Chemistry Notes (2019-20) Final

B.
E II Sem (AICTE Model Curriculum)

Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20)
Unit-I Electrochemistry and Battery Chemistry

Electrochemical cells:
Electrolytic cell:
The cell which converts electrical energy into chemical

energy is called as electrolytic cell. An electrolytic cell
consists of two metallic or graphite rods dipping in solution
of electrolyte and connected to a battery. The rod
connected to a positive terminal of the battery acts as
anode while that connected to negative terminal acts as
cathode. It is to be noted that in an electrolytic cell anode is
of positive sign (+) ,but the cathode is of negative sign (-).
Galvanic Cell: Galvanic cell is a device

which converts chemical energy into
electrical energy by means of a
spontaneous redox reaction. It consists of
two electrodes immersed in the solution
of their respective electrolytes. The two
electrodes called, half cells, are connected
by a salt bridge. The electrodes are
connected to potentiometer or voltmeter
by a electrical wire. The electrode at
which oxidation occurs is called as anode
(Negative (-) Electrode). The electrode at
which reduction occurs is called as
Cathode (Positive (+) Electrode). Eg:
Daniel cell
Salt bridge & Its Role:
Salt bridge is an inverted U-tube consists of a concentrated solution of electrolytes like KCl,
KNO3, and NH4Cl.These electrolytes are preferred because the mobilities of cation and anion
are almost equal.
1. It connects the solutions of two half-cells and completes the cell circuit.
2. It prevents diffusion of the solutions from one half-cell to the other

B.E II Sem (AICTE Model Curriculum)
3. It keeps the solutions in two half-cells electrically neutral.
4. It prevents liquid-liquid junction-potential.
Representation of cell Or Cell Notation:
Difference between Electrolytic cell and Galvanic Cell
EMF of a cell:
When two electrodes are combined current flows from higher potential to lower potential,
the potential difference which is responsible for the flow of current is called EMF of the cell.
Ecell = E Cathode- E Anode
Where, E Cathode and E Anode are reduction potentials of cathode and anode respectively.
Electrode potential:
When a metal is placed in its electrolytic solution, the metal acquires either positive or
negative charge with respect to electrolytic solution which results a potential difference is
developed at the interface between electrode and electrolytic solution. This potential
difference is called electrode potential. Or
Tendency of an electrode to lose or gain electrons when it is in contact with its own ionic
solution is called as electrode potential.
The tendency of an electrode to lose electrons i.e. to get oxidised, is called Oxidation
potential, whereas, the tendency of an electrode to gain electrons i.e.to get reduced, is
called Reduction potential.
Standard electrode potential:
The potential of an electrode, at a given temperature, depends upon the concentration of

solution of its ions.
“The tendency of a pure metal or pure gas at 1 atm pressure to undergo oxidation or
reduction when it is in contact with 1M solution of its ions at 250C, is called as standard
electrode potential”.
SRP: It is the tendency of a pure metal or pure gas at 1 atm pressure to undergo reduction
when it is in contact with 1M solution of its ions at 250 C.
SOP: It is the tendency of a pure metal or pure gas at 1 atm pressure to undergo oxidation
when it is in contact with 1M solution of its ions at 250 C.
Thermodynamics of EMF of cells
(1) Relationship between Enthalpy change and EMF:
From Gibbs-Helmholtz equation, we have

𝜕(∆𝐺)
∆𝐺 = ∆𝐻 + 𝑇 [ ] -------- (1)
𝜕𝑇 𝑃
We know,
∆𝐺 = ∆𝐻 − 𝑇∆𝑆 ------------------ (2)
From equation (1) & (2) , we get

𝜕(∆𝐺)
∆𝑆 = − [ ] ----------------- (3)
𝜕𝑇 𝑃
We also know ,
∆𝐺 = −𝑛𝐹𝐸 ----------------- (4)
Substituting for ∆𝐺 = −𝑛𝐹𝐸 in equation (3) , we get

𝜕(−𝑛𝐹𝐸)
∆𝑆 = − [ ]
𝜕𝑇 𝑃
𝝏𝑬
∆𝑺 = 𝒏𝑭 [ ] --------------- (5)
𝝏𝑻 𝑷
𝜕𝐸
[ ] ---- Temperature coefficient of EMF of a cell.
𝜕𝑇 𝑃
Entropy changes can be calculated the for the cell reaction using equation - (5) , provided
𝜕𝐸
[ ]
𝜕𝑇 𝑃
(2) Relationship between Enthalpy change and EMF:
From Gibbs-Helmholtz equation, we have

𝜕(∆𝐺)
∆𝐺 = ∆𝐻 + 𝑇 [ ] -------- (1)
𝜕𝑇 𝑃
Substituting for ∆𝐺 = -nFE , we get
𝜕(−𝑛𝐹𝐸)
−𝑛𝐹𝐸 = ∆𝐻 + 𝑇 [ ]
𝜕𝑇 𝑃
𝜕𝐸
−𝑛𝐹𝐸 = ∆𝐻 − 𝑛𝐹𝑇 [ ] ------------ (2)
𝜕𝑇 𝑃
On rearranging Equation (2) , we get

𝝏𝑬
∆𝑯 = 𝒏𝑭 (𝑻 [ ] − 𝑬) ------------------ (3)
𝝏𝑻 𝑷
𝜕𝐸
The above Equation is used to calculate Enthalpy changes, provided [ ] & 𝐸
𝜕𝑇 𝑃
Nernst Equation & Its derivation:
The Nernst Equation helps us to determine cell potential or electrode potential under non-
standard and non-equilibrium conditions. It relates the measured cell potential/electrode
potential to the reaction quotient.
𝑄
Cconsider a redox reaction, 𝑎𝐴 + 𝑏𝐵 ⇔ 𝑐𝐶 + 𝑑𝐷
[𝐶]𝑑 [𝐷]𝑑
𝑄=
[𝐴]𝑎 [𝐵]𝑏
The decrease in the free energy of such equilibrium is given as, −∆𝐺 = −∆𝐺 0 − 2.030𝑅𝑇 𝑄
When a system is operating reversibly the work done by the system is equal to the decrease
in the free energy of the system.
If the charge associated with a redox process is “nF coulombs” and potential generated is E
Volts, the net electrical work done by the reversible cell is “nFE Joules”
−∆𝐺 0 = 𝑛𝐹𝐸𝑐𝑒𝑙𝑙 & − ∆𝐺 = 𝑛𝐹𝐸𝑐𝑒𝑙𝑙

0
𝑛𝐹𝐸𝑐𝑒𝑙𝑙 = 𝑛𝐹𝐸𝑐𝑒𝑙𝑙 − 𝑅𝑇𝑙𝑛 𝑄
0
𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑛 𝑄
𝑛𝐹
0
2.303𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔 𝑄
𝑛𝐹
0
2.303𝑅𝑇 [𝐶]𝑐 ][𝐷]𝑑
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔
𝑛𝐹 [𝐴]𝑎 [𝐵]𝑏
At T= 250C = 298 K, R- Gas Constant = 8.314J/mole, F – Faraday = 96500 Coulombs
0 [𝐶]𝑐 ][𝐷]𝑑
Therefore, 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 0.0591 𝑙𝑜𝑔
[𝐴]𝑎 [𝐵]𝑏
Applications of Nernst Equation:
1. Nernst equation is used to study the effect of electrolyte concentration on electrode

potential.
2. Nernst equation can be used to calculate cell potentials / Electrode potentials under
non-standard and non-equilibrium condition.
3. Determination of unknown concentration of one of the ionic species involved in a

0
redox reaction is possible with help of Nernst equation provided 𝐸𝑐𝑒𝑙𝑙 and
concentration of other ionic species is known.
4. The pH of a solution can be calculated from the measurement of EMF and Nernst
equation.
5. It can also be used to find the valency (n) of reactive species.
6. It can be used to calculate equilibrium constant of redox reaction.
Types of Electrodes:
(1) Metal – Metal ion Electrode:

It consists of a pure metal in contact with a solution of its ions. It is constructed by
dipping a pure metal in a electrolytic solution of metal.
Representation of the electrode: M/ M+n
E.g. Zn rod dipped in ZnSO4.
(2) Gas Electrode
Gas electrode consists of a gas bubbling about an inert metal wire or foil immersed
in a solution containing ions to which the gas is reversible. Inert metal wire or foil,
usually platinum, helps to attain the equilibrium between the gas & ions and also
serve as electric contact for the electrode.
Example: Hydrogen electrode
(3) Metal – insoluble salt electrode:
It consists of a pure metal in contact with one of its sparingly soluble salts and a
solution of a soluble salt having a common anion with the sparingly soluble salt.
E.g. Calomel electrode:
Construction and working of Calomel electrode:

Calomel electrode is an example of metal -metal

insoluble salt electrode, which consists of a glass
tube containing two side arms. One of the arms is
to connect to salt bridge and the other one is to
introduce the components of electrode. Pure
Mercury is placed at the bottom of the glass tube.
Mercury is covered with a paste of Mercury and
Mercurous chloride, over which a solution of
potassium chloride is placed. A platinum wire
sealed in a thin glass tube, dipping into the mercury
layer, is used for making electrical contact with the
external circuit.
Calomel electrode is represented as Pt-Hg/ Hg2Cl2/KCl (aq).
Calomel electrode acts as either anode or cathode w.r.to the other electrode to which it is
connected.
If it acts as anode, it involves If it acts as cathode it involves

oxidation. reduction.
2Hg----------> Hg22+ + 2e- Hg2Cl2----------> Hg22++ 2Cl-
Hg22++ 2Cl- ------> Hg2Cl2 Hg22+ + 2e- --------> 2Hg
___________________________________ _____________________________ ____________
2Hg + 2Cl- -----> Hg2Cl2 + 2e- Hg2Cl2 + 2e- -----------> 2 Hg + 2Cl-
________________________ __________________________
When it acts as anode, mercury is When it acts as cathode, Hg22+

converted to Mercurous ions. ions, furnished by the sparingly
Mercurous ions would combine soluble Hg2Cl2, would be
with Cl- ions furnished by KCl to discharged at the electrode and
form sparingly soluble Hg2Cl2 there is an increase in the
which results there is a fall in the concentration of Cl- ions. Thus,
concentration of Cl- ions. Calomel electrode is said to be
reversible to Cl- ions.
0
The reduction potential of calomel electrode is given by,𝐸𝐶𝐸 = 𝐸𝐶𝐸 −
0.0591 [𝐻𝑔]2 [𝐶𝑙 − ]2
𝑙𝑜𝑔 [𝐻𝑔2 𝐶𝑙2 ]
2
0
𝐸𝐶𝐸 = 0.280𝑉 − 0.0591log[𝐶𝑙 − ] Since [Hg] = [Hg2Cl2] = 1 and 𝐸𝐶𝐸 = 0.280 𝑉
The potential of the calomel electrode depends upon the concentration of the
chloride ion. If the concentration of KCl is 0.1 N, 1.0 N and saturated, calomel
electrode is called as Decinormal, Normal and Saturated calomel electrode and their
electrode potentials at 250C are 0.333V, 0.28 V and 0.242V respectively.
Advantages: Its construction is very easy, potential measurements are reproducible.
Disadvantages: Since Hg2Cl2 breaks at 500C, it can’t be used above this temperature.
(4) Redox Electrodes:

A Redox electrode consists of an inert material like Pt or Au dipped into a solution
containing solution of a chemical species in two different oxidation states.
E.g. Quinhydrone Electrode:
Construction and working of Quinhydrone electrode:
The Quinhydrone electrode is an
example of redox electrode, which is
constructed by adding a pinch of
Quinhydrone powder, which is an
equimolar mixture of quinone and
hydroquinone to a acid solution,
under test, taken in a beaker. An
inert Pt electrode is dipped into the
solution for making electrical
contact.
The electrode is represented as H+(aq); Q ; QH2/Pt.
It will either act as anode or cathode depending on the other electrode to which it is
connected.
If it acts as cathode, then the electrode reaction is,

O OH
+ -
2H 2e
O OH
Quinone (Q) Hydroquinone (QH2)
The electrode potential is calculated by using Nernst equation,
0 0.0591 [𝑄𝐻2 ]
𝐸𝑄𝐻𝐸 = 𝐸𝑄𝐻𝐸 − 𝑙𝑜𝑔
2 [𝑄][𝐻 + ]2
0 0.0591
𝐸𝑄𝐻𝐸 = 𝐸𝑄𝐻𝐸 + 𝑙𝑜𝑔 [𝐻 + ]2 ( Since [QH2 =[Q] =1)
2
0
𝐸𝑄𝐻𝐸 = 𝐸𝑄𝐻𝐸 + 0.0591log[𝐻 + ]
0
𝐸𝑄𝐻𝐸 = 𝐸𝑄𝐻𝐸 − 0.0591pH
0
𝐸𝑄𝐻𝐸 = 0.699𝑉 − 0.0591pH (On Hydrogen Scale 𝐸𝑄𝐻𝐸 = 0.699𝑉)
Potential of Quinhydrone electrode depends on pH of the solution with which it is in

contact. Therefore, Quinhydrone electrode can also be used to measure the pH of
solution.
Advantages:
The electrode setup is very easy, pH values obtained are accurate, small quantities of
solution are sufficient for the measurement.
Disadvantages:
It cannot be used in the solutions that would react with quinone or hydroquinone.
Since it is a weak acid, cannot be used above pH 8.5 at which the dissociation of
Quinhydrone becomes appreciable.
It is oxidized by air in strongly alkaline medium.
(5) Ion selective electrode:
Ion-selective electrode possesses the ability to respond only to certain specific ions,
thereby developing a potential with respect to that specific ions in a solution and
ignoring the other ions totally. In other words, the potential developed by an ion –
selective electrode depends only on the concentration of ions of interest.
Eg; Glass electrode
Glass electrode is made up of a special type of glass

having low melting point and high electrical
conductance. The bottom of the glass electrode is

blown in the form a bulb, which is filled with a 0.1
N HCl solution to provide constant hydrogen ion
concentration. A silver wire coated with AgCl is
inserted into the bulb for making electrical contact.
The representation of glass electrode is, Ag/AgCl/0.1N HCl/Glass membrane. The

potential of the glass electrode is given as, 𝐸𝐺 = 𝐸𝐺0 − 0.0591𝑝𝐻
Determination of pH of a solution using quinhydrone electrode:
The electrode potential of Quinhydrone electrode, which is reversible to H+ ions,

depends on pH of a solution; therefore it is used to determine pH of a solution. To
determine pH of a solution, quinhydrone electrode is combined with a reference
electrode like calomel electrode. The cell consists of Quinhydrone and Calomel
electrode is represented as,
Pt, Hg/ Hg2Cl2,Cl-(Sat ,aq) // H+ (aq),Q, QH2/Pt.
𝐸𝑐𝑒𝑙𝑙 = 0.457 − 0.0591𝑝𝐻
0.457 − 𝐸𝑐𝑒𝑙𝑙
𝑝𝐻 =
0.0591
Problems Based on Applications of Nernst Equations:
1. Consider the cell , Zn/Zn+2(aq) //Cu+2(aq) /Cu .The standard electrode potentials are;
Cu+2 +2e- --------> Cu; 𝐸 0 = 0.35𝑉
Zn+2+2e- --------> Zn; 𝐸 0 = −0.763𝑉
(i) Write down the cell reaction (ii) Calculate the EMF of the cell.
Solution: (i) Reduction potential of Zn is less than Cu, hence Zn acts anode and Cu
acts as cathode.
At anode Zn --------> Zn+2+2e- (Oxidation)

