead plates are connected in
parallel and a number of lead dioxide plates are also connected in parallel. The lead plates
fits in-between the lead dioxide plates. Various plates are separated from the adjacent
ones by insulators like strips of wood or rubber or glass fibre. The entire combination is
then immersed in approximately 20 to 21% dil. H2SO4, corresponding to a density of 1.2 to
1.3.
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Discharging: When the storage cell is operating as a voltaic cell, it is said to be

discharging. The lead electrode loses electrons, which flow through the wire. In this
reaction, oxidation of lead takes place at the anode.
At anode: Pb → Pb2+ + 2e-
Pb2+ + SO42- → PbSO4
Pb + SO42- → PbSO4 ↓ + 2e-
The electrons released from the anode flow to the dioxide electrode (cathode). Here
PbO2 gains electrons and reduced from +4 to +2 oxidation state.
At cathode: PbO2 + 4H+ + 2e- → Pb2+ + 2H2O
Pb2+ + SO42- → PbSO4
PbO2 + 4H+ + SO42- + 2e- → PbSO4 ↓ + 2H2O
The net cell reaction during discharging:
Pb + PbO2 + 2H2SO4 → 2PbSO4 ↓ + 2H2O + Energy
It may be noted that lead sulphate is precipitated at both the electrodes. The
voltage of each cell is about 2.0 volts at a concentration of 21.4% H 2SO4 at 250C. Lead cell,
commonly used in automobiles, is combination of six such cells in series to form a battery
with an emf of 12volts.
Charging: When both anode and cathode become covered with PbSO 4, the cell
ceases to function as a voltaic cell. To recharge a lead storage cell, the reactions taking
place during discharging are reversed by passing an external emf greater than 2 volts from
a generator.
At cathode: PbSO4 + 2e- → Pb

At anode: PbSO4 + 2 H2O → PbO2 + 4H+ + SO42- + 2e-
Hence, net reaction during charging: 2PbSO4 + 2 H2O + energy → Pb + PbO2 +

2H2SO4
During the process of charging, the electrodes of cell are restored to their original
conditions. It may be also noted that during discharging operation, the concentration of
acid decreases; while the concentration of acid increases during the charging operation.
Applications of lead storage cells: The lead storage cells are used to supply current for
electrical vehicles, gas engine ignition, in telephone exchanges, electric trains, mines,
laboratories, and hospitals, broadcasting stations, automobiles and power stations.
Limitations of lead storage cells: If the cell voltages exceed 2.39 V, the water breaks
down into hydrogen and oxygen and may lead to explosion. Another problem arising from
this system is that fumes from the acid solution may have a corrosive effect on the area
surrounding the battery.
13. Write a note on Li ion secondary cells.
Lithium ion Battery: It consists of a graphite anode and lithium oxide cathode. Cathode
consists of a layered crystal into which the lithium is intercalated. Electrolytes are usually
LiPF6 although this has a problem with aluminum corrosion, and so alternatives are being
sought one such is LiBF4.
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Cell reactions in Lithium ion battery involve migration of lithium ions between the
positive and negative electrode. No chemical changes are observed at the two electrodes or
in the electrolyte. Lithium-Graphite intercalation can be charged and discharged reversibly
where lithium doping is charging reaction and un-doping is discharging reaction. During
charging of lithium ion batteries, Lithium ions are extracted by oxidation from LiCoO2
cathode and the extracted lithium ions are doped by electrochemical reduction into carbon
anode to form Li-GIC.
During discharging lithium ions are extracted from anode by electrochemical

oxidation and inserted into the cathode by electrochemical reduction.
During discharging:
At anode; x (LiC → C + Li+ + e-)
At cathode: LiCoO2 + x Li+ + x e- → LixCoO2
Over all reaction: x LiC + LiCoO2 → LixCoO2 + C
This cell produces 3.7V.

Applications: These are used in mobile phones and smart phones, laptops and tablets,
digital cameras, electronic cigarettes, hand held game consoles and torches etc.
14. What are fuel cells and their advantages? Describe in detail the working of
Methanol-Oxygen fuel cells? Write its applications?
A fuel cell is a device in which electric energy is obtained without combustion from
oxygen and a gas that can be oxidized. Hence, a fuel cell converts the chemical energy of
the fuels directly to electricity.
Methanol-Oxygen fuel cell: The cell consists of a porous nickel sheet on which
platinum-palladium catalyst is deposited as anode. The cathode consists of silver
impregnated porous nickel sheet. Alkaline electrolyte KOH is used. Methanol fuel is
continuously fed into anode and oxygen is supplied at cathode. These are adsorbed on the
respective electrodes, involves following reactions.
Electrode reactions: At the anode: CH3OH + 6OH- → CO2 + 5H2O + 6e-

At the cathode: 3/2 O2 + 3H2O + 6e- → 6OH-
Over all reaction: CH3OH + 3/2 O2 → CO2 + 2H2O
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Advantages of fuel cells:
• No emission of toxic gases and chemical wastes are in safe limits.

• No noise pollution like in generators and low thermal pollution.
• Low maintenance costs, fuel transportation costs, cell parts are modular and
exchangeable.
• Unlike solar cells, fuel cells are compact and transportable.
• Unlike acid cells used in automotives the fuel cells are far less corrosive.
• Fuel cells are operatable to 2000C and so find applications in high
temperature systems.
Applications of fuel cells: Fuel cells are used as auxiliary energy source in space
vehicles, submarine or other military-vehicles. The weight of the fuel battery sufficient for
15days is space is approximately 250Kg. The product water proved to be a valuable source
of fresh water by the astronauts.
UNIT-II: WATER CHEMISTRY AND CORROSION
1. Describe the estimation of hardness of water sample by EDTA Method.

Principle: This is a complexometric titration in which EDTA is used as a complexing
agent. The structure of disodium salt is shown as:
EDTA is a hexadentate ligand and forms stable complexes with most of the metal
ions in the pH range 10. A buffer solution of NH4Cl + NH4OH is used to maintain the pH.
To determine the equivalence point Eriochrome black-T (EBT) is used as an

indicator. It forms unstable winered colored complexes with Ca2+ & Mg2+ ions in the pH
range 10. When this solution is titrated against EDTA it combines with the free metal ions
in the beginning and the metal ions of the indicator complex at the end, displacing the
indicator. Therefore, the colour changes from wine red to blue at the endpoint.
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pH=10
M2+ + EBT [M-EBT] complex (wine red)
titration
[M-EBT] complex + EDTA [M-EDTA] complex + EBT
(Wine-red) (Blue)
Preparation of reagents:
1. Preparation of standard hard water: Dissolve 1 g of pure CaCO3 in minimum

quantity of dil.HCl and evaporate it to dryness on a water bath. Dissolve it in
distilled water and make up to 1L. Each mL of this solution thus contains 1 mg of
CaCO3 eq hardness.
2. Preparation of EDTA solution: Dissolve 4.0 g of pure EDTA crystals and add 0.1 g
of MgCl2 to it. Make up to 1L using distilled water.
3. Preparation of indicator: Dissolve 0.5 g of Eriochrome black-T in 100 ml of
alcohol.
4. Preparation of buffer solution: Add 67.5 g of NH4Cl to 570 ml of concentrated
ammonia solution and dilute with distilled water to 1L.
Experimental Procedure:
1. Standardization of EDTA solution: Rinse and fill the burette with EDTA solution.
Pipette out 50 ml of standard hard water in a conical flask. Add 10ml of buffer
solution and 3 or 4 drops of indicator, the color changes to wine red. Titrate it
against EDTA till the color changes to blue. Let the volume of EDTA be V1 ml.
50 ml of std. hard water = V1 ml of EDTA
i.e. 50 mg of CaCO3 eq. = V1 ml of EDTA
50
Hence, 1 ml of EDTA = V1
mg of CaCO3 eq.
2. Estimation of Total hardness: Pipette out 50 ml of water sample in a conical

flask. Add 10ml of buffer solution and 3 or 4 drops of indicator to it, the color
changes to wine red. Titrate it against EDTA till the color changes to blue. Let the
volume of EDTA be V2 ml.
50 ml of hard water = V2 ml of EDTA
50
= V1
x V2 mg of CaCO3 eq.
1000
1000 ml of hard water = V1
V2
Total hardness = V1
x 1000 ppm
3. Estimation of permanent hardness: Take 250 ml of the water sample in a large

beaker and boil it to one third of its volume, all the bicarbonates are precipitated as
carbonates. Filter, wash the precipitate with distilled water, and collect the filtrate
and washings in 250 ml volumetric flask. Makeup the volume using distilled water.
Page 12 of 42
Then titrate 50 ml of this water as under standardization. Let the volume of EDTA
be V3 ml.
50 ml of boiled water = V3 ml of EDTA
50
= V1
xV3 mg of CaCO3 eq.
1000
1000 ml of boiled water = V1
V3
Permanent hardness = x 1000 ppm
V1
4. Temporary hardness = [Total – Permanent] hardness

1000(V2 −V3 )
= V1
ppm
2. Discuss the water softening by ion – exchange process?

