ELECTROCHEMISTRY

Introduction, Single electrode potential, Origin of single electrode potential theory, Nernst
ngalvanic cell and electrolytic cell, representation of galvanic cell, Construction and working
of galvanic cell, Liquid junction potential, Functions of salt bridge, EMF of cell,
Determination of EMF of cell by Poggendroff’s method using Standard cell, Construction,
working, application and limitations of calomel electrode, Numerical problems. Construction,
working, applications, advantages and limitations of glass electrode, Numerical problems.
Classification of Batteries – Introduction, primary and secondary with examples;
construction, working and applications of lead acid battery. Construction, working and
applications of Ni-Cd and Li-ion batteries, advantages and disadvantages. Fuel Cells –
Introduction, construction and working of AFC & PEMFC, advantages and disadvantages.
Metal finishing – Electroplating – polarization, over voltage, decomposition potential
including determination of decomposition potential. Characteristics of good deposit, Factors
influencing the nature of the deposit, Methods of cleaning the metal surface.Electroplating of
Cu & Cr & electroless plating of Cu.

1 INTRODUCTION
Electrochemistry deals with the behavior of electrolytes in solution and
interconversion of chemical and electrical energies; that is, the study of chemical
changes due to the flow of an electric current and production of electric current due to
chemical reaction. Electrolysis, electrometallurgy and electroplating use electrical energy to
drive chemical reactions, while chemical energy is transformed into electricity in galvanic
cells, batteries and fuel cells. Substances such as metals and alloys conduct electricity under
the influence of an applied electric potential through a flow of electrons and hence are known
as electronic conductors. The flow of electricity in electronic conductors does not cause any
physical or chemical change in the conductor. On the other hand electrolyte solutions and
molten salts conduct electricity through the migration of ions and are known as electrolytic
conductors or electrolytes. When direct current is passed through an electrolyte solution,
decomposition and changes occur in the composition of the electrolyte. The practical
importance of electrochemistry includes electroplating, electroextraction of metals,
electrorefining of metals, and electro-production of certain compounds.

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1.1 ELECTROCHEMICAL CELLS
An electrochemical cell consists of two electrodes or metallic conductors, in contact
with an electrolyte, an ionic conductor. An electrode and its electrolyte comprise an
electrode compartment. The two electrodes may share the same compartment. If the
electrolytes are different, the two compartments may be joined by a salt bridge, which is a
tube containing a concentrated electrolyte solution in agar jelly that completes the electrical
circuits and enables the cell to function. So an electrochemical cell can be defined as a
single arrangement of two electrodes in one or two electrolytes which converts
chemical energy into electrical energy or electrical energy into chemical energy.
Electrochemical cells can be classified into two types:
• Galvanic Cells
• Electrolytic Cells

external circuit

internal circuit

Fig.1.1. A schematic diagram of Electrochemical Cell

1.1.1 Galvanic Cells
A galvanic cell is an electrochemical cell that produces electricity as a result of the
spontaneous redox reaction occurring inside it. Galvanic cell generally consists of two
electrodes dipped in two electrolyte solutions which are separated by a porous diaphragm or
connected through a salt bridge. It is a single arrangement of two electrodes in one or two
electrolytes which converts stored up chemical energy in the form of electroactive materials
(anode & cathode active materials) directly into electrical energy. The negatively charged
electrons flow from anode to cathode and are attracted to the positive cathode through the
external circuit.

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Anode vs. Cathode:
Anode ;
• the electrode at which oxidation occurs
• is where electrons are produced
• is what anions migrate towards
• has a +ve sign.
Cathode ;
• the electrode at which reduction occurs
• is where electrons are consumed
• is what cations migrate towards
• has a –ve sign
A typical galvanic cell can be illustrated by Daniel cell (Fig. 1.1.1)

-
e
v

Oxidation at Zn reduction at Cu

Half cell(Anode compartment) Half cell(Cathode

compartment)

Fig.1.1.1. A schematic diagram of Daniel cell

A Daniel cell consists of two compartments, one of which contains zinc rod dipped in
zinc sulphate solution and the other with a copper rod dipped in a copper sulphate solution.
The two electrolytes are connected by a salt bridge. When the zinc and copper rod electrodes
are connected externally through a voltmeter by using a wire, the following oxidation-
reduction reactions taking place at the electrodes. At the zinc electrode, zinc goes into the
solution as Zn2+ ions, liberating two electrons. In the process zinc undergoes oxidation
liberating two electrons. The positive ion flows from the salt bridge to the cathode and the
zinc electrode becomes lighter.
⚫ Zn (s) → Zn2+ (aq) + 2e- ---------------------------(1).
At the copper electrode reduction of Cu2+ ions takes place with the deposition of metallic
copper on the copper rod, by consuming two electrons. The negative ions flow from salt

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bridge to anode and copper electrode becomes heavier. The ionic conduction in the solution
is coupled to the electronic conduction in the electrodes.
⚫ Cu2+ (aq) + 2e- → Cu(s) --------------------------- (2)
Each of these reactions is known as half cell reaction. The reaction (1) in which loss of
electrons takes place is called oxidation half reaction; while the reaction 2, in which gain of
electrons takes place, is called reduction half reaction. The net reaction is obtained by adding
reactions 1 and 2. i.e. Zn(s)+ Cu2+ (aq) → Zn2+ (aq) + Cu(s) is called redox or oxidation –
reduction reaction. When the circuit is closed, the electrons flow from zinc to copper through
the external wire to feed the Cu2+ ions in the process of discharging copper and thus electrical
energy or current is produced which may be used for the purpose of external work.
As in the case of Daniel cell, by the combination of any two different electrodes materials
one can construct a galvanic cell. The electrode with a greater tendency to go into the
solution by liberating electrons acts as an anode, & the other one with more tendency
to undergo reduction acts as a cathode. In a galvanic cell anode is negative and the
cathode is positive. The reason to this nomenclature is that oxidation is accompanied
by the liberation of electrons which are given up to that electrode which thereby
acquires a negative charge. Reduction on the other hand, is accompanied by
absorption of electrons by reactant in solution from the electrode, which thereby
acquires a positive charge. Hence the flow of electrons is from the negative
electrode to positive electrode and the direction of flow of positive electricity,
which is known as conventional current, is from the cathode to anode.
1.1.2 Electrolytic cells
An electrolytic cell is an electro –chemical cell in which a non- spontaneous reaction is
driven by an external source of current although the cathode is still the site of reduction, it is
now the negative electrode whereas the anode, the site of oxidation is positive.
The electrolytic cell (Fig.1.1.2) find wide applications in the purification of metals & also in
electro deposition of a metal on to the surface of another metal, alloy or any conductor in
general, by the process of electrolysis.