At Cathode Cu+2 +2e- --------> Cu (Reduction)
______________________________
Zn +Cu+2 --------> Cu + Zn+2
0 0 0
(ii) 𝐸𝐶𝑒𝑙𝑙 = 𝐸𝐶𝑢 +2 /𝐶𝑢 − 𝐸𝑍𝑛+2 /𝑍𝑛
= 0.35𝑉 − (−0.763𝑉)
= 1.113 𝑉
2. Calculate the electrode potential at a copper electrode dipped in a 0.1M solution of

copper sulphate at 250C.The standard electrode potential of Cu+2/Cu system is 0.34V
at 298K.
Ans: 0.31045 Volts

0
3. 𝐸𝑐𝑒𝑙𝑙 of a given cell, Zn(s) /Zn+2 1M(aq) //Cu+2 1M (aq) /Cu(s) , is 1.10 V at 250C
.Calculate equilibrium constant for the cell reaction, Zn(s) +Cu+2(aq)⟺ Cu(s) +
Zn+2(aq).
𝐴𝑛𝑠 : 1.67 x 1037
4. A zinc rod is placed in a 0.1M solution of ZnSO4 at 250C.Calculate the potential of the
0
electrode at this temperature, assuming 96% dissociation of ZnSO4 and 𝐸𝑍𝑛 +2 =
⁄𝑍𝑛
−0.76 𝑉.
Ans: 𝐸𝑍𝑛+2⁄ = −0.79 𝑉.
𝑍𝑛
5. The emf of a cell corresponding to the reaction, Zn + 2H+----------> Zn+2 +H2 (g) 1 atm
is 0.28V at 250C. Write the half cell reactions and calculate the pH of the solution at
0
hydrogen electrode. ( 𝐸𝑍𝑛 +2 = −0.76 𝑉 𝐸𝐻0 +⁄ = 0𝑉)
⁄ 𝑍𝑛 H2
Ans : pH= 8.6218
Batteries
Battery:
Battery is a device consisting of one or more electrochemical cells connected parallelly or in
series that converts stored chemical energy into electrical energy.
What are primary and secondary batteries?
Primary batteries Secondary batteries

(Rechargeable batteries)
Batteries which are not rechargeable The batteries which can be recharged are
after their use are called primary called Secondary batteries.
batteries
The chemical reactions that take place The chemical reaction that take place are
are not reversible reversible
Eg: Zinc – Carbon battery Eg: Lead-Acid battery, Lithium ion battery.
Explain construction, working, advantages and disadvantages of Zinc-Carbon battery.
Zinc – Carbon Battery (Dry Cell)
Construction It is primary battery.
Anode (Negative electrode): Zn Container
Cathode (Positive Electrode): Carbon rod/MnO2
Electrolyte: A moist mixture of NH4Cl, ZnCl2
A Zinc -Carbon battery is a battery packaged in a

zinc container that also serves as a negative
electrode. The positive electrode is carbon rod
surrounded by a mixture of manganese dioxide and
carbon powder. The electrolyte used is a moist
paste of ammonium chloride and zinc chloride.
Working
At Negative Electrode (Anode): Zn(s) -------------------------------------> Zn2+(aq) + 2e- (Oxidation)

At Positive Electrode (Cathode) : 2MnO2(s) + 2H2O (l) + 2e- ----------> 2MnO(OH) (s) + 2OH-(aq) (Reduction)
In addition to main reactions, some secondary reactions also take place within the cell.
2NH4+ (aq) + 2OH- (aq) -------------> 2NH3(g) + 2H2O (l)
Zn2+ + 2NH3(g) + 2 Cl- -------------> [Zn(NH3)2] Cl2(aq)
Overall cell reaction:
Zn(s) + 2MnO2(s) +2NH4Cl (aq) ----> 2MnO(OH) (s) + [Zn(NH3)2]Cl2 (aq)

Voltage of the cell : 1.6 Volt.
Applications Dry cells are used in flashlights, transistor radios, calculators etc.
Advantages Cost of this battery is quite low, Portable.
Disadvantages Batteries are not rechargeable, short shelf life.
Explain the construction, Working, advantages and disadvantages of Lead-Acid battery.
Lead -Acid battery
The lead-acid battery was invented in 1859 by French physicist Gaston Planté. It is the oldest
rechargeable battery.
Construction
Negative electrode: Spongy Lead (Pb)
Positive electrode: Lead plate coated with PbO2
Electrolyte: 30 % H2SO4 solution.
It consists of a group of Lead plates coated with spongy

Lead, which acts as anode and alternating with a group of
lead plates coated with PbO2 acts as cathode. These two
are separated by insulating material like thin wooden or
It is a secondary battery. fibre glass sheets. These plates are immersed in a solution
of about 30% H2SO4.
The cell is represented as,
Pb(s) , PbSO4(s) / H2SO4 (aq) (30%) / PbSO4(s) ,PbO2(s) , Pb(s)
Working
During Discharging During Charging
During discharging, Lead-Acid battery acts as During charging, Lead-Acid battery acts as
electrochemical cell (Voltaic cell). electrolytic cell.
At Negative Electrode (Anode): At Negative Electrode (Cathode):
Pb(s) -----------> Pb2+ + 2e- PbSO4(s)-----------> Pb2+ + SO42-
Pb2+ + SO42------------> PbSO4 (Precipitate) Pb2+ + 2e- -----------> Pb(s)
_____________________________ ___________________________
Pb(s) + SO42- ------------> PbSO4(s) + 2e- PbSO4 + 2e- -------> Pb(s) + SO42-
____________________________ _____________________________
At Positive Electrode (Cathode): At Positive Electrode (Anode):

PbO2(s) + 4H+ + 2e- -------> Pb2+ + 2H2O(l) PbSO4(s) -------> Pb2+ + SO42-
Pb2+ + SO42--------> PbSO4 (Precipitate) Pb2+ + 2H2O -------> PbO2(s) + 4H+ + 2e-
_________________________________________ __________________________________________
PbO2(s)+ 4H+ + 2SO42- + 2e-------> PbSO4(s) +2H2O(l) PbSO4(s) +2H2O(l) ------> PbO2(s) + 4H+ + 2SO42- + 2e-
_________________________________________ __________________________________________
Net cell reaction:
Discharging
Pb + PbO2 + 2H2SO4 2PbSO4 + 2H2O
Charging
During discharging H2SO4 is consumed and its concentration decreases. During charging H2SO4 is
regenerated and its original concentration is restored. The variation of concentration of the acid and
hence the extent of discharge or charge of the cell can be easily monitored by changes in specific
gravity of the acid. During charging, Specific gravity of H2SO4 increases whereas during discharge
specific gravity decreases.
Voltage of each cell is 2V. In general, lead-Acid battery consists of such 6 cells which are connected in
series to get higher voltage(12V)
Applications: Lead acid -batteries are used in telecommunication, power systems, radio, and television
systems, solar, UPS, electric vehicles, automobile, emergency lights.
Advantages Low maintenance, Low Cost,
Disadvantages Heavy in weight, Lead is not environmentally friendly.
Explain the construction and working of lithium ion battery.
Lithium – Ion Battery (LIB)

Lithium ion battery is a secondary battery. Lithium ion batteries are rechargeable batteries.
Construction The primary functional components of a Li-ion
battery are,
Anode (-ve): Porous Graphite
Cathode (+ve): Lithium metal oxide (Li1-xCoO2)
Electrolyte: A non-aqueous medium used as
electrolyte, usually which is a mixture of
organic carbonate (ethylene carbonate)
containing complex ([LiPF6]) of lithium ions.
Anode and cathode are separated by
electrical insulating separator (diaphragm)
which permeable to lithium ions.
Working:
During dischargi ng, Lithium ions travel from Negative electrode to positive
electrode and transition metal Co get reduced from Co+4 to Co+3.
At Negative electrode: 𝒙𝑳𝒊𝑪𝟔 − − − −−→ 𝒙𝑳𝒊+ + 𝒙𝒆− + 𝒙𝑪𝟔
At positive electrode: 𝑳𝒊𝟏−𝒙 𝑪𝒐𝑶𝟐 + 𝒙𝑳𝒊+ + 𝒙𝒆− −→ 𝑳𝒊𝑪𝒐𝑶𝟐

----------------------------------------------------------------------------------------------------------
𝑵𝒆𝒕 𝑹𝒆𝒂𝒄𝒕𝒊𝒐𝒏 𝒅𝒖𝒓𝒊𝒏𝒈 𝒅𝒊𝒔𝒄𝒉𝒂𝒓𝒈𝒆 ∶ 𝒙𝑳𝒊𝑪𝟔 + 𝑳𝒊𝟏−𝒙 𝑪𝒐𝑶𝟐 − − − −−→ 𝒙𝑪𝟔 + 𝑳𝒊𝑪𝒐𝑶𝟐
The electrode reactions that take place during discharging and charging can be summarised as,
The cobalt electrode reaction is only reversible for x < 0.5

Voltage: 3.7 V
Depending on the material choices the voltage, capacity, life and safety of a Li-ion battery can
changes.
Advantages: Light weight, no self-discharge, compact

Disadvantages: Over charging may lead to overheating and battery may explode. Over charge and
discharge makes this battery irreversible.
Applications:
1. As mobile phone batteries, laptop batteries.
2. As a battery in electric cars.
What are fuel cells or Flow batteries?
Fuel cells (Flow batteries): Fuel cell is an Electrochemical cell consisting of two electrodes
and an electrolyte which converts chemical energy (Free energy) of a fuel and oxidant
directly into electrical energy. Fuel cells can supply current if the reactants are supplied.
Methanol -Oxygen fuel cell
Construction;
cathodic compartments and electrolyte compartment.

Usually the electrodes are made up of platinum since
they are inert. Methanol and water is fed into anodic
compartment where CH3OH undergoes oxidation.
Oxygen is fed into cathodic compartment where it
undergoes reduction. These two are separated by a
proton exchange membrane. The protons generated
during oxidation pass through the proton exchange
The methanol –oxygen fuel membrane and reaches to cathodic compartment and
cell consists of anodic, combines with O2 to form H2O
Working: The electrode reactions that take place are,
At anode: CH3OH (l) + H2O(l) → CO2 (g)+ 6H+ + 6e-
At cathode: 3/2 O2 (g) + 6H+ + 6e- → 3 H2O (l)
The overall reaction: CH3OH (l) +3/2 O2 (g)→ 2 H2O(l) + CO2(g)

What are the advantages and applications of fuel cells?
Advantages:
1. Fuel cells have a higher efficiency than diesel or gas engines.

2. Most fuel cells operate silently, compared to internal combustion engines. They are
therefore ideally suited for use within buildings such as hospitals.
3. Fuel cells can eliminate pollution caused by burning fossil fuels; for hydrogen fuelled fuel
cells, the only by-product at point of use is water.
4. Noise and thermal pollution is low.
Applications:
1. Portable electronic applications such as batteries in laptops, smart phones
2. Stationary fuel cells are used for commercial, industrial and residential primary and
backup power generation.
3. Transportation: Fuel cells are used in Automobiles, in military applications, Space vehicles
applications
UNIT–II
Water Chemistry and Corrosion
Soft water produces lather readily with soap, but hard water does not produce lather readily with
soap.
Hardness of Water: Hardness of water is “the characteristic that prevents lathering of soap”. (Or) It
is defined as “the soap consuming capacity of water”.
Cause of Hardness: Hardness of water is caused by the presence of certain soluble salts of Ca, Mg,
and salts of some other heavy metals.
Why hard water does not produce lather with soap?
When a sample of hard water is treated with soap (soluble sodium or potassium salt of higher fatty
acid), insoluble soap is formed (calcium or magnesium salt of higher fatty acid). Therefore, hard
water does not produce lather readily with soap.
2C17H35COONa + CaCl2 ---------------> (C17H35COO)2 Ca ↓ + 2NaCl
Soap (Sodium stearate) (From hard water) Calcium stearate (Insoluble)
2C17H35COONa + MgSO4 ---------------> (C17H35COO)2 Mg ↓ + Na2SO4

Soap (Sodium stearate) (From hard water) Calcium stearate (Insoluble)
Similarly, other salts of Calcium and Magnesium like CaSO4, Ca (NO3)2, MgCl2 , etc, also react to form
insoluble precipitates of Calcium and Magnesium salts of higher fatty acids.
Types o f Hardness: 1. Temporary Hardness 2. Permanent hardness
1. Temporary Hardness:
i. Temporary hardness is caused by the presence of dissolved bicarbonates of calcium,
magnesium and bicarbonates of other heavy metals.
ii. Temporary hardness is removed by boiling of water. During boiling, the bicarbonates
are decomposed to give insoluble carbonates or hydroxides that deposited at the
bottom of the vessel.
Ca (HCO3)2 → CaCO3 ↓ + CO2 ↑ + H2O
Mg (HCO3)2 → Mg (OH)2 ↓ + 2CO2 ↑
iii. Temporary hardness is also known as carbonate hardness or alkaline hardness.
2. Permanent Hardness:
i. It is due to the presence of dissolved chlorides, sulphates and nitrates of Calcium,
Magnesium, Iron and other heavy metals.
ii. Salts mainly responsible for permanent hardness are CaCl2, CaSO4, MgCl2, MgSO4,
Ca(NO2)2, etc.
iii. Permanent hardness cannot be removed by simple boiling but can be removed by
special chemical methods, like Lime soda process, Zeolite method, etc.
iv. It is also called as non-carbonate or non-alkaline hardness.
Degree of Hardness/Hardness in terms of CaCO3 equivalents:

Hardness of water is always expressed in terms equivalent of CaCO3, although hardness is never
present in the form of CaCO3.There are two basic reasons for choosing CaCO3 as the standard,
1. It’s simple molecular weight ,100 ( and equivalent weight is exactly 50)
2. It is the most insoluble salt that can be precipitated in water treatment.
The Weight of any hardness causing substance is expressed as equivalents of CaCO3.
Units of hardness:
1. Parts per million (ppm)
It is the parts of calcium carbonate equivalent hardness per 106 parts of water
1ppm = 1 part of CaCO3 equivalent hardness in 106 parts of water
2. Milligrams per litre (mg/L)
It is the number of milligrams of CaCO3 equivalent hardness per litre of water
1 mg/L = 1 mg of CaCO3 equivalent hardness in 1L of water
(1 mg/L = 1ppm )
3. Clarke’s degree (°Cl):
It is parts of CaCO3 equivalent hardness per 70,000 parts of water Or It is number
of grains (1/7000) of CaCO3 equivalent hardness per gallon of water.
4. Degree French (°Fr):
It is the parts of calcium carbonate equivalent hardness per 105 parts of water
Relationship between various units of hardness:
1ppm= 1mg/L= 0.1°Fr= 0.07 °Cl; 1mg/L= 1ppm= 0.1°Fr= 0.07 °Cl;
1°Cl = 1.433°Fr=14.3 ppm =14.3 mg/L; 1°Fr= 10ppm = 10mg/L = 0.7 °Cl
Problems:
1. A sample of water was analysed as given below:
Mg(HCO3)2 =7.3 mg/L , Ca(HCO3)2 =16.2 mg/L MgCl2 =9.5 mg/L, CaSO4 =13.6mg/L.
Calculate the temporary and permanent hardness of water.
Ans: Temporary hardness = 15 ppm; Permanent hardness = 20 ppm
2. A sample of water was analysed and found to contain the following impurities ;
Mg (HCO3)2 =5.84mg/L , Ca (HCO3)2 =4.86 mg/L ,MgSO4 =8.40 mg/L ,
CaSO4 =6.80mg/L, NaCl = 5.87mg/L. Calculate the temporary and permanent & total
hardness of water.
Ans: Temporary hardness = 7 ppm; Permanent hardness = 12 ppm
Total hardness = 19 ppm
3. Calculate the temporary, permanent & total hardness of water sample analysed as:
Mg(HCO3)2 =16.8 mg/L , MgSO4 =24.0 mg/L ,CaCl2 =22.2 mg/L, MgCl2 =19.0mg/L
Ans: Temporary hardness = 11.5ppm, Permanent hardness = 50 ppm,
Total hardness = 61.5 ppm
Estimation of Hardness of water by EDTA method:
I. Principle: Hardness of water is estimated by a complexometric titration which involves EDTA
(Ethelene Diamine Acetic Acid) as a complexing agent. EDTA forms 1:1 stable, colourless complexes
with Ca+2/Mg+2 ions at pH = 9 -10.
In this titration, Eriochrome Black-T (EBT) is used as indicator which shows blue colour in its free
state. When EBT is added to Hard water sample buffered to pH = 10, the water sample turns to
wine-red colour due to the formation of unstable [Ca-EBT]/[Mg-EBT] complex.
During titration, EDTA first combines with freely available Ca +2/ Mg +2 ions of sample water to form
stable and colourless [Ca-EDTA]/[Mg-EDTA] complex and when all freely available Ca +2/ Mg +2 ions
are complexed with EDTA; further added EDTA displaces EBT from [Ca-EBT/Mg-EBT] complex. Thus,
at the end point the colour of the solution changes from wine red to blue.
II. Preparation of Reagents:

1. Preparation of standard hard water sample: 1g of CaCO3 is dissolved in minimum
amount concentrated HCl; it is heated till it becomes dry and dissolved in distilled water and
made up to 1 L using distilled water.
2. Preparation of EDTA solution: About 4g of EDTA is dissolved in minimum quantity of
water and 0.1 g of MgCl2 is added to it and the solution is made up to 1 L using distilled
water.
3. Preparation of buffer solution: About 67.5g of NH4Cl and 570 mL of NH4OH are mixed
and the solution is made to 1L using distilled water.
4. Preparation of EBT indicator: About 0.5g of EBT is dissolved in 100mL of ethanol.
III. Experimental procedure:
1. Standardization of EDTA solution: 25 ml of standard hard water is taken in a clean
conical flask. The solution changes to wine red colour upon the addition of 10mL of buffer
solution and 2 or 3 drops of EBT indicator. This solution is titrated against EDTA solution
taken in burette till the colour of the solution changes to blue. Let the volume of EDTA
consumed be V1 mL .
2. Determination of Total Hardness: 25 mL of hard water sample is taken in a conical flask and
the experiment is carried out as under standardization. Let the volume of EDTA consumed
be V2mL.
3. Determination of permanent hardness: 1L of same hard water sample is boiled to 1/4th
of its volume. All the bicarbonates are converted to insoluble carbonates or hydroxides. It is
filtered; the precipitate is washed with distilled water, washings are collected in filtrate
&made up to 1L.25 mL of this water sample is pipetted into a conical flask and experiment
carried out as under standardization. Let the volume of EDTA consumed be V3mL.
IV. Calculations:
25 𝑚𝐿 𝑜𝑓 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 ℎ𝑎𝑟𝑑 𝑤𝑎𝑡𝑒𝑟 = 𝑉1 𝑚𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴
25 𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3 = 𝑉1 𝑚𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴
25
1𝑚𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴 = 𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑉1
Total Hardness:
25 𝑚𝐿 𝑜𝑓 𝑡𝑒𝑠𝑡 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 = 𝑉2 𝑚𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴
25
= 𝑉2 × 𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑉1
𝑉2
1000 𝑚𝐿 𝑜𝑓 𝑡𝑒𝑠𝑡 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 = 1000 × 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑉1
𝑉2
𝑇𝑜𝑎𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 1000 × 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑉1
Permanent Hardness:
25 𝑚𝐿 𝑜𝑓 𝑏𝑜𝑖𝑙𝑒𝑑 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 = 𝑉3 𝑚𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴
25
= 𝑉3 × 𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑉1
𝑉3
1000 𝑚𝐿 𝑜𝑓 𝑏𝑜𝑖𝑙𝑒𝑑 𝑤𝑎𝑡𝑒𝑟 𝑎𝑠𝑚𝑝𝑙𝑒 = 1000 × 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑉1
𝑉3
𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 1000 × 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑉1
Temporary Hardness:
𝑇𝑒𝑚𝑝𝑜𝑟𝑎𝑟𝑦 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 − 𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠
𝑉2 𝑉3
= 1000 − 1000
𝑉1 𝑉1
𝑉2 𝑉3
= 1000 ( − ) 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑉1 𝑉1
Problems:
1. 20 ml of standard hard water sample, containing 15 g of CaCO3 per litre, required 25
ml of EDTA solution. 100 mL of water sample required 18 mL of standard EDTA
solution.100 mL of the sample after boiling required 12mL same EDTA solution.
Calculate the temporary and the permanent hardness of the sample.
Solution:
1 L or1000ml of standard hard water = 15 g = 15000 mg of 𝐶𝑎𝐶𝑂3
15000
Therefore, 1 mL of standard hard water = 𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3 = 15𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3
1000
Standardization of EDTA solution:
20 𝑚𝐿 𝑜𝑓 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 ℎ𝑎𝑟𝑑 𝑤𝑎𝑡𝑒𝑟 = 𝑉1 𝑚𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴

20 𝑋15 𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3 = 25 𝑚𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴

300
𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3 = 1𝑚𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴
25
Therefore, 1 mL of EDTA = 12 mg of CaCO3
Total Hardness:
100 𝑚𝐿 𝑜𝑓 𝑡𝑒𝑠𝑡 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 = 𝑉2 𝑚𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴
= 18 × 12 𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3
= 216 𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3
1000𝑚𝐿 𝑜𝑓 𝑡𝑒𝑠𝑡 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 = 2160 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
Permanent Hardness:
100 𝑚𝐿 𝑜𝑓 𝑏𝑜𝑖𝑙𝑒𝑑 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 = 𝑉3 𝑚𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴
= 12 × 12 𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3
= 144 𝑚𝑔 𝑜𝑓 𝐶𝑎𝐶𝑂3
1000 𝑚𝐿 𝑜𝑓 𝑏𝑜𝑖𝑙𝑒𝑑 𝑤𝑎𝑡𝑒𝑟 𝑎𝑠𝑚𝑝𝑙𝑒 = 1440 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
Temporary Hardness:
= (2160 − 1440 )
= 720 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
2. 20 ml of standard hard water sample, containing 1 g of CaCO3 per litre, required 25
ml of EDTA solution.100 mL of test water sample required 18 mL of standard EDTA
solution.100 mL of the same sample after boiling required 12 mL same EDTA
solution. Calculate the temporary and the permanent hardness of the sample.
Solution: Given,
Volume of EDTA consumed for 20 mL of standard water = 25 mL
Therefore, for 100 mL of standard water (V1) = 125 mL
Volume of EDTA consumed for 100 mL of test water sample (V2) = 18 mL
Volume of EDTA consumed for 100 mL of boiled test water sample (V3) = 12 mL
𝑚𝑔 𝑚𝑔
𝑊𝑡.𝑜𝑓 𝐻.𝐶.𝑆 ( )𝑋100 1000 ( )𝑋100
𝐿 𝐿
Hardness of standard hard water (y) = = = 1000 mg/L or ppm
𝑀𝑜𝑙.𝑤𝑡 𝑜𝑓𝐻.𝐶.𝑆 100
Total Hardness:
𝑉2
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑦 × 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑉1
18
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 1000 × 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
125
= 144 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
Permanent Hardness:
𝑉3
𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑦 × 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
𝑉1
12
𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 1000 × 𝑝𝑝𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3
125
= 96 ppm equivalents of CaCO3.
Temporary Hardness:
= (144-96) ppm equivalents of CaCO3
= 48 ppm equivalents of CaCO3
Alkalinity of Water:
 Alkalinity of water is defined as “acid neutralizing capacity of water”
 It is mainly due to Hydroxide (OH-) , Carbonate (CO32-) and Bicarbonate (HCO3 -) ions
present in water.
 The possible combination of ions that causes hardness in water are (i) HCO3- (ii) OH-
(iii) CO32- (iv) CO32-&OH- (v) CO32- & HCO3- (vi) OH-, CO32- & HCO3-
 All the three ions cannot coexist, because of the following chemical reaction.
OH- + HCO3-----------> CO32-+H2O
 Alkalinity also is expressed like hardness in mg/L or ppm equivalents of CaCO3.

(Note: Besides Hydroxide Carbonate and bicarbonates, silicates, Borates and
Phosphate also contributes to alkalinity, but their contribution is very small hence
their discussion is ignored.)
Estimation of Alkalinity of Water
 Principle:
The alkalinity of water due to different ions (OH-, CO32-, HCO3-) can be estimated by
acid-base titration using phenolphthalein and methyl orange indicators.
Reactions that take place during the titration are shown as below:
1. 𝑂𝐻 − + 𝐻 + → 𝐻2𝑂
2. 𝐶𝑂3−2 + 𝐻 + → 𝐻𝐶𝑂3−
3. 𝐻𝐶𝑂3− + 𝐻 + → 𝐶𝑂2 + 𝐻2𝑂
During the titration, phenolphthalein indicator marks completion of the reactions 1

& 2 up to phenolphthalein endpoint and the volume of acid consumed up to this PhH
endpoint (VP) corresponds to neutralization of complete hydroxide (OH-) and half of
the carbonate (½ CO32-) present in water sample.
Similarly, methyl orange indicator marks completion of the reactions 1, 2 & 3 up to

methyl orange endpoint and the volume of acid consumed up to this MeOH
endpoint (VM) corresponds to neutralization of all the ions (OH- , 1\2 CO32-, 𝐻𝐶𝑂3− )
half of the carbonate and complete bicarbonate i.e. present in water sample.
Procedure:
A known volume (VH20) of alkaline water sample taken in a conical flask is added with
1 or 2 drops of phenolphthalein indicator. The alkaline sample turned to pink (If no
colour change, it indicates the absence of OH- & CO32-) is titrated against standard
acid (Nacid) taken in burette till the pink colour disappears. Volume of acid consumed
is noted as phenolphthalein endpoint (VP). The same water sample turned to yellow
after addition of 1 or 2 drops of methyl orange is continued to titrate till the colour
changes from yellow to reddish Orange. Volume of acid consumed is noted as
methyl orange endpoint (VM)
 Calculations:
Two types of alkalinity found in water
1. Phenolphthalein alkalinity (P): It is due to complete OH- and ½ CO32- present

in water.
2. Methyl orange alkalinity (M): It is due to all the ions present in water OH- &
½ CO32- , HCO3- ) , hence methyl orange alkalinity is equal to total alkalinity
of water)
Where, 50= Equivalent weight of CaCO3

When phenolphthalein alkalinity is calculated individual alkalinity due to different ions
can be calculated as shown in the table.
Alkalinity due to -
S .No Observations Carbonate Bicarbonate
Hydroxide (OH-)
(CO32-) (HCO3-)
1. P=0 - - M
2. P=M P or M - -
3. P=½M - 2P -
4. P>½M 2P-M 2(M-P) -
5. P<½M 2P M-2P
Problems:
1. A Sample of water was alkaline to both Phenolphthalein and methyl orange end
point. 100 mL of this sample water required 30 mL of N/50 H2SO4 for
phenolphthalein end point and another 20 mL of N/50 H2SO4 for methyl orange end
point. Mention the type and calculate the extent of alkalinity of water sample.
Given:
Volume of sample water = 100 mL
Normality of H2SO4 = 1/50 N = 0.02N
Volume of Acid Consumed up to phenolphthalein end point (VAcid (P)) = 30 mL
Volume of Acid Consumed up to Methyl orange end point (VAcid (M) ) = 50 mL
Phenolphthalein Alkalinity (P):
Let, Normality of given water sample up to phenolphthalein end point be NH2O (P)
Therefore, 100 mL X NH2O (P) = VAcid (P) x N Acid
NH2O (P) = 30 mL x 0.02 N /100 mL
= 3/500 N
Strength of given alkaline water up to phenolphthalein endpoint = NH2O (P) X 50 g/L
= 3/500 x 50 x 1000 mg /L
= 300 mg/L or ppm equivalents of CaCO3
Therefore, Phenolphthalein Alkalinity (P) = 300 ppm
Methyl Orange Alkalinity (M):
Let, Normality of given water sample up to Methyl Orange end point be NH2O (M)
Therefore, 100 mL X NH2O (M) = VAcid (M) x N Acid
NH2O (M) = 50 mL x 0.02 N /100 mL
= 0.01 N
Strength of given alkaline water up to Methyl Orange endpoint = NH2O (M) X 50 g/L
= 0.01 x 50 x 1000 mg /L
= 500 mg/L or ppm equivalents of CaCO3
Therefore, Methyl Orange Alkalinity (M) = 500 ppm
From the above calculations, we have P = 300 ppm and M = 500 ppm
Therefore, P >1/2 M
So that both OH- & CO3-2 are present .
Hydroxide Alkalinity (due to OH- ) = 2P – M = (2x 300 -500) = 100 ppm
Carbonate Alkalinity (due to CO3-2 ) = 2 (M-P) = 2 (500 -300) = 400 ppm
2. 100 mL of water sample on titration with N/50 HCl, required 8 mL for

phenolphthalein end point and 9 mL of the acid for methyl orange end point.
Mention the type and calculate the extent of alkalinity of water sample.
3. 100 mL of water sample required 40 mL of N/50 H2SO4 for neutralization up to

phenolphthalein end point and another 160 mL of same acid was needed for further
titration with methyl orange end point. Calculate the alkalinity of water.
Water softening: The process of removing of hardness – causing salts from water is known as
softening of water.
Softening of water by ion exchange method: This method is also known as de-mineralization
process.
Principle: When a sample of water containing different salts (Electrolytes) come in contact with an
ion-exchange resin, the ions of same sign are exchanged between the resin and the water sample.
The ion-exchange resins are insoluble, porous; cross linked polymeric materials (generally these are
co-polymers of styrene and di-vinyl benzene). The functional groups attached to the chains of the
polymers are responsible for ion-exchange properties.
Ion exchange resins are of two types;
1. Cation exchange resins:
It consists of fixed anions (SO3–, COO-) and exchangeable cations (H+ ions).
2. Anion exchange resins:

It consists of fixed cations (N+R3) & exchangeable anions (OH- ions).
B.E I Year II Semester (CBCS)
Chemistry ( BS 104 CH) notes (Group -A : CSE, IT, MECH,Auto) (2018-19)
Process:
The hard water is first passed through cation
exchange resin where all the cations are
absorbed by the resin and equivalent amount
of H+ ions released into water. Then the water
is passed through anion exchange resin where
all anions are absorbed and equivalent
amount of OH- ions are released into water.
The H+ and OH- ions released from cation
exchange resin column and anion exchange
resin column respectively combine to form
H2O. Therefore, water is free from all the
electrolytic impurities and neutral. Ion free
water is known as demineralised or deionised
water.
Reactions at cation exchange resin:
Res-SO3 -H+ + Ca+2 / Mg+2 -------> Res-SO3 - Ca+2 / Mg+2 + H+
Res-SO3 -H+ + Na+ / K+ -------------> Res-SO3 - Na+ / K+ + H+
Reactions at anion exchange resin:
Res-CH2N+(CH3)2 OH-+ CO3 -2/ SO4 -2 ------------> Res-CH2N+(CH3)2 CO3 -2/ SO4 -2 + OH-
Res-CH2N+(CH3)2 OH-+ Cl- -----------------------> Res-SO3 - Cl- + OH-
Regeneration of resins:
When resins get saturated they need to be regenerated. The cation exchange resin is regenerated by
using dil. HCl, whereas anion exchange resin is regenerated by dil. NaOH.
Advantages:
1. This method is capable reducing hardness to almost zero.
2. It can be used to soften acidic /alkaline water.
Disadvantages:
1. This method is expensive.
2. It can’t remove organic impurities and colloidal impurities.
Softening of water by Reverse Osmosis method:
Reverse osmosis is the process in which solvent molecules flow from higher concentrated solution to
dilute or lower concentrated solution through semi permeable membrane when pressure, greater
than osmotic pressure, is applied.
If sea water / impure water is kept in contact with fresh water through semi permeable membrane
and a pressure, greater than osmotic pressure, is applied which results water molecules are forced
to flow from sea water/impure water side to fresh water side through semi- permeable membrane.
This is the principle involved in reverse osmosis method. This method is useful to soften sea water
or highly impure water. The commonly employed semi permeable membranes are cellulose acetate
and poly amides.
Specifications of Potable water/Drinking/Municipal water:

Water which is safe to drink is said to be potable water or drinking water. Potable water should have
following specifications,
1. should be sparkling clear and odorless
2. Water should be pleasant in taste.
3. Water should be perfectly cool and its turbidity should not exceed 10 ppm.
4. It should be free of objectionable minerals such as lead, arsenic, chromium
and manganese salts.
5. pH should be around 8
6. Dissolved salts should be less than 500ppm
7. It should be free from disease – producing micro organisms.
8. Chloride, Fluoride & Sulphate contents should be less than 250ppm, 1.5ppm
and 250 ppm respectively.
Sterilization by Chlorination:
Drinking water is disinfected by treating with chlorine. Chlorine can be employed as gas or in the
form of concentrated aqueous solution. When Chlorine is mixed water hypochlorus acid is produced,
which is a powerful germicide.
H2O + Cl2 → HOCl + HCl
Experimentally it is reported that the death of micro organisms, bacteria etc., results from the
chemical reaction of HOCl with the enzymes in the cells of micro organisms.
Bacteria + HOCl → Killed bacteria.
At pH>7, HOCl dissociates to H + and OCl -. HOCl is about 80 times destructive towards bacteria than
OCl- ions. Therefore, Chlorination is effective at pH 5-6.5.
Chlorination makes water free from oxidisable impurities, colour, odor and pathogens.
The quantity of chlorine to be added is important because, disinfection will not complete if chlorine
is insufficient. If excess chlorine is added, it causes irritation, bad taste and odor.
Break Point Chlorination:
It involves addition of sufficient amount of chlorine to oxidize (i) Reducing substances (ii) Organic c
matter (iii) Free ammonia (NH3).At break point chlorination the water is free from oxidisable
impurities, colour, odor & pathogens .The activity of chlorine and residual chlorine left over during
the chlorination is explained by the following graph.
The unreacted chlorine remains in water beyond break point chlorination and it is called free
residual chlorine. Chlorine is carcinogen and its permissible limit is 0.1 -0.2 ppm.
Advantages:
1. It ensures complete destruction of organic compounds which impart colour, bad
odour and unpleasant taste to water.
2. It completely destroys all the disease producing bacteria.
3. It prevents the growth of any weeds in water.
CORROSION
Corrosion of Metals:
Corrosion is a process of gradual deterioration or destruction of metals or alloys from its surface due
to unwanted chemical or electrochemical interaction of metal with its environment.
Examples:
1. Formation of a layer of reddish brown scale of hydrated ferric oxide on the surface of iron.
2. Formation of a green film of basic carbonate [CuCO3+Cu (OH)2] on the surface of Copper.
Cause of Corrosion:
The chemically combined state of metal, ore, possess low energy and is thermodynamically more
stable state for metal. Pure metal is isolated from its ore by supplying considerable amount of
energy. Isolated metal is said to be in excited state, possess high energy and thus thermodynamically
unstable. Thus it is natural tendency of a metal to go back to its thermodynamically stable state.
Metals do this by interacting with its environment to form surface compound and thus undergo
corrosion.
Effects of Corrosion:
(a) Due to corrosion, properties of metals such as malleability, ductility and electrical
conductivity are lost.
(b) Due to corrosion efficiency of metal is reduced.
(c) Contamination of product will also take place if the corroded equipment is used.
(d) The replacement of corroded equipment is time consuming; maintenance cost increases.
Types of corrosion
1. Dry or chemical Corrosion 2. Wet or Electrochemical of corrosion
1. Dry or chemical Corrosion
Dry corrosion occurs under dry conditions. This type of corrosion occurs mainly due to direct
chemical action of atmospheric gases such O2, Cl2 , CO2 , sulphur dioxide, NOx, nitrogen or
anhydrous inorganic liquid on the metal surface.
i. Oxidation corrosion (corrosion by oxygen):

Direct attack on metals by oxygen at ambient temperature in the absence of moisture leads to
oxidation corrosion. Alkali and alkaline earth metals undergo corrosion even at ordinary
temperatures whereas at high temperatures all metals except Ag, Au and Platinum are oxidized.
Nature of the metal oxide (corrosion product) formed on the surface of the metal influences further
rate of corrosion
1) If metal oxide formed is stable, it protects underlying metal from further attack. Oxides of
Pb, Al and Sn, hence inhibit further corrosion.
2) If the metal oxide formed is unstable, it decomposes back into the metal and oxygen. In such
cases oxidation corrosion is not possible. For noble metals like Au, Ag and Pt oxidation
corrosion is not possible because oxide layer formed is very unstable decomposes back into
metal and oxygen.
3) If the metal oxide formed is volatile, it volatilizes as soon it is formed leaving underlying
metal for further attack, therefore, rapid and continuous corrosion takes place.
Molybdenum forms volatile oxide film of MoO3 which accelerates further corrosion.
4) If porous oxide film is formed atmospheric oxygen can have access to the underlying metal
surface through pores, hence continuous corrosion takes place. Porous oxide layer is formed
by alkali and alkaline earth metals.
Pilling Bed worth Rule:
According to Pilling Bed-Worth Rule,
 If volume of metal oxide formed on the surface of a metal is more than or equal to the
volume of metal from which it is formed, the oxide layer will be protective or non porous.
 If volume of metal oxide formed on the surface of a metal is less than the volume of metal
from which it is formed, the oxide layer will be no- protective or porous.
 For example, specific volume ratio (volume of metal oxide /volume of metal) of W is 3.6, Cr =
2.0, Ni = 1.6. Hence, the rate of corrosion is very less in tungsten.
ii. Corrosion by other gases:
Gases such as Cl2, SO2, H2S, NOx, in dry atmosphere react with metal and form corrosion
products, which may be protective or non-protective.
 Dry Cl2 reacts with Ag and forms AgCl that is a protective layer, but when Cl2 reacts Sn
forms SnCl4 which is non – protective.
 In petroleum industries at high temperatures H2S attacks steel forming FeS scale, which
is porous.
iii. Liquid metal corrosion:
Liquid metal corrosion occurs when a liquid metal flows over a solid metal at high temperature.
Example: In nuclear reactors sodium metal corrodes the cadmium rods.
What is wet or electrochemical corrosion and explain principle involved in it?

Wet or Electrochemical corrosion:
Wet or electro chemical corrosion is common type of corrosion which occurs under wet or moist
conditions. It is observed when (i) a metal is in contact with a conducting liquid , and/or (ii) dissimilar
metals are dipped partially in aqueous corrosive environment.
The Wet or electrochemical corrosion involves:

1. Formation of anodic and cathodic areas
2. Presence of conducting medium
3. Corrosion of anodic parts only
4. Formation of Corrosion product closer to the cathodic area.
Explain electrochemical theory of corrosion by taking rusting of iron as an example.

Electrochemical theory of corrosion:
According to this theory, when a metal comes in contact with a conducting liquid a galvanic cell is
formed within the metal. Some parts of the metal act as anode and rest act as cathode. Atmospheric
gases and humidity present in the corrosive environment act as an electrolyte. Corrosion of anodic
parts takes place due to oxidation at anode.
Electrochemical theory of corrosion is explained by taking rusting of iron as an example under
different environmental conditions.
The anodic reaction involves oxidation of Fe to Fe+2
Fe  Fe+2 + 2e- (oxidation)
The cathodic reaction depends on the availability of oxygen at different pH of the corrosive medium.
The cathodic reaction occurs in two ways (i) hydrogen evolution (ii) oxygen absorption
(i) Hydrogen evolution  oxygen is absent
This type mechanism occurs when, (a) In acidic medium:
 anodic areas are large and cathodic 2H+ + 2e- H2 (g)
areas are small (b) In neutral /slightly alkaline medium
H2O +2e- 2OH-+ H2 (g)  Oxygen is present
In both acidic and neutral or slightly alkaline (a) In acidic medium:
medium hydrogen (H2) is evolved, therefore 4H+ + O2+ 4e-  2 H2O (1.22V)
this type of corrosion is called as hydrogen (b) In neutral /slightly alkaline medium
evolution type of corrosion. 2 H2O + O2 + 4e-  4OH - (0.401V)
(ii) Oxygen absorption In both acidic and neutral or slightly alkaline
This type mechanism occurs when, medium oxygen is absorbed, therefore this
 Anodic areas are small and cathodic type of corrosion is called as oxygen
areas are large absorption type of corrosion.
The Fe+2 ions, OH – ions formed at anode and cathode respectively move in the opposite direction and
meet at point which is closer to cathodic area to form ferrous hydroxide [Fe (OH)2] .
Fe+2 +2OH- Fe (OH) 2
In the presence of moisture and high oxygen supply, ferrous hydroxide is converted to hydrated
ferric hydroxide [Fe (OH)3] i.e. yellow rust .
2 Fe (OH)2 +1/2 O2+ H2O  2Fe(OH)3 i.e ( Fe2O3.3 H2O)
If the oxygen supply is limited black anhydrous Fe3O4 is formed.
In general, the rate of corrosion of metals is much faster in acidic medium than in neutral or alkaline
medium, but amphoteric metals like Al, Zn, etc, undergo corrosion with a faster rate even in basic
Types of electrochemical corrosion- Galvanic Corrosion, Differential aeration corrosion, Water line
corrosion and pitting Corrosion.
Galvanic corrosion (Differential metal corrosion)
It is also called as bi-metallic corrosion. Galvanic corrosion occurs when two dissimilar metals
(having different potentials) are electrically connected and jointly exposed to aqueous corrosive
environment. The metal with the lower potential acts as anode and undergoes corrosion. The
metal with higher potential acts as cathode and is protected.
Example: Iron pipes coupled with copper couplings.
In the above example, iron (-0.44V) acts as
anode and undergoes corrosion because its
potential is less than that of copper (0.34V).
If anodic region is small it leads to severe
corrosion.
Galvanic corrosion is controlled by (i) using a pure metal (ii) using metal closer in galvanic
series (iii) Making sure that anodic metal should occupy large surface.
Differential aeration (oxygen corrosion cell) corrosion:
 It is a type of electrochemical corrosion that occurs when a metal in contact with conducting
medium (corrosive medium) is exposed to uneven supply of oxygen on its surface.
 As a result of uneven supply of oxygen, an oxygen concentration cell is formed within the
metal.
 The part of the metal which is exposed to less oxygen concentration acts as ‘anodic area’
and gets corroded; while the part of the metal which is exposed to relatively high oxygen
concentration acts as cathodic area of corrosion cell is protected.
 At anode (poorly oxygenated): M  Mn+ +ne-
 At cathode (more oxygenated): 2 H2O + O2 + 4e-  4OH -
 Examples of this type of corrosion include drop corrosion, crevice corrosion, waterline
corrosion, pitting corrosion.
 Also the areas below nuts, bolts, joints, areas covered by dust particles and welded areas
are suffered from this type of corrosion.
Waterline corrosion:
 Waterline corrosion a type of differential aeration corrosion.
 It occurs when a metal is partly submerged in water or a metallic tank is partially filled with
water.
 The Part of metal below waterline is poorly oxygenated and acts as anodic area; while the
part of the metal above the waterline is more oxygenated and acts cathodic area.
 Corrosion occurs in the anodic area and simultaneously reduction of oxygen to OH- ions
occurs at cathodic area. The corrosion product is formed closer to cathodic area. This type of
corrosion occurs in water tanks, ocean liners, etc.,.
Pitting Corrosion:
 Pitting corrosion is a localized form of corrosion resulting in the formation of pin holes or pits.
 When a small cracking, breaking of protective film on the metal surface occurs, small anodic
areas and large cathodic areas are formed.
 The inner area of it is less aerated and the outer surface of the metal is well aerated.
 Therefore, the inner area of the pit acts as anode and under corrosion, while outer surface acts
cathode and protected.
 Pitting may also be due to the galvanic corrosion;
(i) The preferential attack of the environment on a metal of an alloy may lead to pitting. E.g.;
Alloy of cu and Sn
(ii) The scratches on cathodic coatings also favor pitting.
Factors affecting rate of Corrosion:

(a) Nature of metal
(i) Position of the metal in Galvanic Series:
Galvanic series gives real and useful information regarding the corrosion behaviour of metals
and alloys in a given environment.
When two metals are electrically combined and exposed to corrosive environment the metal
with lower potential acts as anode and undergoes corrosion where as the metal with higher
potential acts as cathode.
(ii) Purity of metal: In general higher the purity of the metal, lesser the rate of corrosion. Thus
zinc of 99.95 % purity undergoes corrosion at rate of about 5000 times more compared to
zinc of 99.999% purity.
(iii) Hydrogen Overvoltage:
If the hydrogen over voltage of the metal is low, the rate of corrosion will be high.
(iv) Relative areas of anode and cathode: The rate of corrosion is more with the combination of
a large cathodic area and small anodic area.
Cathodic area
Therefore , Rate of Corrosion ∝
Anodic area
(v) Nature of surface oxide film
 If the corrosion product formed is stable, non-porous and strongly adherent layer it
prevents further corrosion.
 If corrosion product formed is highly unstable the metals do not undergo corrosion.
 If the corrosion product formed is porous or volatile metals undergo severe corrosion.
 If the corrosion product is soluble in medium to which it is immersed, corrosion of the
metal occurs with a faster rate.
(b) Nature of the environment
(i) Effect of humidity
Higher the humidity (moisture content) higher will be the rate of corrosion. Moisture acts as
solvent for O2, H2S, SO2 etc to furnish the electrolyte essential for setting corrosion cell.
Gases like H2S and SO2 increase the acidity of the medium by their dissolution in water.
Therefore, the rate of corrosion increases as humidity increases
(ii) Effect of temperature: The rate of corrosion increases with an increase in temperature.
(iii) Effect of pH: The rate of corrosion of metals is much faster in acidic pH than in alkaline
or neutral pH, but amphoteric metals like Al, Zn undergoes severe corrosion even in
basic medium.
Corrosion control methods:
Cathodic protection:
The principle involved in this method is to force the metal to be protected (Parent metal) to behave like
cathode. Therefore, corrosion of the parent metal is prevented. There are two types of cathodic
protections, (a) Sacrificial anodic protection (b) Impressed current cathodic protection.
a) Sacrificial anodic protection
In this method, the metallic structure to be protected is electrically connected to a more active or
anodic metal than the metallic structure to be protected. The more active metal acts as anode and
gets corroded slowly; while the parent structure (metallic structure to be protected) is forced to act
as cathode of galvanic cell, hence protected. As this more active metal is sacrificed its life in the
process of saving metallic structure from corrosion, it is known as sacrificial anode and, therefore, this
method is called as sacrificial anodic protection.
The metals which are commonly used as sacrificial anodes are Mg, Zn, Al and their alloys. This
method is used to protect buried pipelines, underground cables, marine structures, ship hulls and
metallic water tanks.
b) Impressed current cathodic protection
In this method, an impressed D.C current is applied, through D.C current source by a battery,
between the metallic structure to be protected which is forced to act as cathode and an insoluble
electrode like platinum, graphite or nickel which is buried in conducting medium adjacent to the
metallic structure to be protected and acts as anode of an electrolytic cell as shown in the figure. The
impressed D.C current applied nullifies the corrosion current thus the metallic structure is protected
from corrosion.
The metals which are commonly used as insoluble anodes are Graphite, Scrap iron, etc.This type of
cathodic protection is applied to buried structures such as tanks and pipelines, since, their operating
and maintenance costs are less, and they are well suited for large structures and long term
operations.
Surface Coating methods :
Hot dipping:
“Coating a high melting point base metal or alloy such as iron, copper or steel with a melt of low
melting point metal such as tin, zinc, lead or aluminium is known as hot dipping”. The process is carried
out by immersing a clean metal in a bath of molten metal.
Examples: Zinc coated Iron (Galvanization), Tin coated Iron (Tinning).
Hot dipping galvanization or galvanizing:
“The process of coating molten zinc on the base metal (Iron) surface by hot dipping is known as
galvanization”. In the process of galvanization, the base metal iron / steel is coated with a thin film of
zinc metal. Since zinc is higher up in the galvanic series the Zn coating acts as anodic with respect to the
base metal (cathodic).With repeated exposure of the galvanized metal to environment, only the coated
active zinc gets corroded. Thus, the base metal iron / steel is protected.
The galvanization process is carried as follows;
1. The metal is cleaned and degreased using organic solvents.
2. The metal is treated with dilute H2SO4 (pickling process) for 10 minutes at about 800C to remove
any rust or scales, if there is any.
3. The metal is further treated with flux materials, ZnCl2 and NH4Cl for the best adhesion property.
4. Finally, the metal is dipped in hot molten zinc at 430 -4700C
5. The excess Zn is removed from the surface of the coated metal by rolling, wiping or air blow
techniques.
Unit-III Engineering Materials

Monomers: The small individual molecules which combine with each other to form large
molecules are called monomers.
Examples: Ethylene, vinyl chloride, styrene, etc.
Functionality of Monomer: “The Number of bonding sites present in a monomer” is called
functionality of monomer.
Examples:
Name of Monomer Structure Functionality

Ethene CH2=CH2 2
1,3- butadiene CH2=CH-CH=CH2 2
Ethylene glycol HO-CH2-CH2-OH 2
2 or 3
Phenol
3
Melamine
Note: The small molecules to act as a monomer, their functionality should be at least two.
: (Poly = many; Mers = Part):
Polymers are high molecular weight giant molecules formed by linking together of small
molecules, monomers, by means of covalent bond/chemical bond.
Examples: poly ethylene, poly (vinyl chloride), Bakelite, etc.
Polymerization: The process of joining together of small molecules by means of covalent
bonds to form extremely large molecule is called polymerization.
Or
Any chemical process which leads to the formation of polymer is called polymerization.
Examples:
Degree of polymerization:
Number of monomers/repeat units present in the polymer is called “Degree of polymerization”.
Example:
Nomenclature of polymers:
 Most of the polymers are known by the trivial or trade names. Polymers derived from
one type of monomer are denoted by prefixing poly to name of the monomer.
Examples: polythene, polypropene etc.
 If a monomer has substituent or has a multi worded name, then the name of the
monomer is enclosed in parenthesis after the prefix poly.
Examples: poly (vinyl chloride).
Classification of polymers:-
Natural and synthetic polymers:
 Natural polymers: Polymers which are obtained from naturally occurring materials
are called ‘Natural Polymers.’
Examples: Cotton, Silk, Wool, Natural rubber etc.
 Synthetic polymers: Polymers which are prepared in the laboratory or from industry
are called ‘Synthetic Polymers’.
Eg: Polythene, PVC, Nylon etc
Homo and co- polymers:
 Homo polymers: The polymers which are made up of identical monomer units are
called as homo polymer.
….
−M−M−M−M−M−M−M−……
Examples: polythene, polystyrene, poly (vinyl chloride), etc.
 Co-polymers: The polymers which are made up of different monomers are known as
co-polymers.
Examples: Nylon 6, 6, Buna-S, etc.
Co-polymers are classified as follows;
 Random copolymer
 Alternative copolymer
 Block co -polymer
 Graft copolymer
Homo and hetero chain polymers:
 Homo chain polymers: A polymer whose backbone is made of same species of
atoms is called as homo chain polymer.
----C-C-C-C-C-------
Examples: PE,PS, PVC, etc
 Hetero chain polymers: A polymer whose backbone is made of different species of
atoms is called as hetero chain polymer.
----C-C-O-C-C-O-C-C-O-----
Examples: Polyesters, Polyamides.
Thermoplastics and thermosetting resins:
 Thermoplastics: Polymers which can be softened on heating and hardened on cooling
reversibly.
 Thermosetting polymers: The polymers which undergo permanent change on heating.
Thermoplastics Thermosetting polymers

They soften on heating and harden on cooling They are not softened on heating once set.
reversibly. Prolonged heating leads to charring.
They are formed by addition or condensation They are formed by condensation
polymerization. polymerization.
They have either linear or branched These have 3D cross linked structures.
structures.
They can be recycled, re-moulded, re-shaped They can’t be re-cycled, re-moulded, re-
and re-used. shaped.
They are soluble in some organic solvents They are insoluble in organic solvents.
They are tough & less brittle They are tough but more brittle.
Ex: PE, PP, PVC, PMMA, Teflon. Ex: PF, UF, MF
Polymerization: Polymerization is a process of linking together small molecules by means of

covalent bonds.
Types of polymerization:
1. Addition polymerization/Chain growth polymerization:
 Addition polymerization is a reaction that yields a polymer which is an exact multiple of
monomers, without the elimination of by-products.
 Monomers having double bonds such as alkenes, alkynes, undergo addition
polymerization.
 It is induced by heat or light or catalyst.
Examples:
i. Poly Styrene
ii. Polyethene
2. Condensation polymerization/step polymerization:

 Condensation polymerization is a reaction occurring between two bi – or poly functional
monomers having polar functional groups.
 It always accompanies with elimination of small molecules like H2O, HCl, NH3, etc.
 For example, >C=O, -COOH, -OH and –NH2 carrying monomers undergo condensation
polymerization.
Examples:
i. Kevlar
ii. PET( Terylene Or Dacron)
3. Co-polymerization:
 Co-polymerization is the joint polymerization of two or more monomers.
 This is mainly to vary the properties of polymers over a wide range.
Examples:
i. Buna-S (SBR)
ii. Butyl Rubber
Free radical mechanism of addition polymerization:
Explain free radical mechanism of addition polymerization of substituted

Polythene
Mechanism of free radical addition polymerization involves 3 steps.
1. Initiation 2. Propagation 3. Termination
Step -1: Initiation:
It involves two steps,
(i) Formation of free radical
(ii) Addition of free radical to first monomer
(i) Formation of free radical

In this step, Acetyl peroxide undergo homolytic cleavage under thermal condition
to give methyl free radicals.
(ii) Addition of free radical to first monomer
In this step free radical produced combine with first monomer to give chain
initiating step.
Step 2: Propagation:
Propagation is process in which reaction intermediate continuously generated

during the reaction.
In this propagation step, chain initiating species reacts with n of monomers to

give growing chain polymer.
Step-3: Termination:
Chain termination is done by (i) Coupling
(ii) Disproportionation
(i) Coupling
Termination by coupling occurs when end of one chain growing polymer

combines with end of another growing chain polymer to give saturated polymer.
(ii) Disproportionation
Termination by disproportionation occurs when β- hydrogen of one chain growing

polymer is shifted to end of another chain growing polymer to give unsaturated
and saturated polymers respectively.
Preparation, Properties & Applications of the polymers:

Plastics: The polymers which can be shaped into hard and tough utility articles are
known as plastics.
Examples: 1. PVC 2. Bakelite:
1. Poly (vinyl chloride)/ PVC
Preparation:
Poly vinyl chloride (PVC) is obtained by heating a water emulsion of Vinyl chloride in presence
of benzoyl peroxide or H2O2 in an auto clave under pressure.
The PVC so obtained is Rigid PVC (unplasticized). It can be softened by adding plasticizers & can
be called as ‘ Plasticized PVC ’.
Properties of Rigid PVC:
1. Rigid PVC is a colourless, odourless and non-inflammable.

2. It has excellent oil resistance and resistance to weathering.
3. Due to the presence of ‘Cl’ atoms, hardness and stiffness of the polymer increases.
4. It has high chemical resistance , but soluble in ethyl chloride & THF.
Uses of Rigid PVC:
1. Due to chemical resistance, it can be used as tank linings in acid plants.

2. Due to resistance to weathering, it is used in building industry.
3. It is also used in making pipes, window frames, edible oil containers, mineral water bottles,
safety helmets, mudguards for vehicles etc.
Plasticized PVC: Addition of plasticizers like DOP (di octyl phthalate), di butyl phthalate, tri
cresyl phosphate etc. to rigid PVC gives plasticized PVC.
Properties of plasticized PVC:

 It is very good insulator for DC & low frequency AC current
 It is flexible and show water proof nature.
Uses of Rigid PVC: It is used for making
1. Leather cloth used for car seat, covers etc

2. Kitchen upholstery, ladies hand bags, plastic rain coats
3. Baby pants, swim suits etc.
2.Bakelite:
It is the condensation polymer of phenol and formaldehyde. It is also known as phenoplast and
PF resin.
Preparation: Bakelite preparation involves the following steps:
Step (i):
Phenol and formaldehyde react to form methylol derivatives which act as monomers for
subsequent polymerization.
OH OH OH
OH
CH2OH CH2OH HOH2C CH2OH
HCHO HCHO HCHO
Mono methylol
derivative CH2OH CH2OH
Dimethylol Tri methylol
Step (ii): In presence of acid catalyst when mole ratio P/F>1.
The methylol derivatives condense with phenol to form dihydroxy diphenyl methane. These on
further condensation give low molecular weight linear polymers which are fusible , soluble and
are known as “Novalacs”.
Step (iii):
Further heating of Novalac in presence of hexamethylenetetramine [(CH2)6N4] as curing agent

produces a hard, rigid , insoluble and infusible 3-D cross linked polymer known as “Bakelite”.
Properties:
 Bakelite is hard, infusible and insoluble strong material.
 They have excellent heat, chemical resistance, but are affected by strong caustic alkalis.
 They have good electrical insulation characteristics.
 They have good abrasion resistance.
Uses:
 For making electrical insulating parts like switches, plug etc.
 For making telephone parts, cabinets for radio & television.
 In paints and varnishes.
 As ion exchange resin in softening of water by ion-exchange method.
Fibers:
The polymers which can be drawn into filament like materials are called ‘fibers. In the fibers,
the polymeric chains are held by strong intermolecular forces like hydrogen bonding.
E.g.: Nylon, Polyester etc.,
Polyamides: The polymers which consists of amide group.

Polyamides occur both naturally and artificially. Examples of naturally occurring polyamides are
proteins, such as wool and silk. Examples of artificially made polyamides such as nylons, Kevlar,
etc,.
Nylon 66:
Preparation: It is prepared by the condensation polymerization of adipic acid with
hexamethylene diamine.
Properties:
 They are translucent, whitish, horny, high melting (160 - 2640C) polymers.
 They are resistance to high temperature and abrasion.
 They are insoluble in benzene and acetone and soluble in phenol, formic acid etc.
 They have good strength and absorb little moisture.
Uses of Nylons:
 Nylon 6:6 is used for making socks, dresses, carpets etc.
 It is also used in making gears, bearings, bushes etc.
 It is used for jacketing electrical ware and protects the electrical insulation.
Kevlar (Aramid) : It is a aromatic polyamide, therefore also known as aramid.
Preparation: It is prepared by the condensation polymerisation of terephthalic acid dichloride
and 1, 4- di amino benzene (P-amino aniline).
O O H H O O
Condensation
H
Cl C C Cl H N N H C C N N
-2nHCl H
n
Terephthalic acid
di chloride P-Amino aniline Kevlar
Properties:
 It is very rigid polymer
 Exceptionally strong (Five times stronger than steel and 10 times stronger than Al) and
has high heat stability.
 The unique properties of Kevlar are due to the benzene rings which are linked to the
amide group. There are stronger inter molecular forces between neighboring chains,
which make it exceptionally strong.
Uses:
 Used in tyres, brakes, clutch lining and other car parts.
 Bullet-proof vests.
 Motor cycle helmets.
 Used in Aerospace and air-craft industries.
Elastomers:
Natural Rubber and its chemical structure:
Natural rubber (Cis -1, 4- polyisoprene) is a polymer of cis isoprene (2-methyl 1, 3-butadiene).
Sources of Natural rubber:

Natural rubber is obtained in the form of milky colloidal emulsion called rubber latex from
rubber trees like Hevea brasiliensis, etc,.
Natural rubber is also obtained from North American shrub Guayule, but it has low molecular
weight than the natural rubber obtained form hevea tree.
The countries which are producing natural rubber are Thailand, Indonesia, Malaysia, Africa,
Brazil, and South America, India.
Vulcanization of Rubber:
The process of heating raw rubber with sulphur at 1000C -1400C is called vulcanization. The
chemical compounds like sulphur monochloride, Benzoyl chloride, Hydrogen sulphide can also
be used as vulcanizing agents.
CH3 CH3
CH3 CH3
CH2 C CH CH2 CH2 C CH CH2 CH2 C CH CH2 CH2 C CH CH2
Vulcanisation S S S S
CH2 C CH CH2 CH2 C CH CH2 CH2 C CH CH2 CH2 C CH CH2
CH3 CH3
CH3 CH3
Vulcanized Rubber
During vulcanization, the sulphur added chemically combines at the double bonds of adjacent
polymeric rubber chains which make rubber stiff.
Toughness and properties of vulcanized rubber depend on the amount of sulphur added during
vulcanization.
Artificial /synthetic rubbers:
Styrene Rubber (GR-S or Buna-S or SBR)
SBR is a copolymer which is prepared by the co-polymerization of 1, 3-butadiene (75%) and
styrene (25%) at 5 0C in the presence of cumene hydroperoxide as catalyst.
SBR is also called as cold rubber.SBR can also be vulcanized in the same way as natural rubber
either by sulphur or sulphur monochloride .However, the amount of sulphur required for
vulcanization is less.
Properties: Buna-S has the following properties,
 High abrasion resistance and load bearing capacity.
 Good Resilience.
 It swells in oils and solvents.
 It gets readily oxidized due to the presence of unsaturation.
Uses: SBR is used for making,
 Automobile tyres, foot wear components.
 Insulation for electrical wires.
 Conveyor belt, tank lining.
Butyl Rubber (GR-I):