Removal of all ions present in water is called demineralization. The demineralization of
water is done by using Ion exchange resins.
Ion exchange resin: Ion exchange resins are insoluble, cross linked, long chain organic
polymers with a microporous structure. The ion exchange property of these polymers is
due to mainly the functional groups attached to them. These functional groups may be
acidic or basic. Based on functional groups the resins may be classified as: a) Cation
exchange resins b) Anion exchange resins.
Cation exchange resins (RH+): They are mainly styrene-di vinyl benzene copolymers,
which on sulphonation or corboxylation, -SO3H or –COOH groups are introduced to
polymers. They become capable to exchange their H+ ions with the cation in water.
Anion exchange resins (R’OH-): They are styrene-di vinyl benzene or amino formaldehyde
copolymers, which contain amino or quaternary ammonium or quaternary phosphonium
groups as an integral part of the resin matrix. These, after treatment with dil.NaOH
solution, become capable to exchange their OH- ion with the anions in water.
Page 13 of 42
Process: It consists of two tanks. Cation resins and anion resins are kept in the 1 st and
2nd tank respectively. The hard water first is passed through cation exchange column,
which removes all the cations like Ca2+, Mg2+ etc. from it, and equivalent amount of H+
ions are released from this column to water.
2 RH+ + Ca2+ → R2Ca2+ + 2 H+
2 RH+ + Mg2+ → R2Mg2+ + 2 H+
After cation exchange column, the hard water is passed through anion exchange
column, which removes all the anions like SO 42-, Cl-, etc. present in the water and
equivalent amount of OH- ions are released from this column to water.
R’OH-- + Cl- → R’Cl- + OH-

2R’OH- + SO42- → R’2SO42- + 2 OH-
2R’OH- + CO32- → R’2CO32- + 2 OH-
The H+ and OH- ions released from both the column get combined to produce water
molecule.
H+ + OH- → H2O
Thus, water coming out from the ion exchanger is free from cations as well as
anions. Ion free water is known as deionized or demineralized water.
Regeneration: When capacities of cation and anion exchangers lost to exchange H + and
OH- ions, they are then said to be exhausted.
The exhausted cation exchange resin is regenerated by passing a solution of dil.HCl

or dil.H2SO4.
R2Ca2+ + 2 H+ → 2 RH+ + Ca2+ (washings)

R2Mg2+ + 2 H+ → 2 RH+ + Mg2+ (washings)
The exhausted anion exchange resin is regenerated by passing a solution of
dil.NaOH.
R’2SO42- + 2 OH- → 2R’OH- + SO42- (washings)
R’2CO32- + 2 OH- → 2R’OH- + CO32- (washings)
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R’Cl- + OH- → R’OH-- + Cl- (washings)

The columns are washed with deionized water and washings which contain Ca 2+,
Mg2+, SO42- , Cl- ions are passed to sink or drain.
Advantages:
• The process can be used to soften highly acidic or basic waters.

• It produces water of very low hardness (2ppm), so it is very good for treating water
for use in high pressure boilers.
Disadvantages:
• The equipment is costly and more expensive chemicals are needed.

• If water contains turbidity, then the output of the process is reduced. The turbidity
must be below 10ppm. If it is more it has to be removed first by coagulation and
filtration.
3. What is reverse osmosis? How is sea water purified by this method? Or explain
the desalination of brackish by reverse osmosis method.
When two solutions of unequal concentrations are separated by a semi permeable
membrane (does not permit the ions, atoms, molecules etc.), flow of solvent takes place
from dilute to concentrated sides.
If, however, a hydrostatic pressure in excess of osmotic pressure is applied on the

concentrated side, the solvent flow reverses, i.e. solvent is forced to move from
concentrated side to dilute side across the membrane. This is the principle of reverse
osmosis.
Thus, in reverse osmosis process methods pure water is separated from its
contaminants, rather than removing contaminants from the water. This membrane
filtration is sometimes also called “super-filtration” or “Hyper filtration”.
Method: In this process, pressure of the order 15 to 40 kg cm 2- is applied to the sea

water/ impure water to force its pure water out through the semi permeable membranes;
leaving behind the dissolved solids.
The membrane consists of very thin film of cellulose acetate, affixed to either side of
a perforated tube. However, more recently superior membranes made of polymethacrylate
and polyamide polymers have come into use.
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Advantages:
• Reverse osmosis process is a distinct advantage of removing ionic as well as non-
ionic, colloidal and high molecular weight organic matter.
• It removes colloidal silica, which is not removed by demineralization.
• The maintenance cost is almost entirely on the replacement of the semi permeable
membrane.
• The life time of membrane is quite high, about 2years.
• The membrane can be replaced within a few minutes, there providing uninterrupted
water supply.
4. What are the specifications of potable water?

• Sparkling clear and odorless.
• Pleasant in taste.
• Perfectly cool.
• Turbidity should not exceed 10ppm.
• It should be free from objectionable minerals such as Pb, As, Cr, Mn salts.
• It should be free from objectionable gases like H2S.
• pH should be in range of 7.0 – 8.0. Alkalinity should not be high.
• Dissolved solid should be less than 500ppm.
• It should be soft and free from disease causing micro-organisms.
• Fluoride content should be less 1.5ppm. And Chloride, Sulphate contents should
be less than 250ppm.
5. What is break-point chlorination? State its significance.
It means that chlorination of water to such an extent that living organisms as well as
other organic impurities in water are destroyed. It involves in addition of sufficient amount
of chlorine to oxidize organic matter, reducing substances and free ammonia in raw water,
leaving behind mainly free chlorine which possesses disinfecting action against pathogenic
bacteria’s. It is also known as free-residual chlorination.
Initially for lower doses of Cl2 , there is no free residual chlorine since all the added
chlorine gets consumed for doing complete oxidation of reducing substances present in
water.
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As the amount of chlorine dosage is increased, amount of residual chlorine also

show steady increase. This stage corresponds to the formation of chloro-organic
compounds without oxidizing them.
At still higher dose of applied chlorine, oxidation of organic and micro-organisms

gets in consequently the amount of free residual chlorine also decrease. When the
oxidative destruction is completed, it reaches minima.
After minima, the added chlorine is not used in any reaction. Thus, the residual
chlorine keeps increasing in proportion to added chlorine. Hence, for effectively killing
microorganisms, sufficient chlorine has to be added. Addition of chlorine in such dosages
is known as break-point or free residual chlorination.
Advantages: it ensures complete destruction of organic matter which impart color, bad
odor and unpleasant taste to water. It completely destroys all the disease-causing
bacteria. It prevents the growth of any weeds in water.
6. Discuss oxidation corrosion.
This type of corrosion occurs mainly through the direct chemical action of environment/atmospheric
gases such as oxygen, halogen, hydrogen sulphide, Sulphur dioxide, nitrogen or anhydrous inorganic
liquid with metal surfaces in immediate proximity.
There are three main types of chemical corrosion: a) Oxidation corrosion, b) Corrosion by
other gases, c) Liquid metal corrosion.
Oxidation corrosion: Direct action of oxygen at high or low temperatures on metals in the absence
of moisture is called oxidation corrosion. The alkali (Li, Na, K, Rb etc.) and alkaline earth (Be, Ca,
Sr etc.) metals are rapidly oxidized at low temperatures, while metals like Fe, Al etc. (except noble
metals Au, Pt etc.) are oxidized at high temperatures by interaction of oxygen.
The reactions in the oxidation corrosion are:

2M → 2 Mn+ + 2n e- (Loss of electron: Oxidation)
n/2 O2 + 2n e- → n O2- (Gain of electron: Reduction)
2 M + n/2 O2 → 2 M + n O2-
n+
Mechanism: Oxidation occur first at the surface of the metal by forming a metal oxide scale which
acts as a barrier between metal surface and environment. The nature of oxide formed plays an
important role in oxidation corrosion process which decides further action.
If the oxide film formed is continues and rigidly adhered to the surface of metal is impervious
in nature, and is called stable oxide layer. It is protective and shields the metal from further
corrosion. Ex: Oxide films on Al, Sn, Pb, Cu etc. acts as a protective coating and further corrosion is
prevented.
If unstable oxide film is formed, it decomposes back into the metal and oxygen.
Consequently, oxidation corrosion is not possible. Ex: Noble metals like Ag, Au and Pt do not
undergo corrosion.
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If oxide layer formed is volatile, it is non-protective and more feasible for further attack of
environment. This causes rapid and continuous corrosion, leading to excessive corrosion. Ex: Mo
forms a volatile oxide layer.
If oxide layer is having pores or cracks, the atmospheric oxygen have access to the underlying
surface of metal, through the pores or cracks of the layer, thereby the corrosion continues
unobstructed till the entire metal is completely converted into its oxide.
7. State and explain Pilling-Bedworth rule.
Pilling-Bedworth rule: According to it, ‘”greater is the specific volume ratio, lesser is the
rate of corrosion.”
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑜𝑥𝑖𝑑𝑒 𝑓𝑜𝑟𝑚𝑒𝑑

𝑆𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑣𝑜𝑙𝑢𝑚𝑒 𝑟𝑎𝑡𝑖𝑜 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑒𝑡𝑎𝑙
If the volume of metal oxide layer is at least as great as the volume of metal from
which it is formed is non-porous and becomes protective layer by tightly adhering to the
base metal. Ex: The specific volume ratios of W, Cr and Ni are 3.6, 2.0 and 1.6
respectively. Hence, the rate of corrosion is least in Tungsten (W).
If the volume of metal oxide is less than the volume of the metal, the oxide layer is
porous, non-continuous and non-protective and faces strains. Hence, cracks and pores
are developed in the layer, creating access to atmospheric oxygen to reach the underlying
metal. In this case corrosion is continuous and rapidly increases. Ex: Li, Na and K.
8. What is corrosion? Explain the mechanism of electrochemical corrosion.

Corrosion is the destruction of metal from its surface due to unwanted chemical or
electrochemical interaction with its environment.
Wet corrosion or electrochemical corrosion takes place under wet or moist
conditions through the formation of short circuited tiny electrochemical cells. Wet
corrosion is more common than dry corrosion.
This type of corrosion can be observed, i) When a metal is in contact with

conducting liquid (or) ii) When two dissimilar metals are dipped partially in a solution.
The electrochemical corrosion involves:

i) The formation of anodic and cathodic areas or parts in contact with each other,
ii) Presence of a conducting medium,
iii) Corrosion of anodic areas only,
iv) Formation of corrosion product somewhere between anodic and cathodic areas.
Formation of Anodic and Cathodic areas: Impact of corrosive environment on a portion
of metal, changes its electrode potential compared to its original value of the electrode
potential of the metal. This creates a potential difference within the metal system. The
area of lower reduction potential created in the metal is known as the ‘anodic area’ and
that with higher reduction potential value is called ‘cathodic area’. The current flows from
the anodic area to the cathodic area through the conducting solution. A galvanic cell is
created in the metal.
Mechanism: Electrochemical corrosion involves flow of electron-current between the
anodic and cathodic areas. The anodic reaction involves in dissolution of metal as
corresponding metallic ions with the liberation of free electrons.
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At anodic area: M → Mn+ + n e- (Oxidation)

The cathodic reaction consumes electrons with either by i) evolution of hydrogen, or
ii) absorption of oxygen depending on the nature of the corrosive environment.
Evolution of hydrogen: It occurs usually in acidic environment. Considering metal like

Fe, the anodic reaction is dissolution of iron as ferrous ion with the liberation of electrons.
Fe → Fe2+ + e- (Oxidation)
These electrons flow through the metal, from anode to cathode, where H + ions are
eliminated as hydrogen gas from acidic solution.
2 H+ + 2 e- → H2  (Reduction)
The overall reaction: Fe + 2 H+ → Fe2+ + H2 
Thus, this type of corrosion causes “displacement of hydrogen ions from the acidic
solution by metal ions. “Consequently, all metals above hydrogen in the electrochemical
series have a tendency to get dissolved in acidic solution with simultaneous evolution of
hydrogen.
It may be noted that in hydrogen evolution type corrosion the anodes are usually
very large in areas where as the cathodes are small areas.
Mechanism of wet corrosion by hydrogen evolution
Absorption of oxygen: Rusting of iron in neutral aqueous solution of electrolytes in the

presence of atmospheric oxygen is a common example of this type of corrosion. Usually
the surface of iron is coated with a thin film of iron oxide. However, if this iron oxide film
develops some cracks, anodic areas are created on the surface while the well-metal parts
act as cathodes. If follows that the anodic areas are small surface parts while nearly the
rest of the surface of the metal forms large cathodes.
At the anodic areas, the metal (iron) dissolves as ferrous ions with liberation of electrons.
Fe → Fe2+ + 2e- (Oxidation)
The liberated electrons flow from anodic to cathodic areas, through iron metal,
where electrons are intercepted by the dissolved oxygen as:
½ O2 + H2O + 2e- → 2 OH- (Reduction)
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The Fe2+ ions at anode and OH- ions at cathode diffuse through medium and when
they meet, ferrous hydroxide is precipitated.
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
This product is called yellow rust, actually corresponds to Fe 2O3.3H2O. If the supply
of oxygen is limited the corrosion product may be even black anhydrous magnetite, Fe3O4.
An increase in oxygen content forces the cathodic reaction to produce more OH -

ions which in turn removes more electrons from anode and accelerates the corrosion.
Mechanism of wet corrosion by oxygen absorption (rusting of iron)
9. Discuss the various factors influencing rate of corrosion?
The rate of extent of corrosion depends on the nature of metal and corrosive
environment.
a) Nature of Metal:
i) Position of metal in the Galvanic series: When the metal is higher up in the
galvanic series, greater is the oxidation potential. Thus, greater is its tendency to
become anodic and hence greater is the rate of corrosion. Thus, extent of corrosion
depends upon the position of the metal in the galvanic series. When two metals are in
electrical contact, greater is the difference in their positions in the electrochemical
series, faster is the corrosion of anodic metal.
ii) Relative areas of anode and cathodes: Corrosion is more rapid and severe, and
highly localized, if the anodic area is small, because the current density at a smaller
anodic area is much greater, and the demand for electrons by cathodic areas can be
met by smaller anodic areas only by undergoing corrosion more briskly.
𝑎𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑎𝑡ℎ𝑜𝑑𝑖𝑐 𝑝𝑎𝑟𝑡
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑟𝑟𝑜𝑠𝑖𝑜𝑛 𝑜𝑓 𝑎𝑛𝑜𝑑𝑖𝑐 𝑝𝑎𝑟𝑡 ∝
𝑎𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑎𝑛𝑜𝑑𝑖𝑐 𝑝𝑎𝑟𝑡
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iii) Overvoltage: When a metal which occupies a high position in galvanic series, say zinc
is placed in 1N H2SO4, it undergoes corrosion forming a film and evolving hydrogen
gas, the initial rate of reaction is quite slow, because of high over voltage of zinc metal,
which reduces the effective electrode potential (= 0.70V) to a small value. However, if a
few drops of copper sulphate are added, the corrosion rate of zinc is accelerated,
because some copper gets deposited on the zinc metal, forming minute cathodes,
where the hydrogen overvoltage is only 0.33V. Thus, reduction in overvoltage of the
corroding metal accelerates the corrosion rate.
iv) Purity of metal: Impurities in a metal cause heterogeneity and form tiny
electrochemical cells at the exposed parts, and the anodic parts get corroded. For
example, zinc metal containing impurity such as Pb or Fe undergoes corrosion due to
formation of local electrochemical cells. The rate and extent of corrosion increase with
the increasing exposure and extent of the impurities. Consequently, corrosion
resistance of a metal may be improved by increasing its purity.
v) Nature of surface oxide film: In aerated atmosphere, practically all metals get
covered with a thin surface film of metal oxide. The ratio of the volumes of the metal
oxide to the metal is known as specific volume ratio. Greater the specific volume ratio,
lesser is the oxidation corrosion rate. For example, the specific volume ratios of Ni, Cr
and W are 1.6, 2.0 and 3.6 respectively. Consequently, the rate of oxidation of
tungsten is least, even at elevated temperatures.
b) Nature of environment:
i) Temperature: The rate of a chemical reaction, in general, increases with rise in
temperature. Corrosion process is one such chemical reaction. Therefore, the rate of
corrosion increases as the temperature increases. Increase in temperature increases
the conductance of the corrosion medium, which also contributes to the increase in
rate of corrosion.
ii) Humidity: The greater is humidity, the greater is the rate and extent of corrosion.
This is due to the fact that the moisture or vapours present in atmosphere acts as a
solvent for O2, H2S, SO2 and NaCl etc. to furnish the electrolyte essential for setting up
an electrochemical cell.
iii) pH: In general, lower the pH of the corrosion medium, higher is the corrosion rate.
However, some metals like Al, Zn undergo fast corrosion in highly alkaline solution.
The pH of the solutions also decides the type of cathodic reaction.
10. What is cathodic protection? Describe the various methods of it?
Cathodic protection: The principle involved in this method of protection is to force the
metal to be protected to behave like a cathode, thereby corrosion does not occur. There are
two types of cathodic protection.
a) Sacrificial anodic protection