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 CuSO4 solution

SO42- Cu2+
Fig.1.1.2 Schematic diagram of an electrolytic cell
Electrolysis involves the conversion of electrical energy into chemical energy i.e. chemical
changes are brought about by the expense of electrical energy. Since electrolysis is a non
spontaneous process, the minimum energy required to carry out such a process is equal to
the free energy increase accompanying the change, & this is equal but opposite in sign to
the free energy decrease accompanying the reverse spontaneous process. This is true when
electrolysis is carried out reversibly. However, in irreversible conditions, the potential to be
applied for electrolysis is higher than the reversible emf of the cell.
1.1.3 Representation of a galvanic cell
According to the present convention, a galvanic cell is represented by keeping in view the
following points:
1. The anode is written on the left hand side and the cathode is written on the right hand
side of cell representation.
2. The anode is written by writing the metal (or solid phase) first and then the electrolyte
along with the concentration in the bracket. The two are separated by a vertical line or
a semicolon. The electrolyte may be represented by the formula of the whole
compound or by ionic species.
Anode representation
Metal/ Metal ion (concentration) i.e. M/Mn+ (c)
Zn│Zn2+ or Zn; Zn2+ or Zn │ ZnSO4 (1M) or Zn; ZnSO4 (1M)
3. The cathode of the cell is represented by metal ion first and then the metal (or solid
phase) thereafter. The two are separated by a vertical line or a semicolon.
Cathode representation:

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 Mn+ (c) / M i.e. Metal ion (concentration) / Metal
e.g. Cu2+│Cu or Cu2+; Cu or Cu2+ (1M); Cu or CuSO4 (1M)/Cu
4. A salt bridge is indicated by two vertical lines, separating the two half-cells. Thus the
Daniel cell, may be represented as:
Zn │ ZnSO4 (1M)║ CuSO4(1M)/Cu
Cu(s) / Cu2+ (aq) ║Ag+(aq) / Ag (s)
Comparisons of Galvanic and Electrolytic cells
Galvanic Cell Electrolytic Cell

1. Cell reaction is spontaneous 1. Cell reaction is non-spontaneous

2. Converts chemical energy to electrical
2. Converts electrical energy into chemical
energy energy
Anode is negative and cathode is positive 3. Anode is positive and cathode is negative
3. Usually have two electrodes and two
4. Single electrolyte and two electrodes
electrolytes
5.
4. Used as a potable source of electrical
Used for electrolysis apparatus like
energy in cars, flashlights and calculators
electroplating and electrorefining
Example. Daniel cell

Example. Electroplating of nickel

1.1.4 LIQUID JUNCTION POTENTIAL

The potential set up at the junction of the two electrolytes because of the difference in the
speeds of the cations in one direction and anions in the other i.e. potential at the junction of
the two electrolytes because of unequal migration of ions across the boundary between the
two solutions is called the liquid junction potential, Ej. In a Daniel cell, if the concentrations
of ZnSO4 (aq) and CuSO4 (aq) are equal SO42- ions do not diffuse across the junction and the
charge cannot flow around the circuit. But Cu2+ ions diffuse into ZnSO4 (aq) and Zn2+ ions
diffuse into CuSO4 (aq) because Cu2+ ions are slightly more mobile than Zn2+ ions. This
produces a small excess positive charge on the ZnSO4 (aq) side of the junction and equal
negative charge on the CuSO4 (aq) side. The liquid junction potential is the difference
between the electric potential developed in the two solutions across their interface
i.e. Ej = Ø soln, R - Ø soln,L where Ø soln. R is the electric potential of the electrolyte solution on
the right hand side half – cell in the cell scheme. Ø soln. L
is the electric potential of the

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electrolyte solution on the left hand side half-cell. Generally, LJPs are of the order of a few
millivolts.
1.1.5 SALT BRIDGE
The contribution of the liquid junction to the potential can be reduced (to about 1 to 2
mV) by joining the electrolyte compartments through a salt bridge containing salts such as
KCl, KNO3, and NH4NO3 whose ions have the same migration velocities. Then the ions
move with equal speed to anode and cathode compartments minimizing the junctions
potentials almost zero. A salt bridge is used to connect electrolytically, the two electrolyte
solutions of a galvanic cell, as shown in the Fig. 1.1.5.

Fig.1.1.5 Daniel Cell indicating the function of a salt bridge

The salt bridge consists of a saturated solution of a salt such as KCl or NH4NO3, whose ions
have almost same migration velocities. The positive and negative ions of the salt in the salt
bridge migrate with equal speed into cathode and anode compartments respectively, thereby
minimizing liquid junction potential.
The salt bridge is prepared by dissolving 5g agar in 100 mL aqueous solution of KCl
containing 35 g of KCl and filling in a U-tube. On cooling, the agar forms a jell with KCl
solution in it.
A salt bridge has the following functions:
1. It provides electrical contact between the two electrolyte solutions of a cell i.e., it
physically separates the two electrolytes but completes the electrical circuit by
altering ions causing charge to move from half-cell to the other.

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 2. It minimizes liquid junction potential in galvanic cells containing two electrolyte
solutions in contact. i.e., it reduces the LJP to a minimum by nearly equal diffusion
rates of cations and anions.
3. It maintains the electrical neutrality of the two half cells i.e., it prevents any net
charge accumulates in the two electrolytes.
1.1.6 ELECTROMOTIVE FORCE OF THE CELL
Electricity cannot flow from one electrode to another unless there is a potential
difference between the two points. The difference of potential, which causes a current to flow
from the electrode at higher potential to an electrode at lower potential is called the
“electromotive force”(e.m.f.) of the cell “or the “cell potential” and is expressed in volts V.
The emf of a cell is denoted by E cell .Mathematically,
Ecell = Ecathode- Eanode
The driving force that pushes the negatively charged electrons away from the anode and pulls
them towards the cathode is known as emf. The E Cell depends on the nature of the electrodes
composition, (combination of electrodes, strong tendency to lose or gain electrons produces
large cell potential) temperature (E∞T) and concentration of the electrolyte solutions. To
facilitate comparison of different galvanic cells, their standard emf, denoted by E0 cell is used.
Standard emf of a cell is defined as the emf of a cell when the reactants & products of the cell
reaction are at a unit concentration or unit activity, at 298 K and at 1 atmospheric pressure
including pure solids and liquids.
The emf of a cell represents the driving force of a cell reaction. As represented by the
thermodynamic relation,
∆G = -nFE
Where ∆G is the free energy change accompanying a cell reaction, n is the number of
electron transfer during the cell reaction, and F is the Faraday constant, F = eNA, the
magnitude of the charge per mole of electrons. Hence the above equation is the key
connection between the electrical measurements on the one hand and thermodynamic
properties on the other.
The cell reaction is spontaneous or feasible when ∆G is negative. ∆G can be negative only if
the emf of the cell is positive, because, the other two factors, n & F are always positive. Thus
emf of a galvanic cell is always positive. The positive emf value indicates the spontaneity of
cell reaction in the given direction. When the cell potential is large, a given number of
electrons traveling between the electrodes can do a large amount of electrical work. When the
cell potential is small, the same number of electrons can do only a small amount of work. A