Preparation:
Butyl rubber is a copolymer which is prepared by copolymerization of isobutene and small
amount of isoprene. It also known as IIR, IIR stands for Isobutylene Isoprene Rubber.
Small amount of isoprene is added to make resultant rubber vulcanizable.
Properties:
1. It is quite resistant to oxidation due to low degree of unsaturation.
2. Though it can be vulcanized cannot be hardened much because of low degree of
unsaturation.
3. Being non –polar, it has good electrical insulation properties.
4. Compared to natural rubber it possesses low permeability to air and other gases.
5. It is soluble in hydrocarbon solvents like benzene but has excellent resistant to polar
solvents like alcohol, acetone and resistant to chemicals like HCl,HF,HNO3,H2SO4 ,etc,.
Uses: It is used for,
1. Insulation of high voltage wires and cables;
2. Inner tubes of automobile tyres;
3. Conveyor belts for food other materials ;
4. Lining of tanks
5. Hoses etc.
Silicone Rubber/Silicones :
These polymers contain Siloxane (-Si-O-Si-O-) units with each tetravalent Si atom linked to one
or two organic groups.
Preparation:
2, 2- dichloro 2,2- dimethyl silicone which on hydrolysis gives dihydroxy silicone
compound which is monomer of silicone rubber.
Properties:
 They are very stable at high temperature.
 They are resistant to sunlight, oils, acids and alkalis.
 They are flexible between the temperature range of 90-250 0C.
Uses:
Silicone rubbers are used as,
Sealants, lubricants, paints, adhesives, insulation material in electrical fittings and air craft
tyres.
Conducting Polymers:
The polymers which can conduct electricity due to extensive conjugation are called as
conducting /conductive polymers.
Usually, the extensive conjugation present in the polymer backbone is responsible for
conduction of electricity.
Examples:
Conducting polymers are classified as follows;

Intrinsically conducting polymers:
These polymers have extensive conjugation in the backbone which is responsible for
conductance.
a) Conducting polymers having conjugated π - electrons in the backbone:
These polymers contain conjugated π - electrons in the backbone which increases
their conductivity to a large extent. This is because, overlapping of conjugated π –
electrons over the entire backbone results in valance and conduction bands. These
bands are separated by a significant band gap. The electrical conduction occurs only
after thermal or photolytic activation of electrons to give them sufficient energy to
jump the gap and reach into the lower levels of the conduction band.
b) Doped conducting polymers:
The conducting polymers with high conjugation can be easily oxidised of reduced as
they have low ionisation potential. Their conductivities can be increased by creating
positive or negative charge on polymer backbone by oxidation or reduction.
Doping is two types:
Doping is “addition of impurities or creation of positive or negative charge.
P-Doping (Oxidative doping):
It is done by oxidation process. Conducting polymer having conjugation is treated with Lewis
acids or I2 vapour of I2 in CCl4.
(CH)x A (CH)x+A- (Oxidation)
Polyacetylene Lewis Acid p-doped
2FeCl3 (CH)x+FeCl4- FeCl2

(CH)x
2(CH)x 3I2 (CH)x+I3-
P-Doping of polyacetylene:
In p-doping, conducting polymer having conjugation is partially oxidised using a suitable
oxidising agent which leads to the formation of delocalised radical ion called, Polaron. A
second oxidation of this Polaron, followed by radical recombination yields two positive
charge carriers on each chain which are mobile. Thus, these delocalised positive charges are
current carriers for conduction.
N-Doping (Reductive doping):

It is done by reduction process. Conducting polymer is treated with Lewis bases or reducing
agents.
(CH)x B (CH)x-B+ (reduction)
Polyacetylene Lewis Base n-doped
(CH)x Na+(C10H8)- Na+(CH)x- C10H8
N-Doping of polyacetylene:
In n-doping, the reduction process leads to formation of Polaron and bi polaron in two
steps. This followed by recombination of radical ion yields two negative charge carriers on
each chain of polyacetylene which are responsible for conduction.
Applications of Conducting Polymers: Conducting polymers are used in the following

applications,
OLED
In photovoltaic
Sensors
cell
Applications
of
conducting
polymers
Electrochromic In rechargeable
displays batteries
Biodegradable polymers:
Biodegradable polymers are defined as “the polymeric materials that undergo degradation
by environmental factors like sunlight, temperature changes or by the action of micro
organisms like algae, fungi and bacteria”
Example: Polylactic acid.
Classification of Polylactic acid:
Polylactic acid:
It is biodegradable thermo plastic, aliphatic polyester derived from renewable resources
such as corn starch (in USA), Tapioca products (roots, starch, mostly in Asia) and sugar cane
in rest of the world.
Preparation/Synthesis:
Properties:
 PLLA has glass transition temperature between 60-650C, melting temperature

between 173-1780C and tensile modulus between 2.7-16 Gpa
 PLA can be processed like most thermoplastics into fibre (using conventional melt
spinning process) and films.
 Heat deflection temperature of PLLA can be increased from 60-190 0C by physically

blending with PDLA.
 PDLA & PLLA form highly regular stereo complex with increased crystalinity.
 Bio-degradation of PDLA is slower than PLLA due to higher crystalinity of PDLA.
 PDLA has useful property of being optically transparent.
Applications:
Bio-Medical Applications of Polylactic acid:

UNIT-IV: CHEMICAL FUELS
Chemical Fuels:
A chemical fuel is defined as any combustible substance used to produce heat by
combustion.
A chemical process which is accompanied by evolution of heat, when a chemical fuel is
subjected to burning in the presence of air or oxygen, is called as combustion.
Classification of fuels:
Ignition temperature: It is defined as “the minimum temperature to which the fuel must be
pre-heated so that it starts burning smoothly”.
Calorific value: It is defined as “the total quantity of heat liberated, when a unit mass or volume
of a fuel is burnt completely” in air or oxygen.
Types of calorific value
1. Higher calorific value or Gross calorific value:
It 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 room
temperature. Measured heat includes latent heat of water vapour produced .
2. Lower calorific value or Net calorific value:

It 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.
Net calorific value = Gross calorific value– Latent heat of water vapour formed
LCV or NCV = HCV – Latent heat of water vapour formed
𝟗𝑯
LCV = HCV – 𝟏𝟎𝟎 x 587 cal/g (Latent heat of steam is 587 cal/g. )
Where, H is the percentage of hydrogen.
Units of calorific value:
The calorific value of a solid or liquid fuel is generally expressed in Calorie/gram (cal/g) or
Kilocalorie/kg (kcal /kg) or British thermal unit /lb (B.Th.U /lb).
In the case of gaseous fuels units used are , (kcal /m3) or(B.Th.U / ft3).
Relation between various units:
1 k.cakg = 1.8 B.Th.U/lb = 1 cal/g
1 k.cal /m3 = 0.1077 B.Th.U/ft3
1 B.Th.U /ft3 = 9.3 k.cal/m3
Problems:
1. Calculate the GCV of a coal sample if its LCV is 6767.45 cal/g and it contains 5%
hydrogen. (Latent heat of steam is 587 cal/g)
Solution: GCV = LCV + 0.09 × H × Latent Heat of steam

= 6767.45 + 0.09 × 5 × 587
= 7031.6 cal/g
2. The Gross calorific value of a fuel containing 6% H was found to be 9804.6 Kcal/Kg.
Find the Net calorific value if the latent heat of steam is 587 cal/g.
Solution: NCV or LCV = GCV - 0.09 × H × Latent Heat of steam

= 9804.6 – 0.09 × 6 × 587
= 9487.62 kcal/Kg]
Characteristics of good fuel:

A good fuel should satisfy the following requirements:
1. It should have a high calorific value.
2. An ideal fuel should have moderate ignition temperature.
3. Its moisture content should be low.
4. Low volatile matter content.
5. It should not produce harmful products like CO2, SO2, H2S and other poisonous gases
on combustion since they pollute the atmosphere.
6. A fuel should have low content of non-combustible matter.
7. It should be economical and easily available.
8. In case of solid fuel, the size should be uniform.
Solid fuels:
Coal: It is highly carbonaceous matter and is regarded as a fossil fuel produced from large
accumulation of vegetable waste and alteration of vegetable matter like plants etc. under
certain favourable conditions by the action of heat and pressure over millions of years. Coal
is mainly composed of carbon, oxygen, hydrogen and nitrogen.
Ranking of coal:
Coal is classified or Ranked based on the carbon content. The following is the sequence of
conversion.
Analysis of coal:
The composition of coal varies widely and hence it is necessary to analyse the coal samples so that it
helps to know the quality of coal.
Proximate analysis:
Proximate analysis involves determination of moisture, volatile matter, ash and fixed
carbon present in the given coal sample. Proximate analysis is easy, quicker and it gives
clear idea of quality of coal.
1. Determination of Moisture:
A known weight (about 1 gm) of finely powdered air-dried coal sample is taken in a
crucible without lid. It is heated at 1050C to 1100C for 1 hour in electric oven. After
one hour crucible is taken out, cooled in desiccator and weighed. Loss in weight is
reported as moisture.
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 𝑑𝑢𝑒 𝑡𝑜 𝑚𝑜𝑖𝑠𝑡𝑢𝑟𝑒
Percentage of moisture = x 100
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛
Significance of moisture:
Moisture in coal evaporates during the burning of coal and it takes some of the
liberated heat in the form of latent heat of vapour. Therefore, moisture lowers the
effective calorific value of coal. Moreover, it quenches the fire in the furnace, hence,
lesser the moisture content; better the quality of coal as a fuel.
2. Determination of Volatile Matter:

A known weight of dried sample is taken in a crucible and it is fitted with a lid. It is
heated at 925 + 200C in an electric furnace or muffle furnace for exactly 7 minutes.
The crucible is taken out from muffle furnace after 7 minutes of heating, cooled first
in air, then in desiccator and weighed. Loss in weight is reported as volatile matter.
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 𝑑𝑢𝑒 𝑡𝑜 𝑟𝑒𝑚𝑜𝑣𝑎𝑙 𝑜𝑓 𝑣𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑚𝑎𝑡𝑡𝑒𝑟

Percentage of volatile matter = x100
Significance of Volatile Matter:
Highly volatile matter is undesirable in coal since a large portion of which escapes
un-burnt. Coal when it is burnt with highly volatile matter gives long flame, high
smoke and low calorific value. Hence, Lesser the volatile matter, better the quality of
the coal.
3. Determination of Ash:
The residual coal sample left over in the crucible is heated without lid at 700 + 50 0C
for ½ hour in. The crucible is taken out, cooled first in air, then in desiccator and
weighed. Heating, cooling and weighing is repeated, till a constant weight is
obtained. The weight of residue is reported as ash.
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑠ℎ 𝑙𝑒𝑓𝑡
Percentage of Ash = x 100
Significance of ash:
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. It also forms clinkers which cause obstruction to air supply. Ash
disposal is also a problem. Therefore, lesser the ash content, better the quality of
coal.
4. Fixed carbon:
Percentage of fixed carbon = 100 - % of (Moisture + Volatile matter + ash)
Significance of carbon:
Higher the percentage of fixed carbon, better the quality of coal and higher calorific
value. The % 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. Hence, high
percentage of fixed carbon is highly desirable.
Problems Based on Proximate analysis:

1. A sample of coal was analysed as follows: Exactly 1.500 g was weighed into a
silica crucible. After heating for an hour at 110°C, the residue weighed 1.415
g. The crucible was then covered with a vented lid and strongly heated for
exactly 7 min at 950 ± 20°C. The residue weighed 0.528 g. The crucible was
then heated without the cover, until a constant weight was obtained. The last
residue was found to weigh 0.254 g.
Calculate (i) The percentage results of the above analysis. (ii) To which type of
analysis does the above description belong?
2. A sample of coal was analysed as follows: Exactly 2.000 g was weighed into a
silica crucible. After heating for an hour at 110°C, the residue weighed 1.975
g. The crucible was then covered with a vented lid and strongly heated for
exactly 7 min at 950 ± 20°C. The residue weighed 1.328 g. The crucible was
then heated without the cover, until a constant weight was obtained. The last
residue was found to weigh 0.204 g. Calculate the percentage results of the
above analysis.
Solution:
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 𝑑𝑢𝑒 𝑡𝑜 𝑚𝑜𝑖𝑠𝑡𝑢𝑟𝑒

i. % Moisture = x 100
2−1.975
= x 100 = 1.25%
2
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 𝑑𝑢𝑒 𝑡𝑜 𝑟𝑒𝑚𝑜𝑣𝑎𝑙 𝑜𝑓 𝑣𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑚𝑎𝑡𝑡𝑒𝑟

ii. % Volatile matter = x100
1.975−1.328
= x 100 = 32.35%
2
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑠ℎ 𝑙𝑒𝑓𝑡 0.204

iii. Ash = x 100 = x 100 = 10.2%
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛 2
iv. % Fixed carbon = 100 - % of (1.25%+ 32.35%+ 10.2%)

=56.2%
Ultimate analysis:
Ultimate analysis is also known as elemental analysis that involves determination of
chemical constituents such as carbon, hydrogen, nitrogen, sulphur and oxygen, ash , etc.
present in the coal. It gives an idea of air quantities required for combustion and volume,
composition of combustion products and helps for calculating heat balances in any process
for which coal is employed as fuel.
1. Determination of Carbon and Hydrogen:
A known weight of coal sample is burnt in dry oxygen in a combustion apparatus. C and H of
the coal are converted into CO2 and H2O respectively. H2Oand CO2 formed will be absorbed
in CaCl2 and KOH tubes of known weights respectively.
C + O2 --------> CO2 2KOH + CO2 -----> K2CO3 + H2O
H2 + ½ O2 ---------> H2O CaCl2 + 7 H2O ---------> CaCl2.7H2O
Increase in the weight of KOH tube represents weight of CO2 formed. Increase in the weight
of CaCl2 tube represents weight of water formed
𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 weight 𝑜𝑓 𝐾𝑂𝐻 𝑡𝑢𝑏𝑒 𝑋 12 𝑋100
%C =
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛 𝑋 44
𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 weight 𝑜𝑓 𝐶𝑎𝐶𝑙2 𝑡𝑢𝑏𝑒 𝑋 2 𝑋100

%H =
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛 𝑋 18
Significance of Carbon and Hydrogen:
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.
2. Determination of Nitrogen:
1 gram of accurately weighed powdered coal is digested in conc. H2SO4 in Kjeldahl’s flask
and heated. It is treated with excess of KOH when the solution becomes clear. Liberated
ammonia is distilled over and absorbed in a known volume of standard solution of acid. The
unused acid is determined by back titration with standard solution of NaOH.
From the volume of acid consumed by liberated ammonia, the percentage of N in coal is
determined as,
𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 𝑋 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑐𝑖𝑑 𝑋1.4
%N =
Significance of Nitrogen:
Nitrogen is inert and non-combustible gas with no calorific value, its presence in coal is undesirable.
3. Determination of Sulphur:
Sulphur is determined from the washings obtained from the known mass of coal burnt in
bomb calorimeter for determination of a calorific value. During this determination, S is
converted into Sulphate. The washings are treated with Barium chloride solution to convert
sulphate into Barium-sulphate which is precipitate. Precipitate is filtered, washed and
heated to constant weight.
weight 𝑜𝑓 𝐵𝑎𝑆𝑂4 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 𝑋 32 𝑋100