b) Impressed current cathodic protection
a) Sacrificial anodic protection: In this method of protection, the metallic structure

to be protected is connected to more anodic metal through a wire, so that all the corrosion
is concentrated at the more anodic metal. The more anodic metal itself gets corroded
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slowly; while the parent structure is protected. The more active metal so employed is
called “sacrificial anode”. The corroded sacrificial anode block is replaced by a fresh one,
when consumed completely.
Metals commonly used as sacrificial anodes are Zn, Al, Mg and their alloys. Mg is
used in high resistivity electrolytes such as soils due to its most negative potential and it
can provide highest current output.
Applications: Important applications of this technique are
a) Protection of underground cables and pipelines from soil corrosion.
b) Protection of ships and boat hulls from marine corrosion.

c) The formation of rusty water is prevented by the insertion of Mg sheets or rods into
domestic water boilers or tanks.
b) Impressed current cathodic protections: In this method current from an external

source is impressed in the opposite direction to nullify the corrosion current. Thus, the
anodic corroding metal becomes cathodic and protected from corrosion.
The anode may be either an inert metal or one which deteriorates and will have to
be replaced periodically. The commonly used anodic materials are graphite, carbon,
stainless steel, scrap iron, high silica iron and platinum. The anode is buried in back fill
such as gypsum to increase the electrical contact between itself and the surrounding soil.
This protection method is useful when electrolyte resistivity and current

requirements are high. It is well suited for large structures and long-term applications.
Applications: This protection technique is employed in the case of open water box coolers,
water tanks, buried pipe-lines, marine pipes etc.
11. What is galvanizing? Explain.
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Galvanizing: It is a process of coating iron or steel sheets with a thin coat of Zn to prevent
them from rusting. The base metal iron or steel sheet is cleaned by acid pickling method
with dil.H2SO4 for 15-20 minutes at 60-90oC. The sheet is then washed well and dried. It is
dipped in a bath of molten zinc maintained at 425-435oC. The surface of the bath is kept
covered with ammonium chloride flux to prevent oxide formation. The sheet is taken out
and excess Zn is removed by passing it between a pair of hot rollers. Then the sheet is
subjected to annealing process at 650oC and cooled slowly. An alloy of iron and zinc were
formed at the junction of the base metal and coating metal.
Applications: It is mostly used to protect iron used for roofing sheets, wires, pipes, nails,
bolts, screws, buckets and tubes.
Galvanizing utensils cannot be used for preparing and storing food stuffs especially
acidic in nature, because zinc dissolves to form highly toxic or poisonous compounds.
UNIT-III POLYMER
1. Define the terms: (i) Polymer (ii) Monomer (iii) Functionality (iv) Degree of
Polymerization
Polymers or Macromolecules can be defined as the large molecules built-up by the linkage
together of small molecules. (in Greek language, poly means many and mer means unit).
Monomers are the small molecules which combine with each other to form polymer
molecules.
Degree of Polymerization: The number of monomer units present in a polymer is known

as degree of polymerization. The “repeat unit” in a polymer is called “mer”. There may be
hundreds or thousands or tens of thousands or more monomer molecules linked together
in a polymer molecule. Most of the polymers usually fall into the 5000-200000 molecular
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mass range.
Functionality: The number of bonding sites in a monomer is referred to as its

functionality. In an olefin, the double bond can be considered as a site for two free
valencies. When the double bond is broken, two single bonds become available for
combination. Thus, ethylene is considered to be bifunctional. Other reactive groups are
hydroxyl, acid, amino-acid, di-ol, polyalcohols, di-amino acids, di-acids, etc. Depending on
functionality of monomeric units, it is possible to obtain different types of structures. In
case of a bifunctional monomer, two reactive groups attach side by side to each other
forming a linear or straight-chain molecule. When a trifunctional monomer is mixed in
small amounts with a bifunctional monomer and polymerized, it results branched-chain
polymer.
2. Discuss addition, condensation and copolymerization with suitable examples?
Addition or Chain polymerization: It is a reaction that yields a product, which is an

exact multiple of the original monomeric molecule. Such a monomer molecule, usually
contains one or more double bonds, which by intermolecular rearrangement, may make
the molecule bifunctional. The addition polymerization reaction must be instigated by the
application of heat, light, pressure or a catalyst for breaking down the double covalent
bonds of monomers.
Condensation or step-polymerization: It may be defined as “a reaction occurring

between simple polar group containing monomers with the formation of polymer and
elimination of small molecules like water, HCl, etc.” For example, hexamethylene diamine
and adipic acid condense to form a polymer, nylon 6:6
Thus, condensation polymerization is an intermolecular combination, and it takes

place through the different functional group in the monomers having the affinity for each
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other.
Copolymerization: It is the joint polymerization of two or more monomer species. High

molecular-weight compounds obtained by copolymerization are called copolymers. For
example, butadiene and styrene copolymerize to yield Buna-S rubber.
3. Differentiate between thermoplastic and thermosetting polymers.

Thermoplastics Thermosettings
They are softened on heating and They do not soften on heating. On prolong
hardened on cooling. heating, however, they burn.
These are formed by additional These are formed by condensation

polymerization. Polymerization
These are long chain linear Their set molecules have three
macromolecules dimensional cross –linked network
structure.
The adjacent polymer chains are held Polymer chains are held together by
together by either vander wal forces or by strong covalent bonds.
dipole-dipole or H-bonds.
They can be remoulded, reshaped and They cannot be remoulded.
reused.
They can be reclaimed from waste. They cannot be reclaimed from waste.
Thermoplasts are soluble in organic These are insoluble in almost all the
solvents solvents.
These are soft, weak and less brittle. These are hard, strong and more brittle.
Ex: PE, PVC andTeflon. Ex: Bakelite and Urea Formaldehyde
resins.
4. Discuss the preparation, properties and uses of Bakelite?

It is a phenol formaldehyde resin. It is prepared by condensing phenol with
formaldehyde in presence of acidic or basic catalyst. The initial reaction results in the
formation of ortho and para hydroxy methyl phenol, which reacts to form linear polymer,
Novolac.
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During moulding, hexamethylene tetramine [(CH 2)6N4] are added. It provides

formaldehyde, which converts the soluble and fusible novolac into a hard, infusible and
insoluble solid of cross-linked structure.
Properties:
 Bakelite is set to rigid, hard, scratch-resistant, infusible, water-resistant, insoluble
solid which is resistant to non-oxidizing acids, salts and many organic solvents.
 It is attacked by alkalis, because of the presence of free hydroxyl group in their
structure.
 It possesses excellent electrical insulating character.
Applications:
 It is used for making electric insulator parts like switches, plugs, switch-boards,
heater-handles, etc.
 For making moulded articles like telephone parts, cabinets for radio and television.
 For impregnating fabrics, wood and paper.
 As adhesives for grinding wheels.
 In paints and varnishes.
 As hydrogen-exchanger resins in water softening.
 For making bearing, used in propeller shafts for paper industry and rolling mills.
5. Describe the preparation, properties and uses of Kevlar?
It is an aromatic polyamide in which benzene rings linked to the amide groups. It is
prepared by condensation between aromatic dichloride and aromatic diamines.
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Properties:
 Kevlar is exceptionally strong, 5 times stronger than steel and 10 times stronger
than Al on a weight-for-weight bases.
 It has high heat stability and flexibility.
 The unique properties of kevlar are due to the delocalized bonding which causes the
benzene rings to be inflexible.
 The high electron-density in the chains of Kevlar also results in relatively stronger
vander waals intermolecular forces between neighbouring polymer molecules.
Applications:
 Kevlar is used extensively in the aerospace and aircraft industries, a car parts such
as tyres, brakes, clutch linings, etc.
 For making ropes, cables, protective clothing, bullet-proof vests, motorcycle helmets
and other high performance materials.
6. Give the preparation properties and uses of Buna-S?