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cell in which the overall reaction is at equilibrium can do no work, and then the cell potential
is zero.
1.1.7 Measurement of emf of a cell
The emf cannot be measured accurately by connecting directly a voltmeter between the
two electrodes, because during such a measurement, a part of the cell current is drawn to
deflect the needle as part of the emf is used to overcome the internal resistance of the cell.
Consequently, such a measurement would indicate a potential difference less than the actual
emf of the cell. For precise emf measurements potentiometers are used, which require
extremely small current at the balance point.
The potentiometric measurement of emf of a cell works based on Poggendorff’s
compensation method. In this method, emf of a test cell is opposed by the impressed emf
from an external source of emf, and the measurement is made when there is no net flow of
current in the circuit. The basic principle is that the emf of the cell to be measured is exactly
balanced by an equal and opposite known emf so that no current flows in the circuit (null
point) A schematic diagram of the potentiometer is shown in Fig.1.1.7
S Rh
+ - C

D D
A
B
Ex
J
G
Es

Fig.1.1.7. Potentiometric arrangement for the measurement of EMF of a galvanic

cell.1.1.5

AB- Potentiometric wire

S- Storage battery
ES- Standard cell
Ex- unknown cell
G- Galvanometer
J- Sliding contact.
Rh – adjustable resistance
The two terminals of a storage battery(S) which has a constant and higher emf than the test
cell, is connected to two ends of a long uniform wire AB of high resistance. The positive
terminal of the test cell is connected to the end A, to which the positive terminal of S is
connected & the negative terminal is connected to a sliding contact J through a galvanometer
(G). The sliding contact is moved along the wire AB until the null point is reached, which is

9
indicated by no current flow in the galvanometer. The position of a null point is noted & the
distance AD is measured. The emf of the unknown cell Ex is proportional to the length AD.
• Ex α AD
Then the test cell Ex is replaced by a standard cell Es, whose emf, is known the position of
the sliding contact is readjusted by moving it over AB, as before, till null point D1 is
reached .The length AD1 is measured. The emf of the standard cell Es is proportional to the
length AD1.
• Es α AD1
• Ex ═ AD
• Es AD1
• Ex = AD x Es
ADI
Thus the emf of the test cell is calculated by substituting the emf of the standard cell in the
above equation.
1.1.8 Standard cell requirements:
1. Its emf should remain constant for a longer period of time.
2. It should be capable of providing highly reproducible emf.
3. The temperature coefficient of emf should be negligibility small i.e (δ E/ δT)= 0
4. The cell reaction should be reversible.
5. It should not be subjected to permanent damage due to the passage of current.
6. A standard cell is one which has a constant and reproducible known emf with a
negligible variation of emf with temperature e.g. Weston standard cell or Weston
cadmium cell.
1.2 Energetic of cell reactions:
1.2.1 The relation between E and ∆G:
A cell in which the overall reaction has not reached chemical equilibrium can do electrical
work as the reaction drives electrons through an external circuit. The work that a given
transfer of electrons can accomplish depends on the cell potential.
The maximum electrical work as per thermodynamics, chemical reaction can do is given by
the value ∆G for the reaction.
We, max = ∆G----------------- 1
Where, We is electrical work. It follows that, to draw thermodynamic conclusions from
measurements of the work a cell can do, we must ensure that the cell is operating reversibly.
Only then it is producing maximum work and only then we can relate electrical work to ∆G.
Both these conditions are achieved by measuring the cell potential when it is

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balanced by an exactly opposing source of potential so that the cell reaction occurs
reversibly, the composition is constant, and no current flows.
The net electrical energy and the emf of the cell produced in a cell is the product of the
quantity of electricity that passes through the cell and the emf of the cell.
We = QE Joules. -------(2)
Q is the quantity of electrical charge in coulombs produced by the reaction and E is the emf
of the cell in volts.
Charge on 1 mol (6.02 x 10 23) electrons is F coulombs, where F is Faraday constant. When n
electrons take part in the cell reaction, n mols of electrons are involved per mol of a reactant
of the reaction. Hence charge on n mol of electrons = nF coulombs. This is the charge, Q in
coulombs produced by the reaction. For 1 mole of electrons transferred in the cell reactions,
the quantity of electricity = 1F
If n moles of electrons are transferred in the cell reactions, the quantity of electricity = n F
Therefore electrical energy= nFE, ----------(3)
In a large number of reactions, electrical energy produced is not equal to chemical energy.
Electrical energy produced = decrease in free energy for cell reaction i.e. - ∆G = nFE or
∆G = -nFE Joules-------(4)
If we know emf E, ∆G can be calculated. The larger the value of cell potential the further the
reaction is equilibrium.
1.2.2 Relation between E and ΔH
Enthalpy Change ΔH = nF[T(δE/δT)P –E] --------(5)
If we know emf and temperature coefficient of emf, ΔH can be calculated..

1.2.3 Relation between E and ΔS :

ΔS = nF(δE/δT)P ------------------(6)
1.2.4 Numerical Problems
1. Emf of Weston Cadmium cell is 1.0183 V at 293 K and 1.0l81 V at 298 K. Calculate
∆G, ΔH and ΔS of the cell reaction at 298 K.
Solution:- ∆G: ∆G = - n FE n = 2 for the cell reaction;
F = 96,500 C E= 1.0181 V at 298 K
∆G = -2 x 96,500 x 1.0181 J = -196.5 KJ
∆H: ∆H = nF [ T (δE /δT)P – E]
(δE/δT)p = 1.0181 – 1.0183 / 298-293 = -0.0002 / 5
= - 0.00004VK-1
T = 298 K
∆H = 2 x 96,500 { [298 x (-0.00004)] – 1.0181}
= -198. 8 KJ
ΔS: ΔS = nF(δE / δT) P

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 = 2 x 96,500 x (0-00004) = -7.72JK-1
2. The emf of the cell Cd|CdCl2. 2.5 H2O (saturated) || AgCl(s)| Ag is 0.6753V and 0.6915 V at
298 K and 273 K respectively. Calculate ∆G, ΔH and ΔS of the cell reaction at 298 K.
Solution. Here n = 2, E = 0.6753 V at 298 K and 0.6915 at 273 K.
(δE/δT)p = (0.6753-0.6915) V/ (298-273) K = - 0.00065 V/K
Now at 298 K, ∆H = nF [ T (δE /δT)P – E]
= 2 mol x 96,500 C mol-1{ [298 K x (- 0.00065 V/K)] – 0.6753 V }
= -167. 7 KJ
∆G at 298 K ; ∆G = - n FE = -2 x 96,500 x 0.6753 = -130.33 KJ
ΔS = nF(δE / δT) P
= 2 x 96,500 x (0-00065) = -125.45 J.K-1

1.3 SINGLE ELECTRODE POTENTIAL

The potential of the single electrode is the difference of potential between a metal and
the solution of its salt. i.e the tendency of an electrode to lose or gain electrons when in
contact with its own ions in the solution. In a cell, the electrode with lower electrode potential
has less tendency to undergo reduction and acts as an anode. The electrode with higher
electrode potential has a higher tendency to undergo reduction and acts as a cathode.
Example: In case of Zn in ZnSO4 solution acquires a negative charge (Fig. 1.3a).
M(s) → Mn+ + ne -(aq) (1) Dissolution reaction and conversely, the metal
shows the tendency to go into the solution as metal ion by losing electrons (Fig. 1.3b).
Mn+ (aq) + ne -(aq) → M(s) (2) Deposition reaction

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 Fig.1.3a. Zinc ions move Fig.1.3b.Copper ions get deposited as
into solution leaving copper leaving behind free negatively
behind electrons making it charged sulfate ions in solution makes
electron rich the electrode electron poor

The rate of this reaction depends on,

(i) the nature of the metal
(ii) the temperature
(iii) the concentration of metal ions in solution.