%S=
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛 𝑖𝑛 𝑏𝑜𝑚𝑏 𝑋 233
Significance of Sulphur:
Though, sulphur contributes to the calorific value of a coal its presence in coal is
undesirable. Its oxidised products like SO2, SO3, in the presence of moisture cause corrosion
of equipment and pollution. Presence of sulphur is highly undesirable in coal which is used
in steel making because it badly affects the quality and properties of iron and steel.
4. Determination of Ash:
The known weight of coal in a crucible is heated without lid in a muffle furnace at 700+500C
for ½ hour. The crucible is taken out, cooled first in air, then in desiccator and weighed.
Heating, cooling and weighing is repeated till a constant weight is obtained. The residue left
over in the crucible is reported as ash %.
Thus,
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑠ℎ 𝑙𝑒𝑓𝑡
% Ash = x 100
Significance of ash:
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. It also forms clinkers which cause obstruction to air supply. Therefore, lesser
the ash content, better the quality of coal.
5. determination of Oxygen:
It is determined indirectly by subtracting the sum of percentages of carbon, hydrogen,
nitrogen, sulphur and ash from 100 %
% Oxygen = 100 % – % of (C + H + S + N + Ash)
Significance of Oxygen:
Oxygen content Moreover, oxygen is a combined form with decreases the calorific value of
coal. 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.
Problems based on Ultimate Analysis:

1. 0.26 g of a sample of coal was analysed by combustion gave 0.039 g of water
and 0.245 g of carbon dioxide. Calculate the percentage of carbon and
hydrogen in the coal. [Ans. % of carbon = 25.69%; % of hydrogen = 1.66%]
2. 0.1 g of a sample of coal was used in a bomb calorimeter for the

determination of calorific value. The ash formed was extracted with acid and
the acid extract was heated with BaCl2 solution and a precipitate of BaSO4
was obtained. The precipitate was filtered, dried and weighed. The weight of
precipitate was found to be 0.01 g. Calculate the percentage of sulphur in the
coal sample. (Ans: % sulphur = 1.3734%)
3. 3.12 g of the coal sample was Kjehldahlized and NH3 gas was absorbed in 50
ml of. 0.1 N H2SO4. After absorption, the excess (residual) acid required 12.5
ml of 0.1 N NaOH for exact neutralization. Determine the percentage of
nitrogen in the coal sample. [Ans. % Nitrogen = 1.683%]
4. 3.0 g of the coal sample was Kjehldahlized and NH3 gas was absorbed in 45
ml of. 0.1N H2SO4. After absorption, the excess (residual) acid required 8.5 ml
of 0.1 N NaOH for exact neutralization. Determine the percentage of nitrogen
in the coal sample. [Ans. % Nitrogen = 1.7033%]
Theoretical calculation of calorific value of a fuel by Dulong’s formula:

𝟏 𝑶
𝑮𝑪𝑽 = (𝟖𝟎𝟖𝟎 𝑪 + 𝟑𝟒𝟓𝟎𝟎 (𝑯 − ) + 𝟐𝟐𝟒𝟎 𝑺) Cal/g or Kcal/kg
𝟏𝟎𝟎 𝟖
Where, C = % of carbon, H = % of hydrogen, S = % of sulphur, O= % of oxygen.
Problems based on Dulong’s formula:

1. A sample of coal has the following composition:
Carbon = 83%; hydrogen = 7.5%; sulphur = 1.5%; nitrogen = 0.6%; oxygen = 8.4%
find the gross calorific value using Dulong Formula.
Solution:
1 𝑂
𝐺𝐶𝑉 = (8080 𝐶 + 34500 (𝐻 − ) + 2240 𝑆) Cal/g or Kcal/kg
100 8
1 8.4
= (8080 𝑋 83 + 34500 (7.5 − ) + 2240 𝑋1.5) Cal/g or Kcal/kg
100 8
1
= (670640 + 22525 + 3360) Cal/g or Kcal/kg
100
= 8965.25 Kcal/g
2. Calculate the gross and net calorific value of coal having the following composition:
Carbon = 80%; hydrogen = 7%; sulphur = 3.5%; nitrogen = 2.1%; ash = 4.4%; Latent
heat of steam = 587 Kcal/Kg [Ans. (i) 8828.02 Kcal/Kg; (ii) 8458.21 Kcal /Kg]
LIQUID FUELS:
Petroleum/Crude oil: Petroleum is a naturally occurring flammable liquid consisting of a
complex mixture of hydrocarbons with small quantities of organic compounds containing
oxygen, nitrogen and sulphur. It is a fossil fuel formed, when large quantities of dead
organisms, usually zooplankton and algae, are buried underneath sedimentary rock and
subjected to intense heat and pressure over several millions of year. Petroleum is collected
mostly through oil drilling.
Composition of Petroleum as follows,
C=80-87% , H=11.1 - 15% , S=0.1-3.5% , O = 0.1-0.9% and N =0.4-0.9%
Refining of petroleum or Crude oil:
The crude oil is separated into various fractions having different boiling points by fractional
distillation. The fractions are finally converted into desired products by removing
objectionable impurities. This process is called refining of crude oil or petroleum. The plants
set up for this purpose are called oil refineries.
1. Removal of water (Cottrell’s process):
The crude emulsion is passed through highly charged electrodes where the
colloidal water droplets coalesce and separate out from crude oil.
2. Removal of sulphur compounds:
The crude which is free from water is passed over copper oxide where the
sulphur present in crude oil gets precipitated as copper sulphide which is
separated by filtration.
3. Fractional distillation:
Heating of crude oil at around 4000C in an iron retort produces hot vapours
which are allowed to pass through a fractionating column. Fractionating
column 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 vapours go up, the vapours get cooled gradually and
fractional condensation takes place. Higher boiling fractions condense first
and lower boiling fractions in turns.
Some important fractions of petroleum: Gasoline, kerosene and diesel:

Property/ Fraction Gasoline Kerosene Diesel
0 0
Boiling range of 40 to 120 C 180 to 250 C 250 to 3200C
fraction
Approx.Carbon C5-C8 C10-C15 C15-C18
chain length
Calorific Value 11,250kcal/kg 11,100 kcal/kg 11,000 kcal/kg
Specific Gravity 0.71 – 0.77 0.75 - 0.85. 0.86 - 0.95
Uses As fuel for IC As a fuel for domestic As a fuel in diesel
engines, as a purposes, Jet engine engines.
solvent, used in fuel, for preparing
dry-cleaning. laboratory gas.
Cracking and its significance:

Cracking is defined as “the decomposition of higher boiling fractions of hydrocarbons having
high molecular weight into low boiling fractions of hydrocarbons having low molecular
weight”
Gasoline has the highest demand as a motor fuel but the yield of this fraction is only 20 % of
the crude oil and the quality of the gasoline obtained from crude is also not so good. Hence
it is used only after suitable blending. Moreover, there is a surplus of heavier petroleum
fractions. Therefore, middle and heavier fractions are subjected to cracking to more
valuable low boiling fractions.
Catalytic cracking:
The quality and quantity of gasoline produced by cracking can be greatly improved by using
suitable catalyst like aluminium Silicate Al2(SiO3)3 or Alumina (Al2O3).
Lower temperature & pressures are required for catalytic cracking comparative to thermal
cracking.
Moving Bed Catalytic Cracking:
In moving bed catalytic cracking, the feed oil is first passed through a pre-heater. The pre-
heated oil vapours along with very finely powdered catalyst are then passed in a reactor
which is maintained at 500˚C for catalytic cracking. The cracked oil vapours are then passed
to the fractionating column through a centrifugal separator, called cyclone which allows
only the cracked oil vapours, but retains the catalyst powder in the reactor, where heavy oil
is separated. The vapours are then passed through the cooler, where gasoline condenses
along with some gases and is then sent to a stabilizer to remove the dissolved gases and
pure gasoline is recovered.
The catalyst powder gradually becomes heavier, due to the coating with carbon and settles
to the bottom from where it is forced by an air blower to regenerator (maintained at
600˚C).In regenerator, carbon is burnt and the regenerated catalyst then flows through
stand-pipe for mixing with fresh batch of the incoming cracking oil. At the top of the
regenerator, there is a separator, which permits only gases (CO2 etc) to pass out, but holds
back the catalyst.
Knocking:
“A sharp metallic /rattling sound produced in an internal combustion engine due to improper
ignition of air and fuel mixture is called knocking”.
Generally, in petrol engine knocking is due to pre-ignition where as in diesel engine knocking
is due to ignition delay.
Knocking depends on i) Engine design (ii) Running conditions of engine (iii) chemical
structure of hydrocarbons.
Knocking tendency decreases in the order,
n-alkanes > Branched chain alkanes > Cyclo alkanes > alkenes > Aromatics
 For Straight chain hydrogen carbons, the tendency to knock increases with molecular
weight and boiling point, e.g., n-butane < n-pentane < n-hexane
 Aromatic hydrocarbons have higher antiknocking properties than alkanes and
alkenes.
Consequences of knocking, (i) Decreased output (ii) Mechanical damage by overheating of
the cylinder parts.
Fuel rating:
Octane Number/ Octane rating:
It was proposed by Graham Edgar in 1926.
n- Heptane knocks very badly; its anti-knocking value is fixed as zero. Iso-octane
(2, 2, 4 - trimethyl pentane) gives little knocking, its anti-knocking value is fixed as 100.
Octane number of a gasoline is defined as “the % of iso – octane in mixture of iso- octane
and n-heptane which has same knocking characteristics with the gasoline under test.
E.g., 60 – octane fuel is one which has the same knocking characteristics as 60:40 mixture
of iso-octane and n-heptane respectively.
Higher the octane number better is the quality of gasoline.
Cetane Number /Cetane Value:
n- Hexadecane (Cetane) knocks very little, its anti-knocking value is fixed as 100 and
2-methyl naphthalene knocks very badly, and its anti-knocking value is fixed as 0.
Cetane number is defined as “the % of hexadecane in a mixture of Cetane and 2-methyl
naphthalene which has the same ignition properties as the diesel fuel under test”.
E.g., 55 – cetane fuel is the one which has the same knocking characteristics as 55:45
mixture of cetane and 2-methyla naphthalene respectively.
Higher the Cetane number, greater is the resistance to knocking.
Gaseous Fuels:
LPG (Liquefied Petroleum Gas):
It is obtained as a by-product during cracking of heavy oils. Since LPG is normally odourless,
small amounts of a pungent gas such as ethanethiols are added to help people smell
potentially dangerous gas leaks.
Main constituents: n-butane, iso butane, propane, butylene and propylene.
Calorific Value: 27,800 Kcal/m3
Uses: LPG is mostly used as domestic fuel for heating and cooking, it is used as fuel for cars
and also for industry.
CNG (Compressed Natural Gas):
It is a natural gas compressed to high pressure.
Composition: Methane (CH4) = 70 -90%, Ethylene (C2H2) = 5-10% , H2 =3% & Rest = CO + CO2
Calorific Value: 12,000 – 14000 Kcal/m3
Uses: Mainly used as automobile fuel, as a domestic fuel.
What are the differences between solid, liquid and gaseous fuels? Or
What are the advantages, disadvantages of solid, liquid and gaseous fuels
Calculation of air quantities required for the combustion of a fuel:
• The oxygen for the combustion of a fuel is to be obtained from the atmospheric air
although in some cases a certain amount of oxygen is a constituent of the fuel.
• Air is a mixture of oxygen, nitrogen, a small amount of carbon dioxide and small
traces of rare gases such as neon, argon, krypton, etc.
• For all practical purposes we assume that air is made up of 23% by weight of oxygen,
the remaining 77% being nitrogen.
• If considered by volume, air consists of 21% of oxygen and 79% of nitrogen.
• When we know the amount of oxygen necessary for the combustion of a fuel, we
can determine the amount of air necessary for the complete combustion of one kg
of fuel.
1. Minimum oxygen required = Theoretically calculated value – oxygen present in the

fuel
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛
2. Available hydrogen = Mass of hydrogen –
8
Therefore, theoretically required quantity of oxygen for complete combustion of
fuel,
32 𝑂
= [( 𝑋 𝐶) + 8 (𝐻 − ) + S]
12 8
Therefore, the quantity of air required (by weight) for complete combustion of fuel,
32 𝑂 100
= [(12 𝑋 𝐶) + 8 (𝐻 − 8 ) + S] 𝑋 23
Calculation of air quantities required by weight for the combustion of a fuel:
Solved Problems:
1. Calculate the mass of air required for complete combustion of 5 kg of coal containing;
C = 80%, H = 15 %, O = rest.
80
Solution: Weight or mass of C = 𝑋 5 = 4 kg
100
15
Weight of H = 𝑋 5 = 0.75 kg
100
5
Weight of O = 𝑋 5 = 0.25 kg
100
32
Amount of air required for the complete combustion of 4kg of carbon = (12 𝑋 𝐶)
32
= 12 𝑋 4𝑘𝑔
=10.66 kg
Amount of air required for the complete combustion of 0.75 kg of hydrogen
16
= ( 𝑋 𝐻)
2
=
16
𝑋 0 .75𝑘𝑔
2
= 6 kg
Therefore, theoretically required oxygen = (10.66 kg + 6 kg)
= 16.66 kg
Minimum oxygen required = theoretically calculated value – oxygen present in the fuel
= 16.66 kg – 0.25 kg
= 16.41 kg
Therefore, the quantity of air required for the complete combustion of fuel,
100
= Minimum oxygen required 𝑋
23
100
= 16.41 𝑘𝑔 𝑋
23
= 71.34 kg
2. Calculate the amount of air required for the complete combustion of 1 kg of carbon.
Sol; we know that,
C + O2 -------------> CO2
12g 32 g 44 g
From the above equation it is clear that every 12 g of carbon requires 32 g of oxygen.
Then, ‘C’ g of carbon requires how many grams of oxygen?
12g -------- 32 g
‘C’ g --------? Of oxygen
32𝑔
? Of oxygen required = 12𝑔 𝑋 ‘C’ g
32
Hence, amount of oxygen required = 12
𝑋 ‘C’ g
Calculation of air quantities required by volume for the combustion of a fuel:
1. Calculate the volume of air required for complete combustion of one cubic meter of
producer gas, the composition of which [by volume] is: H2 = 30%, CO = 10%, CH4 = 4%, N2 =
56%.
Solution: 1m3 of the producer gas contains H2 = 0.30m3, CO = 0.10m3, CH4 = 0.04m3 and N2 =
0.56m3. The various combustion reactions are
1
H2(g) + O2(g) → H2O(l)
2
1
CO(g) + O2(g) → CO2(g)
2
CH4(g) + 2O2(g) → CO2(g) +2H2O(l)
Volume of oxygen required for complete combustion of 1m3 of producer gas
0.30 x 0.5 + 0.10 x 0.5 + 0.04 x 2m3 = 0.28m3

0.28 ∗ 100
Volume of air required for complete combustion of 1m3 of producer gas = =
21
1.333m3.
2. The composition of a producer gas has been found to be : H2 = 14%, CH4 = 2%, CO = 22%,
CO2 = 5%, N2 = 55% and O2 = 2%. Calculate the air required for the complete combustion of
1m3 of this gas if 40% excess air is used.
Solution: 1m3 of the producer gas contains H2 = 0.14m3, CO = 0.22m3, CH4 = 0.02m3 and CO2
= 0.05m3, N2 = 0.55m3 and O2 = 0.02m3. The various combustion reactions are:
1
H2(g) + O2(g) → H2O(l)
2
1
CO(g) + O2(g) → CO2(g)
2
CH4(g) + 2O2(g) → CO2(g) +2H2O(l)

Amount of O2 needed for combustion = 0.14 x 0.5 + 0.02 x 2 + 0.22 x 0.5m3 = 0.22m3. Net
mass of oxygen required = Oxygen required – Oxygen in fuel = 0.22 – 0.2m3 = 0.20m3
0.20 ∗ 100
Volume of air required for complete combustion of 1m3 of producer gas = =
21
0.952m3.
But volume of air actually used, (i.e., 40% in excess). Hence = 0.952 + (40% of 0.952) = 1.4 x
0.952 = 1.333m3.
Numerical Problems based on air quantities required for combustion:

1. A fuel is found to contain: C = 90%; H = 3.5%; S = 0.5%; O = 1.0%; N = 0.5% and
ash = rest. Calculate the minimum amount of air required for complete combustion
of 1 Kg of fuel. [Ans. 11.6739 Kg]
2. A sample of coal is found to contain: C = 81%; H = 5.0%; S = 1%; O = 8.0%; N = 1% and

ash = 4%. Calculate the amount of air required for complete combustion of 1 Kg of
fuel. Oxygen in air is 23% by weight.
[Ans. (i) 10.826 kg
3. Calculate the volume of air required for the complete combustion of one litre of CO.
(Volume % of oxygen in air = 21) [Ans. 2.381 L]
4. Calculate the volume of air required for the complete combustion of 1 m3 of gaseous
fuel having the composition: CO = 46%; CH4 = 10%; H2 = 40%; C2H2 = 2.0%; N2 = 1.0%
and remaining being CO2. [Ans. 3.238m3]
5. A gaseous fuel has the following composition by volume - CO = 26%; CH4 = 4.0 % ;
H2 = 10%; N2 = 0.5% and remaining being CO2. Calculate volume of air supplied per
m3 of fuel ,if 20 % of excess air supplied.
`
UNIT-V: Green chemistry and Composites

Green Chemistry:
Definition:
Green Chemistry is the science which utilizes a set of chemistry principles in the design of
chemical products and processes that reduce or eliminate the use and generation of
hazardous substances”.
The concept of Green chemistry was proposed by Paul Anestas in 1994.
Green Chemistry Is About...