It is produced by copolymerization of butadiene and styrene. (about 75% and 25% by
weight).
Properties:
• It resembles natural rubber in processing characteristics as well as quality of
finished products.
• It possesses high abrasion-resistance, high load-bearing capacity and resilience.
• It gets readily oxidized in presence of traces of ozone present in the atmosphere.
• It swells in oils and solvents.
• It can be vulcanized in the same way as natural rubber either by sulphur or
sulphur monochloride (S2Cl2). However, it requires less sulphur, but more
accelerators for vulcanization.
Applications:
• Mainly used for the manufacture of motor tyres.
• As floor tiles, shoe soles, gaskets, foot-wear components, wire and cable
insulations, carpet backing, adhesives, tank-lining etc.
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7. Explain preparation, properties and uses of silicone rubbers.

Silicone rubbers: These are obtained by hydrolysis of dimethyl silicone dichlorides and followed by
polymerization. On mixing high molecular-weight linear dimethyl silicon polymers with fillers like
finely divided silicon dioxide and peroxide-containing curing agents, causes the formation of
dimethyl bridge between methyl groups of adjacent chains.
CH3 CH3 CH3

2H2O
n Cl Si Cl n HO Si OH n O Si O
-2HCl -H2O
CH3 CH3 CH3
Dimethyl silicone dichloride Unstable

Polymerization
CH3 H3C
O Si O Si O
CH3 CH3 n
Dimethyl silicone polymer
Properties:
• They possess exceptional resistance to prolonged exposure to sunlight, weathering, most

common oils, boiling water, dilute acids and alkalis.
• They remain flexible in the temperature range of 90 – 2500C and here, find use in making
tyres of fighter aircrafts, since they prevent damage on landing.
Applications:
• As a sealing material in search-lights and in aircraft engines.

• For manufacture of tyres for fighter aircrafts.
• For insulating the electrical wiring in ships.
• In making lubricants, paints and protective coatings for fabric-finishing and water-proofing.
• As adhesive in electronics industry.
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• For making insulation for washing machines and electric blankets for iron board covers.
• For making artificial heart valves, transfusion tubings, and padding for plastic surgery.
For making boots for use at very low temperature, since they are less affected by temperature
variation.
8. What are conducting polymers? Write mechanism of conduction in
polyacetylene?
Polymers which show electrical conductivity on par with metallic conductors are
known as conducting polymers.
Conducting polymers have backbones of conjugated -electrons, which are

responsible for electrical charge. In an electrical field, conjugated -electrons of the
polymer get excited; thereby can be transported through the solid polymeric material.
Overlapping of orbitals of conjugated -electrons over the entire backbone results in the
formation of valence bands as well as conduction bands, which extend over the entire
polymer molecule.
Ex: Polyacetylene, polyaniline, polyanthrylene, polyphenanthrylene, polypyrrole,

polythiophene etc.
Mechanism of conduction in polyacetylene:
9. Applications of conducting polymers?
Conducting polymers are finding increased use because they are light weight, easy to
process and have good mechanical properties.
• In rechargeable light weight batteries based on perchlorate doped polyacetylene-

lithium system. These are about 10 times lighter than conventional lead storage
batteries. Such batteries are sufficiently flexible to fit a variety of designed
configuration.
• In optically display devices based on polythiophene. When the structure is
electrically biased, the optical density of the film changes, i.e., its colour changes.
Such electrochromic systems produce coloured displays with faster switching time
and better viewing than conventional LED devices.
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• In wiring aircrafts and aerospace components.

• In telecommunication systems.
• In antistatic coatings for clothing.
• In electromagnetic screening materials.
• In electronic devices such as transistors and diodes.
• In solar cells.
• In drug delivery system for human body.
• In photo voltaic devices.
• In non-linear optical materials.
• In molecular wires and molecular switches.
10. What is biodegradable polymer? Explain preparation, properties and

applications of polylactic acid?
Biodegradable Polymers: Biodegradable polymers are the polymers that breakdown and lose their
initial integrity after their end use.
Polylactic Acid: Poly(lactic acid) or polylactide (PLA) is a thermoplastic aliphatic polyester derived
from renewable resources, such as corn starch (in the United States), tapioca roots, chips or starch
(mostly in Asia), or sugarcane.
Bacterial fermentation is used to produce lactic acid from corn starch or cane sugar. Lactic
acid cannot be polymerised to a useful product because each reaction generates one molecule of
water, presence of which degrades the forming polymer chain. Due to this low molecular weight
polymers will be formed. Instead, two lactic acids are dimerized to di-lactic ester. Although
dimerization generates water, it can be separated prior to polymerisation. PLA of high molecular
weight is produced from di-lactic ester by ring opening polymerization using stannous octate catalyst.
Properties:
Polylactic acid can be processed like most thermoplastics into fibre and film. The melting
temperature of PLA can be increased 40-50 °C and its heat deflection temperature can be increased
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from approximately 60°C to up to 190 °C by physically blending the polymer with PDLA (poly-D-
lactide).
Applications:
Poly (lactic acid) can be processed by extrusion, injection moulding, film & sheet casting, and
spinning, providing access to a wide range of materials. Being able to degrade into innocuous lactic
acid, PLA is used as medical implants in the form of anchors, screws, plates, pins, rods, and as a
mesh. Depending on the exact type used, it breaks down inside the body within 6 months to 2 years.
In the form of fibres and non-woven textiles, PLA also has many potential uses, for example as
upholstery, disposable garments, awnings, feminine hygiene products, and diapers.
UNIT-IV: CHEMICAL FUELS
1. What are chemical fuels? Give complete classification of chemical fuels with
examples.
A chemical fuel is a substance which on combustion in air or oxygen produces

significant amounts of heat which can be used economically for domestic and industrial
purposes.
Ex:- wood, coal, crude oil, natural gas, etc.
Classification of fuels: Chemical fuels are broadly classified as solid, liquid and gaseous
based on their physical state in which they are used. These are further classified as
primary and secondary fuels.
A fuel that occurs in nature is called a “primary fuel” while all others, which are
derived from primary fuels are called “secondary fuels”.
Physical state Primary fuels (Natural) Secondary fuels (Derived)

1. Solid Wood, Coal, Lignite, Bituminous, Charcoal, Coke
Anthracite, Peat
2. Liquid Petroleum (Crude oil) Gasoline, Diesel, Kerosene,
Synthetic petrol
3. Gaseous Natural gas Producer gas, Water gas, Coal
gas, LPG, Biogas
2. Define Higher calorific value and Lower calorific value?
Higher (Gross) calorific value (HCV): It is defined as the amount of heat released when
unit quantity of a fuel is burnt completely in air and the combustion products are cooled
to room temperature.
Lower (Net) calorific value (LCV): It is defined as the amount of heat released when a
unit quantity of a fuel is burnt completely in air, and the products of combustion are let
off into the atmosphere.
LCV = HCV – latent heat of steam

9 x %H
= HCV – 100 X 587 cal/g
Because 1 g hydrogen gives 9 g of water and the latent heat of steam is 587 cal/g.
Page 31 of 42
3. Explain the proximate analysis of coal? What is its significance?
Proximate analysis: The following contents are determined in proximate analysis.
1) Moisture: 1 g of finely powdered air-dried coal sample is taken in a crucible which