When a metal is placed in the solution of its own salt, the chemical reaction (1) or (2), takes
place depending on whether the dissolution reactions are faster than deposition or vice versa.
A dynamic equilibrium is established, because negative or positive charge developed on the
metal attracts the positively or negatively charged free ions in the solution. Due to this
attraction, the positive or negative ions remain quite close to the metal. Thus, a short layer of
positive ions or negative ions as in the figure is formed at the junction of the electrode and the
solution. This layer is called a Helmholtz electrical double layer. A difference of potential
is consequently, set up between the metal and the solution. This potential difference will
persist as long as the charge is allowed to remain on the metal; and this will prevent any
further passing of the positive ions from or to the metal. At equilibrium the potential
difference between the metal & solution becomes a constant value. The equilibrium potential
difference so established is called the “electrode potential” of the metal. Thus, the electrode
potential of a metal is the measure of the tendency of a metallic electrode to lose or gain
electrons, when it is in contact with a solution of its own salt of unit molar concentration at
298K. Consequently, the tendency of an electrode to lose electrons is a direct measure of its
tendency to get oxidized & this tendency, is called oxidation potential. Similarly, the
tendency of an electrode to gain electrons is a direct measure of its tendency to get reduced
and this tendency is known as reduction potential. By concentration, electrode potential refers
to reduction potential.
1.3.1 Measurement of electrode potential
It is impossible to determine the absolute half cell potential
We can only measure the difference in potential between two electrodes
potentiometrically, by combining them to form a complete cell. All voltage measuring
devices determine differences in potential. If one knob of voltameter is connected to a test
electrode, another one will make contact with the solution in the electrode compartment via
another conductor. This second contact involves solid/ solution interface and acts as a record
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half cell. The redox reaction must take place if the charge is to flow and potential is to be
measured. A potential is associated with this second reaction and absolute half cell potential
is not obtained. What we measure ultimetaly is the difference between the half cell potential
of test electrode and a half cell made up of the second contact and the solution. Therefore,
absolute electrode potentials cannot be measured. We can only determine the relative value of
electrode potential, if we can fix arbitrarily the potential of any one electrode. For this
purpose, the potential of a standard hydrogen electrode (SHE) or normal hydrogen electrode
(NHE) (i.e., a platinum electrode in contact with 1 M H+ ion concentration and hydrogen
gas at 1 atmospheric pressure is constantly bubbled through it) has been arbitrarily fixed as
zero and the numerical values of electrode potentials of different electrodes are relative
values w.r.t SHE. Therefore, single electrode potentials of electrodes are referred to as
potentials on the hydrogen scale.
Sign of electrode potential: When an electrode is coupled with a SHE, if reduction occurs
then EP is given a +ve sign e.g Copper electrode + SHE
• Cu2+ +2e- → Cu(s) reduction at copper electrode (cathode)
• H2(g) → 2H+ +2e- oxidation at hydrogen elecrode (anode) → E0 = 0.34 volt
A +ve sign on the EP value indicates that the half cell acts as cathode and acepts electrons
from the hydrogen electrode.
Similarlly, when an electrode is coupled with SHE, if oxidation occurs then EP is given a -ve
sign e.g . Zinc electrode + SHE
• Zn (s) → Zn2+(aq) +2e- (oxidation at Zinc elecrode)
• 2H (aq) + 2e → H 2 (g)
+ -
(reduction at Hydrogen elecrode) → E0 = - 0.76 volt
A –ve sign on the electrode potential value indicates that the half cell acts as an anode by
releaseing electrons to the hydrogen electrode.
1.3.2 Standard electrode potential:
Standard electrode potential is the electrode potential when the electrode is in contact with a
solution of unit concentration at 298 K involving pure solids and liquids. If the electrode
involves a gas, then the gas is at 1 atmospheric pressure. It is denoted by Eo. When elements
are arranged in increasing order (downwards) of their standard electrode potential, a series
called electrochemical series is obtained. In a cell, the electrode with lower electrode
potential has less tendency to undergo reduction and it acts as anode similarly electrode with
higher electrode potential has higher tendency to undergo reduction and acts as cathode.
Reducing agents Stable ions Electrode half reaction E0 volts
Lithium Li+ -3.03

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 Potassium K+ -2.92
Aluminium Al3+ -1.66
Zinc Zn2+ -0.76
Iron Fe3+ -0.44
Lead Pb2+ -0.13
H2 2H+ 0
Copper Cu2+ 0.34
Silver Ag+ 0.80
Gold Au3+ 1.52

Fig. 1.3.2. Selected standard electrode potentials

1.3.3 Nernst equation
Nernst equation is an expression of a quantitative relationship between electrode
potential/cell potential and concentration of the electrolyte species in an electro-chemical
reaction. i.e. mathematical expression that relates the potential of an electrode to the
concentrations of those species in solution that are responsible for the potential. Consider a
general redox reaction: Mn+(aq) + ne- M(s)
E = Eo + 2.303RT/nF log [Mn+]
E= Electrode potential at some moment in time
E0= Standard electrode potential
R= Universal gas constant (joules per mol K)
T= Temperature in Kelvin scale F= Faraday constant (96,500 Coulumbs)
n = Number of electrons transferred in the half reaction/ cell reactions
[Mn+]= Concentration of metal ion at that moment in time (moles per litre).
At 298 K, when the values of R.T and F are substituted, the equation reduces to,
E = Eo + (0.0592/n) log [Mn+]
This expression is known as the Nernst equation for electrode potential at 298 K. From these
equations, it is clear that,
i) If the concentration of the solution (Mn+) is increased, the electrode potential
increases and vice versa.
ii) If the temperature is increased, the electrode potential increases and vice versa.
The Nernst equation can also be applied for the calculation of emf of a cell. Consider the cell
reaction aA+ bB cC +dD

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The Nernst equation for the emf of the cell is
Ecell = Eocell – 2.303RT/nF log [C]c [D]d /[A]a [B]b
At 298 K,
Ecell = Eocell – (0.0591/n) log [C]c [D]d /[A]a [B]b