Waste
Materials
Hazard
Risk
Energy
Environmental
Impact
COST
Principles of Green Chemistry:
1. Atom Economy: The Atom Economy is a measure of efficiency of particular

reaction. It is an assessment which tells that the extent to which the atoms of reactants
are incorporated into the desired final product.
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

% 𝐴𝑡𝑜𝑚 𝑒𝑐𝑜𝑛𝑜𝑚𝑦 = 𝑥100
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠.
A reaction to be considered as green synthesis, the atom economy must be very high,
approaching or equal to 100 %.
2. Improved Process: The process should use renewable feed stock rather than
depleting material or feedstock whenever technically and economically practicable.
3. Minimize: Minimize energy consumption and material use.
4. Environment friendly: The products produced or the processes developed should

not show negative impact on environment.
5. Less hazardous chemical synthesis: Synthetic methods should be designed to use and
generate substances that possess no or little toxicity to human health and the environment.
6. Prevent Waste: It is better to prevent waste than to treat or clean up waste after it has
been created.
7. Real–time analysis for pollution prevention: Chemical reactions and procedures
should be monitored during the progress of the reaction to detect the formation of any
unwanted and toxic products. Analytical methods should be adopted to allow process
monitoring, control and minimize the formation of toxic substances.
8. Omit/Reduce derivatives: Unnecessary derivatization (blocking group, protection or

deprotection, and temporary modification of physical or chemical process) should be
avoided whenever possible.
9. Design safer chemicals and degradable products:
Chemical products should be designed in such a way that they achieve their desired
goal and degrade in the environment without creating any hazardous or toxic effects.
10. Use safer chemicals and methods:
Substances and the form of substances used in chemical process should be chosen to
minimize the potential for chemical accidents including releases, explosions and fires.
11. Catalysis: Catalytic Reagents (as selective as possible) are superior to stoichiometric
reagents. Use of selective catalysts increases specificity of the reaction and reduces
the formation of by products. A catalyst also lowers activation energy of the energy
,thereby reducing the energy consumption.
12. Technology: Technology where ambient temperature and pressure conditions are
used to minimize the potential for chemical accidents, including releases, explosions,
and fires.
“AIM Environment friendly Less Hazardous PRODUCT”
Examples :
1. Examples of Atom Economic reactions:
Calculate % atom economy for cyclo addition reaction of ethene and butadiene to
form cyclohexene .
Sol.
1,3-Butadiene(54)Ethene(28) Cyclo hexane(82)

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
% 𝐴𝑡𝑜𝑚 𝑒𝑐𝑜𝑛𝑜𝑚𝑦 = 𝑥100
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠.
82
= 𝑥 100= 100%
82
2. Methylmethacrylate is industrially important monomer for the synthesis of

PMMApolymer. It can be synthesized by one of the following two approaches
:{Example for Atom Economy & Catalysis }
Predict which one approach is qualifying as Green synthesis.

(Hint: Calculate the mass of atoms of all the reactants in both approach and Moecular
weight of desired product)
Now, make use of above formula and find out atom economy for both the approaches.
The approach with the higher atom economy is qualified as green synthesis.
Ans: Approach-II is qualified as green synthesis.
Examples of Catalysis and Clean technology
1. Preparation of MMA is done in two approaches as shown below Approach –II is

qualified as green synthesis since catalyst used and minimization of use of reactants
and atom economy is 100%.
2. Ethylene oxide is widely used in the synthesis of ethylene glycol (anti- freeze),
polyesters, ethanolamine etc.
Consider the synthesis of ethylene oxide via stoichiometric chlorohydrins route. It
requires expensive & hazardous chlorine gas as a reagent. It also produces 3.5 kg of
waste CaCl2per kg of ethylene oxide product. However, the catalytic route gives an
approximately 80% product yield without generating by products. The unreacted
reagents can simply be recycled through the synthesis.
3. Toluene can be converted into p-xylene by shape selective Zeolite catalyst avoiding
o-xylene & m-Xylene.
4. Preparation of Hydrazine:
Hydrazine is traditionally produced by the Olin Raschig process from sodium

hypochlorite and ammonia. The net reaction produces one equivalent of sodium
chloride for every equivalent of the targeted product hydrazine
NaOCl + 2 NH3 → H2N-NH2 + NaCl + H2O
In the greener peroxide process , hydrogen peroxide is employed as the oxidant, the
by product is water. The net conversion follows:
2 NH3 + H2O2 → H2N-NH2 + 2 H2O (clean reaction)
Bio diesel:
Biodiesel is alternative diesel fuel produced from biomass (i.e., vegetable oil or animal oils
/fats).
The Largest possible source of suitable oil comes from oil crops such as rape seed, palm,
sunflower, and soybean.
Most of the biodiesel at present is produced from waste vegetable oil sourced from
restaurants, chip shops and industrial food producers.
Concept of Transesterfication:
Transesterfication is “the process of conversion of vegetable oils/animal oils /fats into
biodiesel”.
In transesterfication, the organic group R″ of an ester exchanges with the organic group R′ of
an alcohol. These reactions are often catalyzed by an acid or base.
Strong acids catalyze the reaction by donating a proton to the carbonyl group, thus making
it a stronger electrophile.
Bases catalyze the reaction by removing a proton from the alcohol, thus making it stronger
nucleophile.
E.g.; Triglycerides (1) reacts with alcohols (2) to give alkyl esters (3) of a fatty acid and
glycerol (4)
Base catalyzedtransesterfication predominantly is used for production of biodiesel.

Advantages:
1. Biodiesel has better lubricating properties and much higher cetane ratings.
2. Biodiesel has very good lubricating properties, significantly better than standard
diesel which can prolong engine's life.
3. Biodiesel has shorter ignition delay compared to standard diesel.
4. Biodiesel has no or less sulphur content.
5. Biodiesel can be easily blended with standard diesel, and it can be used in most of
today's vehicles.
6. Bio-diesel is a source of renewable source of energy.
Disadvantages:
1. Biodiesel may contain small amount of water which reduces the heat of combustion
or may cause corrosion.
2. Pure biodiesel has significant problems with low temperatures.
3. Biodiesel is significantly more expensive compared to standard diesel.
4. Its calorific value is about 10% less than standard petroleum diesel.
5. Biodiesel can release nitrogen oxide which can lead to the formation of smog.
Carbon neutrality:
It is the term used to describe the action of organizations, businesses and individuals taking
to remove as much carbon dioxide from the atmosphere as each put into it.
 The overall goal of carbon neutrality is to achieve a zero-carbon footprint.
 This practice is often called carbon offset or offsetting.
 For example, a business may plant trees in different places around the world to
offset the electricity the business uses.
COMPOSITES:
Composite: A Composite is a material made from two or more different materials which
have distinct physical and chemical properties those individual materials that combined.
Examples:
1. Wood (a composite of cellulose fibres & lignin)

2. Bone ( a composite of strong protein Collagen, and hard material apatite)
3. The earliest man-made composite materials were straw and mud combined to form
bricks for building construction
4. Concrete is the most common artificial composite material of all and typically
consists gravel (aggregate) held with a matrix of cement.
Constituents of composites:
The two essential constituents of composites are, 1.Matrix phase 2.Dispersed phase
1. Matrix phase:
It is a continuous body constituent of composite, enclose the composite and gives it
bulk form. The Matrix phase may be a metal, ceramic or polymer.
2. Dispersed phase or Reinforcement:
It is a structural constituent of composite, which determines the internal structure of
composite.
Dispersed phase may be fibres, particles, flakes and whiskers.
What are fibres?
Fibres: Any polymer, metal or ceramic that has been drawn into long and thin
filament, is termed as fibre. It is characterized by high aspect ratio (length to diameter
ratio) and near crystal sized diameter. They have high strength and stiffness.
 Fibres may be, glass fibres, carbon fibres, aramidefibres, boron fibres and
ceramic fibres.
What are particulates?
Particulates (Particle): Particulates are small pieces of hard solid material (Metallic
and non-metallic).The distribution of particles in a given matrix is usually, random
thereby the resulting isotropic composite.
What are flakes?
Flakes: Flakes are thin solids having a two-dimensional geometry. Examples: mica
flakes
What are Whiskers?
Whiskers: These are thin strong filaments or fibres made by growing crystals
Examples: Graphite, Silicon carbide, Silicon nitride and aluminium oxide.
Characteristic properties of Composite Materials:
 The composite materials show properties distinctively different from those of the
individual materials of the composite.
 The composites show extraordinary combination of properties like toughness and

strength with low weights & high temperature resistance.
 Compared to steel and aluminium, composites are lighter, have low coefficient of
thermal expansion and have superior strength, stiffness & fatigue resistance.
 They have better corrosion & oxidation-resistance.
The properties of the composites depend on:

The properties composites depend on relative amounts (i.e. Concentration), distribution and
orientation of the constituent materials and geometry of the dispersed phase namely the
shape, size.
Types of composites:
Advantages of composites
1. The greatest advantage of composite materials is strength and stiffness combined with
light weight.
2. Composites are less likely than metals to break up completely under stress. A small
crack in a piece of metal can spread very rapidly with very serious consequences. The
fibres in a composite act to block the widening of any small crack and to share the
stress around.
3. The right mix of constituent materials often results in composites which are heat and
corrosion resistant.
4. Composite materials are also very durable.
5. They provide design flexibility, as they can be molded into complex shapes.
6. The manufacturing processes are often more efficient when composites are used.
Applications of composites:
1. Transportation: Composites are used in the manufacturing of automobile parts,
racing vehicle components and engine parts.
2. Marine: They are used as propeller shafts, hulls, spars (for racing boats) etc.
3. Aerospace: They are used in military aircrafts, helicopters, missiles and rocket
components etc.
4. Consumer product: They are used in sporting goods like tennis rackets, and in
musical instruments etc.
5. Composite Applications in Building & Construction
Components made of composite materials find extensive applications in shuttering
supports, special architectural structures imparting aesthetic appearance, with the
advantages like corrosion resistance, longer life, low maintenance, ease in
workability, fire retardancy etc
6. Composites are frequently used in industrial and scientific equipments like high speed
machinery, electronic circuit boards (PCB) , communication antenna etc.
7. Safety equipment like ballistic protection and air bags of cars etc.

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B.

E II Sem (AICTE Model Curriculum)

Unit-I Electrochemistry and Battery Chemistry

The cell which converts electrical energy into chemical

Galvanic Cell: Galvanic cell is a device

Salt bridge & Its Role:

2. It prevents diffusion of the solutions from one half-cell to the other

3. It keeps the solutions in two half-cells electrically neutral.

4. It prevents liquid-liquid junction-potential.

Representation of cell Or Cell Notation:

Difference between Electrolytic cell and Galvanic Cell

Ecell = E Cathode- E Anode

Standard electrode potential:

The potential of an electrode, at a given temperature, depends upon the concentration of

Thermodynamics of EMF of cells

(1) Relationship between Enthalpy change and EMF:

From Gibbs-Helmholtz equation, we have

∆𝐺 = ∆𝐻 − 𝑇∆𝑆 ------------------ (2)

From equation (1) & (2) , we get

∆𝐺 = −𝑛𝐹𝐸 ----------------- (4)

Substituting for ∆𝐺 = −𝑛𝐹𝐸 in equation (3) , we get

(2) Relationship between Enthalpy change and EMF:

From Gibbs-Helmholtz equation, we have

Substituting for ∆𝐺 = -nFE , we get

On rearranging Equation (2) , we get

Nernst Equation & Its derivation:

−∆𝐺 0 = 𝑛𝐹𝐸𝑐𝑒𝑙𝑙 & − ∆𝐺 = 𝑛𝐹𝐸𝑐𝑒𝑙𝑙

Applications of Nernst Equation:

1. Nernst equation is used to study the effect of electrolyte concentration on electrode

3. Determination of unknown concentration of one of the ionic species involved in a

5. It can also be used to find the valency (n) of reactive species.

6. It can be used to calculate equilibrium constant of redox reaction.

(1) Metal – Metal ion Electrode:

(2) Gas Electrode

Example: Hydrogen electrode

(3) Metal – insoluble salt electrode:

E.g. Calomel electrode:

Construction and working of Calomel electrode:

Calomel electrode is an example of metal -metal

Calomel electrode is represented as Pt-Hg/ Hg2Cl2/KCl (aq).

If it acts as anode, it involves If it acts as cathode it involves

When it acts as anode, mercury is When it acts as cathode, Hg22+

(4) Redox Electrodes:

If it acts as cathode, then the electrode reaction is,

The electrode potential is calculated by using Nernst equation,

Potential of Quinhydrone electrode depends on pH of the solution with which it is in

Eg; Glass electrode

Glass electrode is made up of a special type of glass

conductance. The bottom of the glass electrode is

The representation of glass electrode is, Ag/AgCl/0.1N HCl/Glass membrane. The

Determination of pH of a solution using quinhydrone electrode:

The electrode potential of Quinhydrone electrode, which is reversible to H+ ions,

Pt, Hg/ Hg2Cl2,Cl-(Sat ,aq) // H+ (aq),Q, QH2/Pt.

𝐸𝑐𝑒𝑙𝑙 = 0.457 − 0.0591𝑝𝐻

Problems Based on Applications of Nernst Equations:

Cu+2 +2e- --------> Cu; 𝐸 0 = 0.35𝑉

Zn+2+2e- --------> Zn; 𝐸 0 = −0.763𝑉

At anode Zn --------> Zn+2+2e- (Oxidation)

2. Calculate the electrode potential at a copper electrode dipped in a 0.1M solution of

Ans: 0.31045 Volts

𝐴𝑛𝑠 : 1.67 x 1037

What are primary and secondary batteries?

Primary batteries Secondary batteries