is placed inside an electric hot air-oven at 1050-1100C for 1 hour. Then crucible is
taken out and cooled in a desiccators and weighed. Loss in weight is reported as
moisture on percentage basis.
𝑳𝒐𝒔𝒔 𝒊𝒏 𝒘𝒆𝒊𝒈𝒉𝒕
𝑷𝒆𝒓𝒄𝒆𝒏𝒕𝒂𝒈𝒆 𝒐𝒇 𝒎𝒐𝒊𝒔𝒕𝒖𝒓𝒆 = 𝒙𝟏𝟎𝟎
𝑾𝒕. 𝒐𝒇 𝒄𝒐𝒂𝒍 𝒕𝒂𝒌𝒆𝒏
Significance: Moisture in cola evaporates during the burning of coal and it takes
some of the liberated heat in the form of latent heat of vaporization. It lowers the
effective calorific value of coal and quenches the fire in the furnace. Hence, lesser
the moisture content, better the quality of coal. However, presence of moisture up
10% produces a more uniform fuel-bed and less of “fly-ash”.
2) Volatile matter: The dried sample of coal left in the crucible covered with a lid and
placed in an electric furnace maintained at 9250C. The crucible is taken out of the
oven after 7 minutes of heating and cooled first in air, then inside a desiccator and
weighed again. Loss in weight is reported as volatile matter on percentage basis.
𝑳𝒐𝒔𝒔 𝒊𝒏 𝒘𝒆𝒊𝒈𝒉𝒕 𝒅𝒖𝒆 𝒕𝒐 𝒓𝒆𝒎𝒐𝒗𝒂𝒍 𝒐𝒇 𝒗𝒐𝒍𝒂𝒕𝒊𝒍𝒆 𝒎𝒂𝒕𝒕𝒆𝒓
% 𝒐𝒇 𝒗𝒐𝒍𝒂𝒕𝒊𝒍𝒆 𝒎𝒂𝒕𝒕𝒆𝒓 = 𝒙𝟏𝟎𝟎
Significance: High volatile matter content means that a high proportion of fuel will
distill over as gas or vapours, a large proportion of which escapes unburnt. So,
higher volatile content in coal is 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 cool.
3) Ash: The residual coal in the crucible is then heated without lid in a muffle furnace
at 7000C for ½ hour. The crucible is taken out cooled first in air, then in desiccators
and weighed. Heating, cooling and weighing is repeated till a constant weight is
obtained. The residue is reported as ash on percentage basis.
𝑾𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝒂𝒔𝒉 𝒍𝒆𝒇𝒕
% 𝒐𝒇 𝒂𝒔𝒉 = 𝒙𝟏𝟎𝟎
Significance: It 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
become irregular. Hence, lower the ash content better is the quality of coal.
4) Fixed carbon: Percentage of fixed carbon = 100 - % of (moisture+volatile
matter+ash)
Significance: Higher the percentage of fixed carbon greater is its calorific value
and better the quality of coal.
Page 32 of 42
4. Discuss the ultimate analysis of coal and its significance.
Ultimate analysis:
1) Carbon and Hydrogen: About 1-2 g 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 increases in weights of
these are determined.
C + O2 CO2
H2 + ½ O 2 H 2O
2 KOH + CO2 K2CO3 + H2O

CaCl2 + 7 H2O CaCl2.7H2O
𝑰𝒏𝒄𝒓𝒆𝒂𝒔𝒆 𝒊𝒏 𝒘𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝑲𝑶𝑯 𝒕𝒖𝒃𝒆 𝑿 𝟏𝟐

% 𝒐𝒇 𝑪 = 𝒙𝟏𝟎𝟎
𝑾𝒕. 𝒐𝒇 𝒄𝒐𝒂𝒍 𝒕𝒂𝒌𝒆𝒏 𝑿 𝟒𝟒
𝑰𝒏𝒄𝒓𝒆𝒂𝒔𝒆 𝒊𝒏 𝒘𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝑪𝒂𝑪𝒍𝟐 𝒕𝒖𝒃𝒆 𝑿 𝟐

% 𝒐𝒇 𝑯 = 𝒙𝟏𝟎𝟎
𝑾𝒕. 𝒐𝒇 𝒄𝒐𝒂𝒍 𝒕𝒂𝒌𝒆𝒏 𝑿 𝟏𝟖
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
matter and hence it affects the use to which the coal is put.
2) Nitrogen: About 1 g of accurately weighed powdered cola is heated with
concentrated H2SO4 along with K2SO4 in a long-necked flask. After the solution
becomes clear, it is treated with excess of KOH and the liberated 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 nitrogen in
coal is calculated.
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒂𝒄𝒊𝒅 𝒖𝒔𝒆𝒅 𝑿 𝑵𝒐𝒓𝒎𝒂𝒍𝒊𝒕𝒚 𝑿 𝟏. 𝟒

% 𝒐𝒇 𝑵 = 𝒙𝟏𝟎𝟎
Significance: It has no calorific value and hence its presence in coal is

undesirable. Thus, a good quality coal should have very little nitrogen content.
3) Sulphur: It is determined from the washings obtained from the known mass of coal,
used in bomb calorimeter for determination of calorific value. During this
determination S is converted into sulphate. The washings are treated with BaCl 2
solution, then BaSO4 is precipitated. This precipitate is filtered, washed and heated
to constant weight.
𝑾𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝑩𝒂𝑺𝑶𝟒 𝒐𝒃𝒕𝒂𝒊𝒏𝒆𝒅 𝑿 𝟑𝟐
% 𝒐𝒇 𝑺 = 𝒙𝟏𝟎𝟎
𝑾𝒕. 𝒐𝒇 𝒄𝒐𝒂𝒍 𝒕𝒂𝒌𝒆𝒏 𝒊𝒏 𝒃𝒐𝒎𝒃 𝑿 𝟐𝟑𝟑
Significance: Sulphur although contributes to the heating value of coal, yet on

combustion produces acids which have harmful effects of corroding the equipment
and also cause atmospheric pollution. Sulphur is usually present to the extent of
0.5 to 3.0% and derived from ores like pyrites, gypsum etc. mines along with the
coal.
Page 33 of 42
5) Ash: The dried coal is taken in a crucible. It is heated without lid in a muffle
furnace at 7000C for ½ hour. The crucible is taken out cooled first in air, then in
desiccators and weighed. Heating, cooling and weighing is repeated till a constant
weight is obtained. The residue is reported as ash on percentage basis.
𝑾𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝒂𝒔𝒉 𝒍𝒆𝒇𝒕
% 𝒐𝒇 𝒂𝒔𝒉 = 𝒙𝟏𝟎𝟎
Significance: It 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
become irregular. Hence, lower the ash content better is the quality of coal.
4) Oxygen: % of O = 100 - % of (C+H+S+N+Ash)

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 in 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 about1.7% and hence, oxygen is
undesirable. Thus, a good quality coal should have low percentage of oxygen.
5. What is cracking? Give its significance.

Cracking: It is defined as the decomposition of high molecular weight hydrocarbons of
high boiling points into simpler, lower molecular weight hydrocarbons of low boiling
points.
C10H22 cracking C5H12 + C5H10

Decane n-pentane pentene
Significance: Of all the B.P.=174
fractionsCobtained byB.P.=36
0 fractionation
0
C of petroleum, gasoline has the
highest demand as a motor fuel, but the yield of this fraction is only 20% of the crude.
Also, the quality of so-called ‘straight run’ gasoline is not so good. Hence, it is used only
after suitable blending. Moreover, there is a surplus of heavier petroleum fractions.
To overcome these difficulties, the middle and heavy fractions are cracked to get
more valuable low boiling fractions. For instance, the petrol made by cracking has far
better characteristics than straight-run petrol.
Page 34 of 42
6. Describe the method of moving bed catalytic cracking with a neat labeled
diagram.
The solid catalyst (zeolite) is very finely powdered, so that it behaves almost as a
fluid, which can be circulated in gas stream. The vapours of cracking stock mixed with
fluidized catalyst is forced up into a large reactor ‘bed’ in which cracking of the heavier
into lighter molecules occurs. Near the top of the reactor there is a centrifugal separator
called cyclone, which allows only the cracked oil vapours to pass on to the fractionating
column, but retains all the catalyst powder in the reactor itself. The catalyst powder
gradually becomes heavier, due to coating with carbon, and settles to the bottom, from
where it is forced by an air blast to regenerator maintained at 6000C.
In regenerator, carbon is burnt and the regenerated catalyst then flows through a
stand-pipe for mixing with fresh batch of incoming cracking oil. At the top of the
regenerator there is a separator, which permits only flue gases to pass out, but holds back
catalyst particles.
The cracked oil vapours from reactor is passed to the fractionating column where
heavy oil is separated. The vapours are then passed through the cooler where gasoline
condenses along with some gases. This is then sent to a stabilizer where the dissolved
gases are removed and pure gasoline is recovered.
7. Explain the composition and applications of different fractions obtained during

fractional distillation method.
Fractional distillation: The crude oil is heated to about 4000C in an iron retort, whereby
all volatile constituents are evaporated. The hot vapours are then passed through a tall
cylindrical tower, known as fractionating column, containing number of horizontal
stainless steel trays at short distances. These trays are provided with individual chimneys
which are covered with a loose cap. As the vapours go up, fractional condensation takes
place at different heights of column. Higher boiling fractions condense first; while the
lower boiling fractions condense later.
Page 35 of 42
Gasoline or Petrol: It is a mixture of hydrocarbons from pentane to octane. It is

obtained between 40 to 1200C. Its calorific value is 11,250 kcal/kg. It is highly volatile and
inflammable. It is used as fuel for internal combustion engine.
Name of Boiling
S.No Composition Applications
fraction range
Uncondensed As domestic or industrial fuel
1 < 300C C1 to C4
gas under the name LPG.
Petroleum
2 300 to 700C C5 to C7 As a solvent.
ether
Gasoline or
As motor fuel, solvent, in dry
3 Petrol or Motor 400 to 1200C C5 to C9
cleaning.
spirit.
Naptha of 1200 to
4 C9 to C10 As solvent, dry cleaning.
Solvent spirit 1800C
1800 to As jet engine fuel, to prepare
5 Kerosene oil C10 to C16
2500C laboratory gas.
2500 to
6 Diesel oil C10 to C18 As diesel engine fuel.
3200C
3200 to
7 Heavy oil C17 to C30 For getting gasoline by cracking.
4000C
Asphalt or C30 and
8 Above 4000C Water proofing, road making.
Petroleum coke above
Diesel oil: It is a mixture of higher hydrocarbons C10 to C18. It is obtained between