Where n is the number of electrons transferred during the cell reaction and Eocell is the
standard emf of the cell.
1.3.3.1 Significance of the Nernst equation
1. It can be used to calculate the potential of a cell that operates under non-standard
conditions. The Nernst equation tells us that a half-cell potential will change by 59 millivolts
per 10-fold change in the concentration of a substance involved in one-electron oxidation or
reduction; for two electron processes, the variation will be 28 millivolts per ten fold
concentration change. Thus for the dissolution of metallic copper
Cu(s) → Cu 2+ + 2e–
the potential E = (– 0.337) – .0295 log [Cu 2+
] becomes more positive (the reaction has a
greater tendency to take place) as the cupric ion concentration decreases.
2. It can be used to measure the equilibrium constant for a reaction. At equilibrium the
overall cell potential for the reaction is zero. i.e. E=0
Nernst equation,
0 = Eo - RT/nF lnKc
Kc = e nFE° / RT

1.4 Calomel electrode

The calomel electrode (Fig.1.4.1), a mercury mercurous chloride electrode develops + 0.242
V at 289 K when the KCl solution is saturated. It has been found that the potential of the
calomel electrode, on the hydrogen scale varies with the concentration of the potassium
chloride solution used. The concentration of KCl solution used is either decinormal, normal
or saturated. Correspondingly, the electrode is known as decinormal, normal or saturated
calomel electrode respectively.
1.4.1 Construction & Working:

16
 Fig.1.4.1 Schematic diagram of calomel electrode.

It consists of a tube, in the bottom of which is a layer of mercury, over which is placed a paste
of mercury and mercury chloride.The remaining portion of the cell is filled with a solution of
normal or decinormal or saturated solution of KCl. A platinum wire sealed at its end fixed
into the main tube dipping into the mercury layer is used for making electrical contact. The
electrode can be represented as Hg (l) /Hg2Cl2 (sat’d) /KCl-(sat’d/ xM)
The calomel electrode can act as anode or cathode depending on the nature of other electrode
of the cell. When it acts anode, the electrode reaction is
• 2Hg (l) → Hg22+ (aq) + 2e-

• Hg22+(aq) + 2Cl- (aq)→Hg2Cl2

----------------------------------------------------
• 2Hg(l) + 2Cl- (aq) → Hg2Cl2 (s)+ 2e-
When it acts as cathode, the electrode reaction is,
• Hg22+(aq) + 2e-→ 2Hg(l)
• Hg2Cl2 (s) → Hg22+ (aq) + 2Cl-
__________________
• Hg2Cl2(s) + 2e- → 2Hg (l) + 2 Cl-(aq)
The net reversible electrode reaction is,
Hg2Cl2(s) + 2e- 2 Hg (l) + 2 Cl-(aq)
Electrode potential is given by
E = Eo – 2.303 RT log [Cl-]2
2F

17
 = Eo - 0.0591 log [Cl-] at 298 K
1.4.2 Uses:
Since the electrode potential is a constant it can be used as a secondary reference electrode to
replace the inconvenient SHE for potential measurements.
i) To determine the electrode potential of the unknown electrode
For example: The test electrode, Zn(s) /Zn2+(aq) is coupled with a saturated calomel electrode.
Zn(s) / Zn2+ (aq) ││ Cl- (saturated soln) /Hg2Cl2(s) / Hg (l)
The emf of the so formed cell is determined experimentally by potentiometric method.
Then
E cell = E cathode – Eanode = 0.2444 – Ezn
Ezn = 0.2444 – E cell
ii) To determine the pH of a solution cell: Hg(l) / Hg2Cl2 (s) // H+ /pt,H2 (g)
E cell = E cathode – E anode
= 0.242 – (- 0.0592 pH)
pH = E cell – 0.242/0.0592
1.4.3 Advantages
➢ It is very simple to construct.
➢ It can be used for a long time without much attention.
➢ Electrode potential is stable over a long period (reproducibly).
➢ It hashes the low temperature coefficient of emf.
➢ It is less prone to contamination because the mercury/ mercurous chloride interface is
protected inside a tube not in direct contact with the electrolyte.
1.4.4 Disadvantages
➢ Calomel electrodes should not be used above 50oC because the mercurous chloride
breaks down, yielding unstable readings. This is important if substantial temperature
changes occur during measurement.
➢ Calomel electrode should be used with proper precaution as mercury compounds are
toxic.
1.5 Ion Selective Electrode.
The electrode which is sensitive to a specific ion present in an electrolyte whose
potential depends upon the activity of a specific ion in the electrolyte is called an ion selective
electrode. The magnitude of the potential of this electrode is an indicator of the activity of the
specific ion in the electrolyte. Example for this type of electrode is glass electrode.
18
 1.5.1 Glass electrode: Construction

Glass Membrane
Electrical contact

Protective sleeve

Ag/AgCl wire

HCl, 0.1 mol dm-3(Referrence solution of dilute

HCl)
Thin walled glass Outer Inner
membrane
E1 E2
Solution of 1
unknown pH

Fig.1.5.1a. Schematic diagram of the Glass Fig. 1.5.2b. Line sketch of a glass membrane
electrode showing outer analyte solution and internal
reference solution.

The electrode consists of a thin glass membrane, typically about 0.03 to 0.1 mm thick, sealed
onto one end of a heavy–walled glass tube. A special variety of glass (corning 0l5 glass with
approximate composition 20 % Na2O, 6 % CaO & 72 % SiO2) is used which has a low
melting point and high electrical resistance. The glass bulb is filled with a solution of

19
constant pH (0.1 M HCl). A small volume of saturated silver chloride is contained in the tube.
A silver wire in this solution forms a silver/silver chloride reference electrode which is
connected to one of the terminals of a potential measuring device. The internal reference
electrode is a part of the glass electrode and it is not the pH sensing element. Only the
potential that occurs between the outer surface of the glass bulb and the test solution responds
to pH changes.
1.5.2 Working: A silicate glass used for membranes consists of an infinite 3D- network of
SiO44- groups in which each silicon is bonded to four oxygen and each oxygen is shared by
two silicons. There are sufficient cations to balance the negative charge of the silicate groups
within the interstices of this structure. Singly charged cations such as sodium and lithium are
mobile in the lattice and are responsible for electrical conduction within the membrane. The
glass is a partially hydrated aluminosilicate containing sodium or calcium ions. The
hydration of a pH sensitive glass membrane involves an ion-exchange reaction between
singly charged cations in the interstices of the glass lattice and protons from the solution. The
process involves univalent cations exclusively because divalent cations are too strongly held
within the silicate structure to exchange with ions in the solution and hence immobile. The
ion-exchange reaction can be written as

• H+ + Na+ Na+ + H+
Solution glass solution glass

The Na+ ions on the glass membrane are exchanged for H+ ions in the solution. The potential
of the electrode is controlled by the difference between the hydrogen ion concentration inside
and outside the thin glass membrane. Since the H+ ion concentration inside the electrode is
constant, the electrode’s potential varies only with the concentration of H+ in the solution
outside. Thus the potential arises from the difference in positions of ion-exchange
equilibrium on each of the two surfaces. The surface exposed to the solution having the
higher H+ concentration becomes positive with respect to the other surface. This charge
difference or potential serves as the analytical parameter when the pH of the solution on one
side of the membrane is held constant. Evidently the selectivity of glass electrodes is related
both to the ability of the various monovalent cations to penetrate into the glass membrane and
to the degree of attraction of the cations to the negative sites within the glass.

20
1.5.3 Electrode Potential of GE
The overall potential of the glass electrode has three components; 1) The boundary potential
Eb, which varies with the pH of the analyte solution. It is made up of two potentials, E1 & E2
which develop at the two surface of the glass membrane i.e. the potential developed at the
inner glass surface & the potential developed at the outer glass surface.
Eb = E1-E2 _______________________ (1)
Where Eb is the boundary potential
E1 = potential developed at the interface between the exterior of the glass and the
analyte solution
E2 = Potential developed at the interface between the internal solution and the interior
of the glass. The boundary potential is related to the concentration of hydrogen
ion in each of the solution by the Nernst-like equation.

Eb = E1 – E2 = 0.0592 log Cl / C2 _________________ (2)

Where C1 = concentration of the analyte solution
C2 = concentration of the internal solution
For a glass pH electrode the hydrogen ion concentration of the internal solution is held
constant.
So eqn. (2) becomes
Eb = K + 0.0592 log C1 __________________(3) (Recall pH= -log [H+]
Eb = K - 0.0592 log pH where K= -.0592 log C2
The boundary potential is then a measure of
1) the hydrogen ion concentration of the external solution.
2) The potential of the internal Ag/AgCl reference electrode. E Ag/AgCl.
3) A small unpredictable contribution called the asymmetry potential, E asym.
The sources of the asymmetry potential include the following.
i) Differing conditions of strain in the two glass surfaces during manufacture
ii) Mechanical abrasion on the on the outer surface during use
iii) Chemical etching of the outer surface during use.
The asymmetry potential changes slowly with time. The glass electrode potential can be
written in the equation form as
EG = Eb + EAg/ AgCl + E asym __________________ (4)
Substitution of eqn – (3) for Eb, gives

21
EG = K + 0.0592 log C1 + EAg/AgCl + E asym
= K – 0.0592 log pH + E Ag/AgCl + E asym ___(5)
EG = EoG – 0.0592 pH __________________(6)
where EoG = K + EAg/AgCl + E asym. a combination of three constant terms = constant To
measure the hydrogen ion concentration of the test solution, the glass electrode (indicator
electrode) must be combined with an external reference electrode, which is required for all
kinds of ion-selective electrode determinations.
1.5.4 Applications: Determination of pH:
The glass electrode has an emf that changes with hydrogen ion concentration, i.e the glass
electrode is the most important indicator electrode for hydrogen ion. It is used for the
measurement of pH under many conditions and normally calomel electrode is used as
reference electrode to complete the cell (Fig.1.4.4)
Cell: SCE / Test solution / GE

Fig.1.4.4. Set up of indicator electrode and reference electrode for the measurement of pH.

E cell = E glass – E calomel where E glass = the E.P. of the glass electrode.
E calomel = the E.P. of the SCE
E cell = EoG – 0.0592 pH – 0.2444
The EoG value of a glass electrode can be determined by dipping the glass electrode in a
solution of known pH. Typical fields are the clinical & food analysis, environmental
monitoring (industrial waste acidity of rain) and process control (fermentation, boiler water,
galvanization & precipitation)

22
1.5.5 Advantages:
➢ It can be used without interference in solutions containing strong oxidants, strong
reductants, proteins, viscous fluids and gases as the glass is chemically robust.
➢ The glass electrode gives accurate results in the pH range 2 – 10. With some special
glass (by incorporation of Al2O3 or B2O3) measurements can be extended to pH
values up to 12.
➢ It is immune to poisoning and is simple, robust and easy to operate.
➢ The equilibrium is reached quickly & the response is rapid.
➢ It can be used for very small quantities of the solutions. Small electrodes can be used
for pH measurement in one drop of solution in a tooth cavity or in the sweat of the
skin (micro determinations using microelectrodes)
➢ The glass electrode is much more convenient to handle than the inconvenient
hydrogen gas electrode.
➢ Glass electrodes which are selective for Li+, Na+, Cs+, Ag+ and NH4+ ions are
commercially available and these special electrodes are useful for measuring the
above ions.
1.5.6. Disadvantages:
➢ The bulb of this electrode is very fragile and has to be used with great care. The
sensitive tip is easily scratched and ruined.
➢ The alkaline error arises when a glass electrode is employed to measure the pH of
solutions having pH values in the 10-12 range or greater. In the presence of alkali
ions, the glass surface becomes responsive to both hydrogen and alkali ions. Hence
the measured pH values are low and thus the glass pH electrode gives erroneous
results in highly alkaline solutions.
➢ The acid error results in highly acidic solutions (pH less than zero) Measured pH
values are high.
➢ Dehydration of the working surface may cause erratic electrode performance. It is
crucial that the pH electrode be sufficiently hydrated before being used. When not in
use, the electrode should be stored in an aqueous solution because once it is
dehydrated; several hours are required to rehydrate it fully.
➢ As the glass membrane has a very high electrical resistance (50 to 500 MΩ), the
ordinary potentiometer cannot be used for measurement of the potential of the glass

23
 electrode. Thus special electronic potentiometers are used which require practically
no current for their operation.
➢ Standardization has to be carried out frequently because asymmetry potential changes
gradually with time. It is better to determine EoG for a glass electrode before use.
➢ The commercial version is moderately expensive.
➢ To some extent, the constant EoG is a function of the area of glass in contact with the
acid analyte. For this reason, no two glass electrodes will have the same value of E oG.
Note that EoG depends on a particular glass electrode used & it is not a universal
constant.
1.6 BATTERY TECHNOLOGY

1.6.1 Introduction

Can you imagine a world without batteries? The clock on your wall requires a battery for it to

work. The watch on your wrist goes on a battery. The motor vehicle needs a battery for it to

start and take you to your destination. Battery is the backbone of UPS to run your computer

without interruption. After a days work, if you pick-up the remote control of the television, it

is again the battery that helps you to change channels of the T.V. Cameras, laptop computers,

cellular phones, key chain laser, heart pacemaker and children toys – they all require

batteries.

Batteries are used for so many different purposes and different applications require batteries

with different properties. The battery required to start a car must be capable of delivering a

large electrical current for a short period of time. The battery that powers a cardiac

pacemaker must be small, rugged, leak proof, compact and capable of delivering a steady

current for an extended period of time. In UPS systems, longer and consistent backup is

needed. Batteries for hearing aids must be above all tiny. Batteries for torpedoes and

submarines must be stable during storage and give high power for short times & certainly

rechargeable. For a lap-top computer, a battery in the form of a flexible sheet distributed

24
around the case is much preferred. Batteries remain an enormous industry with a turnover of

billions of pounds worldwide.

1.6.2 Classification of commercial cells

Primary Cells: They are galvanic cells which produce electricity from chemicals that are

sealed into it when it is made. This type of cells cannot be recharged as the cell reaction

cannot be reversed efficiently by recharging. Once the cell reaction has reached equilibrium

the cell must be discarded. No more electricity is generated and we say the battery is ‘dead’.