250 to 3200C. Its calorific value is 11,000 kcal/kg. It is used as a fuel for diesel engine.
Kerosene oil: It is a mixture of hydrocarbons C10 to C16. It is obtained between 180
to 2500C. Its calorific value is 11,100 kcal/kg. It does not vaporize easily due to its
high boiling point. It is used as domestic fuel in stoves, as jet engine fuel and for
making oil gas.
8. Write short notes on: i) Octane number, ii) Cetane number, iii) Knocking, iv)
LPG, v) CNG
Page 36 of 42
Knocking: It is a sharp rattling sound produced in the internal combustion engine due to
immature ignition of the air gasoline mixture. The presence of some constituents in the
gasoline used causes the rate of oxidation becomes so great that last portion of the fuel-air
mixture gets ignited instantaneously producing an explosive violence called ‘Knocking’.
Knocking causes huge loss of energy, damages the piston and cylinder there by loss
of efficiency. Knocking is high when the fuels have straight chain paraffin’s and low when
fuels contain aromatic and branched chains. Knocking can be minimized by adding anti
knocking agents like Tetraethyl lead, Isopentene, methyl tertiary butyl ether etc. in
gasoline.
Octane number: It is defined as the percentage of iso-octane in a mixture of iso-octane

and n-heptane that has the same knocking characteristics of the fuel under examination.
For Ex: A fuel with octane number 60 will give the same knocking as the mixture by
volume of 60% iso-octane and 40% n-heptane.
The n-heptane knocks very badly and hence its anti-knocking value has arbitrarily
been given zero. Whereas isooctane gives very little knocking so its anti-knocking value
has been given as 100.
CH3-(CH2)5-CH3
n-Heptane
Cetane number: It is defined as the percentage of cetane (n-hexadecane) in a mixture of

cetane and 2-methyl naphthalene that will have the same ignition characteristics as the
diesel fuel under examination. Diesel engines require a fuel of cetane number greater than
45.
CH3-(CH2)14-CH3
n-Hexadecane
Straight chain alkanes have high ignition quality where as aromatic have poor
ignition quality. Thus, the hydrocarbons which are poor gasoline fuels are quite good
diesel fuels.
LPG: Liquefied Petroleum Gas is the mixture of propane and butane with small amounts
of ethane and propene obtained from gas wells. These are compressed to form liquid. It is
supplied in cylinders with brand names such as Bharath, HP and Indane gas. The calorific
value of LPG is 27,800 kcal/m3.
Advantages: It is highly knock resistant with high calorific value and burns cleanly. It is
having good flexibility and portability to supply.
Disadvantages: Due to faint odour, leakage cannot be detected.
Uses: It is used as domestic fuel, industrial fuel and motor fuel.
Page 37 of 42
CNG: Natural gas is a mixture of mainly methane (60-95%) with small amounts of ethane,
H2, CO2 and He. It is stored and supplied as compressed natural gas (CNG) at a pressure
of 16 to 25 bar in cylinders. The calorific value of CNG is 12000-14000 kcal/m3.
Advantages: It is cheaper than LPG and does not release any harmful gases during
combustion. Hence, it is eco-friendly.
Uses: as motor fuel.
UNIT-V: COMPOSITES, BIODIESEL GREEN CHEMISTRY
1. What is trans-esterification? Discuss biodiesel properties.
It is a natural and renewable domestic fuel alternative for diesel engines made from
vegetables oils, mostly soya and corn. It contains no petroleum, is non-toxic and biodegradable.
Vegetable oils contain 90-98% triglycerides along with small quantities of mono and
triglycerides, free fatty acids, phospo lipids, phosphotides, carotenes etc. Triglycerides are esters of
long chain fatty acids such as stearic acid, palmitic acid, linoleic acid, oleic acid.
Biodiesel is produced from the seeds of Jetropa. Vegetable oils are not used directly as diesel
fuel due to their high viscosities; therefore trans-esterification of vegetable oils is done to reduce the
viscosity.
Trans-esterification is the process of exchanging the alkyl group of an ester with the alkyl
group of an alcohol. These reactions can be catalyzed acids, bases or enzymes.
Properties:
• The color of biodiesel ranges from golden to dark brown, depending on the production
method.
• It is slightly miscible with water, has a high boiling point and low vapor pressure.
• The calorific value of biodiesel is about 37.27 MJ/kg. This is 9% lower than regular
petrodiesel.
• The flash point of biodiesel exceeds 130 °C, significantly higher than that of petroleum diesel
which may be as low as 52 °C.
• Biodiesel has a density of ~0.88 g/cm³, higher than petrodiesel (~0.85 g/cm³).
Significance: 1). It can be produced from renewable domestic resources. 2). Energy efficient. 3). It is
a fuel manufactured from methanol, vegetable oils, animal fats and recycled cooking fats hence it
Page 38 of 42
burns clean, which results in significant reduction of all types of pollutants that contribute to smog
and global warming and omits up to 85% fewer cancer causing agents.
Limitations: 1). Generally has higher cloud and pour point, so it will freeze at higher temperature
than conventional diesel. 2). It is not compatible with some metals and plastics.Explain the
carbon neutrality of biodiesel?
Carbon neutrality means having a balance between emitting carbon and absorbing
carbon from the atmosphere. Plants absorb carbon in the form of CO2 and emit the same
during their combustion, there by achieving carbon neutrality. Biodiesel is a renewable
fuel obtained from the plants.
2. What are composites? Explain the constituents/composition of composites and

their advantages?
The materials obtained by combining dissimilar materials together so that they work as
single mechanical unit are called composite materials. They have properties different from
the constituents.
Constituents of composite materials:
1. Matrix phase or Matrix: It is the main constituent of composite. It is bonding

material which encloses and adheres to reinforcing material like fibre. It may be
metal, polymer or ceramic giving Metal Matrix Composite (MMC), Polymer Matrix
Composite (PMC), Ceramic Matrix Composite (CMC).
2. Dispersed phase:
i) Fibre: It is long thin filament of ceramic, metal or polymer having high length to
diameter ratio. Its stiffness gives high tensile strength to composite. It also
causes lowering the overall density of composite. The different types are Glass
fibres, Carbon fibres, Aramid fibres (made of liquid crystals).
ii) Particulates: These are small pieces of hard solid material. They distribute
randomly in a matrix. They increase surface hardness, reduce shrinkage and
friction and modify thermal and electrical conductivities. Concrete, Cermet
(ceramic bonded with metals) are particulate composites.
iii) Flakes: These are thin solids having a two-dimensional geometry. They impart
equal strength in a plane compared to fibres. Mica flakes are used in
electrical and thermal insulating appliances.
iv) Whiskers: These are thin strong filaments or fibres made by growing a crystal.
They are several mm in length and diameter in micros. They are made of
graphite, silicon carbide, aluminum oxide. They give high elastic modules, high
strength.
Advantages/Characteristics of composite materials: The important advantages of

composite materials over other bulk materials are as follows.
• They have high specific strength.

• They do not lose their strength even at high temperatures. The loss of strength near
melting point is very low.
• They are hard, tough with good impact and thermal shock resistance.
Page 39 of 42
• They have high corrosion and oxidation resistance compared to metals.

• They have low specific gravity and low cost.
• Thermal expansion, conductivity and electrical conductivity are low and can be
controlled.
• They have better creep and fatigue strength.
3. Discuss fibre-reinforced composites? Give their application?
Fibre-reinforced composites have three components namely filament, a polymer matrix

and a bonding agent which binds filament to polymer. Generally Glass fibres and metallic
fibres are used for this purpose. They have high specific strength, high specific modulus,
stiffness and low density and good mechanical properties.
The characteristics of fibre-reinforced composites depend upon nature and

properties of both matrix and fibre, Orientation and distribution of fibres in matrix,
strength of bonds between them and length to diameter ratio.
For preparing such composites , it is essential that the coefficient expansion of both
fibre and matrix should be very close, both should not react chemically and fibre should
be stable and should retain high percentage of strength at high temperature.
Fibre-reinforced composites are further divided in different types.