These are also known as ‘throw – away’ batteries or irreversible batteries.

Eg: Dry cell, Lithium copper sulfide cell

Secondary cells: A secondary cell is rechargeable by passing current through it. In the

charging process, an external source of electricity reverses the spontaneous cell reaction and

restores a non- equilibrium mixture of reactants. After charging, the cell can be used for

supplying current when required, as the reaction sinks toward equilibrium again. Thus as the

secondary cell can be used through a large number of cycles of discharging and charging.

Such cells are also known as rechargeable cells, storage cells, or accumulators.

Eg. Lead-acid batteries, Nickel-cadmium cell, Lithium- ion battery

1.6.2.1 Requirements of Primary Battery:

• Compact, lightweight and must be fabricated from easily available raw materials.

• Economic and have benign environmental properties

• Should have a high energy density, longer shelf life

• Provide constant voltage and should have a long discharge period

1.6.2.2 Requirements of Secondary Battery

• Long shelf-life in both charged & discharged conditions

• Longer cycle life and design life

25
• High power to weight ratio

• Short time for a recharge.

• High voltage & high energy density

1.6.2.3 Differences between Primary and Secondary batteries

Primary Batteries Secondary Batteries

1.Cell reaction is irreversible Cell reaction is reversible
2. They must be discarded after its They may be recharged a number of
active elements have been consumed times from an external d.c. source
during its useful life
3. Have a relatively short shelf life Have a very long shelf life
4. Function only as galvanic cells Function as galvanic cells during
discharge as & as electrolytic cells
during the charging process.
5. They cannot be used as energy They can be used as energy storage
storage devices devices (e.g. solar/ thermal energy
converted to electrical energy)

6. They cannot be recharged They can be recharged.

e.g. Dry cell, Li-MnO2 battery e.g.Lead acid battery, Ni-cd battery

1.6.3 Lead Storage Battery (Lead Accumulator or Car Battery or The acid battery)

Construction: The electrodes are lead grids to maximize its surface area. The anode grid is

filled with finely divided spongy lead (Pb) and the cathode grid is packed with lead dioxide

(PbO2). Both electrodes are submerged in a sulfuric acid solution (H2SO4) having a specific

gravity of about 1.25 that acts as the electrolyte. Anode and cathode grids are separated by

insulators like strips of wood, rubber or glass fiber. In car batteries, six cells are connected in

series (anode to cathode) to produce a 12–volt battery. The battery is encased in a plastic

container or hard vulcanized rubber vessel. The cell doesn’t need to have a separate anode

and cathode compartments because the oxidizing and reducing agents are both solids (PbO2 &

Pb) that are kept from coming in contact by the presence of insulating spacers between the

grids. Both anode and cathode are immersed in a common electrolyte (i.e. cell without liquid

26
junction). This is an example of a ‘wet cell’, because the electrolyte is an aqueous solution

of sulphuric acid. The lead acid battery is very widely manufactured – 300 million units are

made each year.

At the cathode:

• PbO2(s) + 4H+(aq) + 2e− → Pb2+(aq) + 2H2O(l)

• Pb2+(aq) + SO42−(aq) → PbSO4(s)

____________________________________________________
• PbO2(s) + 4H+(aq) + SO42−(aq) + 2e− → 2 PbSO4(s) + 2H2O(l)
_____________________________________________________

Overall: Pb(s) + PbO2(s) +4H+(aq) + 2SO42−(aq) → 2PbSO4(s) + 2H2O(l)

Explanation:At the anode, lead atoms lose two electrons (e-) and become positively charged

lead ions (Pb2+). The lead ions combine with the sulfate ions (SO42-) in the sulfuric acid

solution to produce lead sulfate (PbSO4). At the cathode, lead dioxide gains electrons,

releasing oxygen, which attaches to hydrogen ions (H+) to produce water (H2O (l) and lead

ions. The lead ions react with sulfate ions to produce lead sulfate. As this reaction progresses,

the flow of electrons creates an electric current. Lead sulfate adheres on each electrode and

water increases. The concentration of sulfuric acid decreases and the amount of lead and lead

dioxide decrease. When the reactants are depleted, the battery stops producing electricity.

The reaction can be reversed by recharging the battery & the PbSO4 formed during discharge

remains adhered on each electrode and is available at the site during recharging. The nominal

voltage of each cell is about 2.1 V. The lead storage battery is designed to operate reversibly,

so that it can be used for the storage of electrical energy. They are called storage batteries

because their essential function is to store electrical energy. It is used to store energy in

chemical form.

Reactions during Charging:

Anode: PbSO4(s) + 2e- → Pb(s)+ SO42-(aq)

Cathode: PbSO4(s) + 2H2O(l) → PbO2(s) + SO42-(aq) + 4H +(aq) +2e-

27
Net reaction: 2PbSO4(s) + 2H2O(l) → Pb(s) + PbO2(s) +2H2SO4

Recharging is possible because PbSO4 formed during discharge adheres to the electrodes. By

attaching an external power source to a battery ( >2 volts), a current runs through the poles in

the opposite direction from normal discharge. This changes the lead sulfate and water back

into the original reactants, lead dioxide and sulfuric acid, i.e. the electrodes return to their

former composition and the sulfuric acid is regenerated. Charging, therefore, produces a

gradual increase in the sulfuric acid concentration. Since the level of charge on a storage

battery is related to sulfuric acid concentration, the specific gravity of the H2SO4 solution is a

measure of the operational condition of a battery. A charged battery at room temperature

with its electrolyte at normal concentration supplies a potential difference of 2.1 to 2.2 V. The

complete reaction cycle of a lead acid storage battery is as follows.

Disch
Pb(s) + PbO2 + 2 H2SO4(aq) arge 2 PbSO4(s) + 2 H2O(l)
H2SO4 Ch
arg
In an automobile, the energy necessary for recharging the battery is provided by the generator

driven by the engine. As the external source forces electrons from one electrode to another,

the PbSO4 is converted to Pb at one electrode & to PbO2 at the other.

Overcharging:

Electrolysis of water: The net reaction can be summarized by the equation.

2H2O (l) + electrical energy → 2H2(g) + O2(g)

No gases will be liberated on charging as long as lead ions are present in solution. If the

electrolysis is permitted to proceed further, hydrogen gas is formed at the cathode and oxygen

gas is evolved at the anode. The hydrogen ions are discharged at the cathode through the

reaction

2H+(aq) + 2e-→ H2(g)

28
Sulphate ions are resistant to oxidation and are not discharged at the cathode. Water is

oxidized at the anode in preference to SO42-

2H2O(l) →O2(g) + 4H+(aq) +4e-

Consequences: (i) Excessive charging may reduce the acid level and may damage the

exposed electrode grids (ii) In extreme cases, there will be dangerous high-pressure build-up

that can lead to a serious risk of explosion. In more normal circumstances, the older version

of the battery needs to be ‘topped up’ from time to time.