1. Glass fibre-reinforced composites: They contain Glass fibres with polymeric
matrix like Nylon, Polyester to improve characteristics. They have low density, high
tensile strength, impact resistance and good chemical and corrosion resistance.
Uses: They are used in automobile parts, plastic pipes, storage tanks, floorings and
transportation industries.
Limitations: Limited service temperature, because most polymeric matrices begin

to deteriorate or flow at high temperature.
2. Carbon fibre-reinforced composites: High performance carbon fibres are used in

polymer matrix composites, which require retention of derived properties even at
higher temperatures and excellent resistance to corrosion along with lighter
weights.
Uses: Military and commercial aircraft structural compounds such as wing, body,
stabilizers, finishing rods, used in military and commercially used helicopters, for
making sports materials like golf sticks and bats. The use of these materials is
limited because of their high cost.
3. Aramid fibre-reinforced composites: These are manufactured fibers where “the

fiber‐forming substance is a long‐chain synthetic polyamide in which at least 85%
of the amide linkages, (‐CO‐NH‐) are attached directly to two aromatic rings. Kevlar
is a very well known and widely used aramid fiber. They possess high resistance to
abrasion and organic solvents. Tough and strong non-conductive materials.
Uses: Used for making automobile brakes and clutches, structural materials of
commercial aircrafts, helicopter parts like rotor blades, motor housing etc.
Page 40 of 42
4. Metallic fibre-reinforced composites: These consist of a metal or alloy (Al, Ni, Co)
matrix and reinforcing materials like metal oxides (Al 2O3) or carbon fibres. They
possess improved specific strength, stiffness, abrasion resistance, creep resistance
and dimensional stability.
Uses: For making the components of turbine engines.
4. What is green chemistry? Discuss the twelve principles of green chemistry.

Green chemistry is the design of chemical products and processes that reduce or
eliminate the use and generation of hazardous substances.
There are twelve basic principles of green chemistry:

1. Prevention of waste.
2. Atom economy.
3. Less hazardous chemical synthesis.
4. Designing safer chemicals.
5. Safer solvents and auxiliaries.
6. Design for energy efficiency.
7. Use of renewable feed stocks.
8. Reduce derivatives.
9. Catalysis.
10. Design for degradation.
11. Real-Time analysis for pollution prevention.
12. Inherently Safer Chemistry for Accident Prevention.
1. Prevention of Waste/ By products: In a manufacturing process, in addition to by
products the unrelated starting materials also form a part of waste. If the waste is
disposed in the atmosphere, sea or land it adds to the pollution.
2. Atom Economy: The maximum incorporation of the atoms of the reactants and
reagents into the final products is called atom economy.
𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒅𝒆𝒔𝒊𝒓𝒆𝒅 𝒑𝒓𝒐𝒅𝒖𝒄𝒕
𝑨𝒕𝒐𝒎 𝒆𝒄𝒐𝒏𝒐𝒎𝒚 = 𝒙 𝟏𝟎𝟎
𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒂𝒍𝒍 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
3. Less hazardous chemical synthesis: It is important to prevent or minimize the

formation of hazardous products which may be toxic or environmentally harmful.
Therefore, for the same conversion an alternative process may be used.

4. Designing safer chemicals: The chemicals or pharmaceuticals synthesized should
be safe to use. For example: A drug “thalidomide” prescribed for nausea and
vomiting during pregnancy had adverse effects, led to birth defects like deformed
limbs.
5. Safer solvents and auxiliaries: The solvents used in a reaction should not cause
environment pollution.
For example: Benzene and CCl4 are highly carcinogenic. Alternative solvents
like water, ethanol are green solvents.
Page 41 of 42
6. Design for energy efficiency: Conventional heating methods are not energy
efficient and the rate of reaction may be slow. The alternative energy sources like
microwave, ultrasound or sunlight/UV may be used.
7. Reduce derivatives: Rearrangement reactions are 100% atom economic.
8. Catalysis: Phase transfer catalysts in organic synthesis and biocatalysts (yeast,
enzymes etc.) may be used.
5. What do you mean by clean technology?
Clean technology refers to energy efficient processes which gives 100% atom economy
by avoiding conventional prolonged heating methods, to help save raw materials,
natural resources and reduce pollution. Photochemical, microwave and ultrasound
assisted reactions are best examples for clean technology.
6. Write any two examples of Clean Technology?
Ultra sound assisted Cannizaro reaction:
Williamson synthesis (microwave/ultrasound simulated):
Page 42 of 42

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Matrusri Engineering College B.E.

1. Differentiate single electrode potential and standard electrode potential.

Role of salt bridge:

4. Derive Nernst equation? Give its applications.

Nernst equation can be derived from Vant Hoff’s isotherm

∆G = ∆G0 + RTlnQ --------------(1)

From the thermodynamics ∆G = - nFE and ∆G0 = -nFE0

By substituting the above values in equation (i)

-nFE = -nFE0 + RTlnQ

By dividing the equation with -nF on both sides,

For a Redox reaction: Zn + Cu2+ → Zn2+ + Cu

For a reduction reaction: Mn+ → M + ne-

Applications of Nernst Equation:

= 1.565 – 0.0592 = 1.5058 V

It is a secondary reference electrode consisting of mercury-mercurous chloride (Hg-Hg2Cl2)

Construction: It consists of a plug at the bottom of which a small amount of Hg is placed.

The calomel electrode is reversible to Cl- ion concentration.

The standard reduction potential of calomel electrode at 250C is

0.1M KCl | Hg2Cl2(s) | Hg, Pt 0.3338V Decinormal Calomel Electrode(DNCE)

1.0M KCl | Hg2Cl2(s) | Hg, Pt 0.2800V Normal Calomel Electrode (NCE)

Sat. KCl | Hg2Cl2(s) | Hg, Pt 0.2415V Saturated Calomel Electrode (SCE)

7. What is Quinhydrone? Explain the determination of pH of a solution using

Quinhydrone electrode is setup by adding a pinch of Quinhydrone to the solution

at 250C the equation may written as

Since, pH = - log [H+]

EQHE = E0QHE – 0.0591pH

Determination of pH using Quinhydrone electrode: The potential of Quinhydrone

Pt | Hg, Hg2Cl2(s) | KCl(saturated) || H+ (unknown) | Q, QH2 | Pt

The emf of the cell Ecell = EQHE - ESCE

Ecell = (0.6996 – 0.0591pH) – 0.242 V

8. What is ion selective electrode? Explain construction and working of glass

It is represented as: Pt | Ag, AgCl | 0.1N HCl | Glass membrane

Electrode Reaction: AgCl + e- AgCl

Eglass = E0glass + 0.0592 pH

Enthalpy and EMF:

Entropy and EMF:

Then equation (1) can be written as

Ex;- dry cell ( Leclanche cells)

Ex:- Lead-acid cells, Nickel-Cadmium cell, Lithium cells

At cathode: 2MnO2 + H2O + 2e- → Mn2O3 + 2OH-

The overall cell reaction: Zn + 2MnO2 + H2O → Zn2+ + Mn2O3 + 2OH-

Zn2+ + 2NH3 + 2Cl- → [Zn(NH3)2]Cl2

Discharging: When the storage cell is operating as a voltaic cell, it is said to be

The net cell reaction during discharging:

Pb + PbO2 + 2H2SO4 → 2PbSO4 ↓ + 2H2O + Energy

At cathode: PbSO4 + 2e- → Pb

Hence, net reaction during charging: 2PbSO4 + 2 H2O + energy → Pb + PbO2 +

13. Write a note on Li ion secondary cells.

During discharging lithium ions are extracted from anode by electrochemical

This cell produces 3.7V.

Electrode reactions: At the anode: CH3OH + 6OH- → CO2 + 5H2O + 6e-

Advantages of fuel cells:

• No emission of toxic gases and chemical wastes are in safe limits.

UNIT-II: WATER CHEMISTRY AND CORROSION

1. Describe the estimation of hardness of water sample by EDTA Method.

To determine the equivalence point Eriochrome black-T (EBT) is used as an

1. Preparation of standard hard water: Dissolve 1 g of pure CaCO3 in minimum

i.e. 50 mg of CaCO3 eq. = V1 ml of EDTA

2. Estimation of Total hardness: Pipette out 50 ml of water sample in a conical

3. Estimation of permanent hardness: Take 250 ml of the water sample in a large

4. Temporary hardness = [Total – Permanent] hardness

2. Discuss the water softening by ion – exchange process?

R’OH-- + Cl- → R’Cl- + OH-