Recent years have seen the introduction of “maintenance – free batteries” without a gas –

release vent. Here the gassing is controlled by careful choice of the composition of the lead

alloys used i.e. by using a Pb-Ca (0.1 % ) as the anode which inhibits the electrolysis of

water.

Alternatively, some modern batteries contain a catalyst (e.g. a mixture of 98% ceria (cerium

oxide) & 2% platinum) that combines the hydrogen and oxygen produced during discharge

back into the water. Thus the battery retains its potency and requires no maintenance. Such

batteries are sealed as there is no need to add water and this sealing prevents leakage of cell

materials.

Applications: The many battery designs available for a wide variety of uses can be classified

into three main categories. (a) Automotive (b) Industrial & (c) Consumer batteries.

The automotive type is used in cars and trucks, to provide a short burst of power for starting

the engine. It is incorporated as an essential accessory into the starting circuit of internal

combustion engines for starting, lighting & ignition (SLI). Units normally have nominal

voltages of 12 V for LMVS and 24 V for HGVS. It is still playing a major role in

transportation, powering literally millions of ICES in automobiles. The industrial batteries are

used for heavy–duty applications such as motive and standby power. This class of batteries is

used to operate electric trucks, submarines and mine locomotives. They also provide power

29
for the air conditioning and lighting systems. It is used in the stationary back–up power

applications such as telecommunication systems, to ensure that, for example, the telephone

network will continue to operate even in the event of a mains power failure. Such batteries

are kept in hospital operating theaters, railway signal centres and other places where a power

failure might be disastrous and is used to supply electrical power during emergencies.The

consumer batteries are used in aemergency lighting systems, security and alarm systems,

public address systems, power tools, UPS in computers, and small engine starting including

electronic vehicles.

Advantages:

• A lead storage battery is highly efficient. The voltage efficiency of the cell is defined

as follows.

• Voltage efficiency = average voltage during discharge

• average voltage during charge
• The voltage efficiency of the lead – acid cell is about 80 %.

• The near reversibility is a consequence of the faster rate of the chemical reactions in

the cell i.e. anode oxidizes easily and cathode reduces easily leading to an overall

reaction with a high negative free energy change.

• A lead – acid battery provides a good service for several years. The number of

recharges possible range from 300 to 1500, depending on the battery’s design and

conditions. The sealed lead-acid batteries can withstand up to 2000 – recharging.

Time required for recharging is relatively low i.e about 2-8 hours.

• The battery has low internal self – discharge.

• A typical car battery provides a voltage of 12 V. This is not a large voltage, but the

battery can provide a large current. E.g. over 10 A, without being destroyed.

Disadvantages:

30
 • If left unused in partially charged condition, it can be ruined in a short time by

nucleation and the growth of relatively large PbSO4 crystals, which are not easily

reduced or oxidized by the charging current. This disaster is known as ‘sulfation’.

• The lead acid battery has low energy storage to weight ratio i.e. its chief

disadvantages is its great weight.(energy density ~ 35 wh / kg)

• The cell potential decreases with a decrease in concentration of sulfuric acid. During

the discharge process sulfuric acid is consumed and water is produced. So the solution

of sulfuric acid in the cell becomes less concentrated. The state of charge of the cell

can be judged by the concentration of sulfuric acid in the liquid and this is usually

done with a simple device to measure the density of the liquid. The density of a

healthy, fully charged battery is ≥ 1.25 g/mL.

• The battery is not efficient at a lower temperature. Foe a battery to function properly,

the electrolyte must be fully conducting. There will be an increase in the viscosity of

the electrolyte due to a decrease in the temperature. This leads to a decrease in the cell

potential.

• Overcharging may damage the exposed electrodes and may also lead to an explosion

in extreme cases. Sulfuric acid is highly corrosive liquid. In the event of an explosion,

the electrolyte is sprayed on to the individual who is working on the battery.

Therefore, safety goggles must be worn when working with these batteries.

• Lead is toxic and hence environmental & health problems arise due to careless

disposal by consumers.

• The corrosion of the lead grid at the lead dioxide electrode is one of the primary

causes of lead acid battery failure.

1.6.4 Nickel-Cadmium Cell

31
Construction: NiCad cell consists of a nickel wire gauze electrode grids. The anode grid

consists of spongy cadmium metal and the cathode grid contains the nicked (III) compound

NiO(OH). The electrolyte is a concentrated solution of KOH. It is the electrolyte of choice

because of its compatibility with the various electrodes, good conductivity and low freezing

point temperature (about – 30o C). Anode and cathode are separated by a very thin separator.

The contents are encased as a sealed unit in a steel case.

Figure 1.6.4 Schematic representation of NiCad cell

Working:

Discharging reactions

Anode: Cd(s) + 2OH-(aq) → Cd(OH)2(s) + 2e-

Cathode: 2NiO(OH)(s) + 2H2O + 2e- → 2Ni(OH)2(s) + 2OH-(aq)

___________________________________________________
Cd(s) + 2NiO(OH)(s) + 2H2O → 2 Ni(OH)2(s) + Cd(OH)2(s)
Charging reactions:

Anode: Cd(OH)2(s) + 2e-→ Cd(s) + 2OH-(aq)

Cathode: 2 Ni(OH)2(s) + 2OH-(aq) → 2 NiO(OH)(s) + 2H2O+2e-

____________________________________________________

Overall reaction: 2 Ni(OH)2(s) + Cd(OH)2(s) → 2 NiO(OH)(s) + Cd(s) +2H2O(l)

Explanation: At anode cadmium metal undergoes oxidation from 0 to +2, leaving behind

two electrons for every atom oxidized, as the cell discharges. At cathode nickel is reduced

from the +3 oxidation state (in nickel oxide hydroxide) to +2 (in nickel hydroxide). Note that
32
OH- is not used up as the cell is discharged. Therefore, there is no voltage drop through most

of the useful life of the battery as it discharges. The net reaction can take place until the

active materials are exhausted, during charging process, the cadmium hydroxide is re-

converted into cadmium and the nickelous hydroxide is reconverted to nickeloxide

hydroxide. The overall chemical reaction of the Ni-Cd system may be represented as

Cd + 2 NiO(OH) + 2H2O Cd(OH)2 + 2Ni(OH)2

The cell must be recharged by applying the correct dc charging voltage.

Applications: Nicad cells are available in standard sizes (AA, D, C,F etc.) for use in flash

lights, photoflash units and portable electronic equipment such as radios, micro tape

recorders, calculators, cordless phones, electronic shavers, drills & garden tools. It is also

used in emergency lighting systems, alarm systems, personal audio equipment (walkman type

cassette players), kitchen appliances and other battery powered small tools, toys & games.

Advantages:

➢ Ni-cad batteries can be recharged many times because the solid products of the electrode

reactions adhere to the surface of the electrodes. Normally this battery can withstand up

to 3000 – recharging (longer cycle life)

➢ They maintain nearly constant voltage level throughout their discharge. Note that there

is no change change in the electrolyte composition during the operation.

➢ It can be left unused for long periods of time at any state of charge without any

appreciable damage (i.e. long shelf life).

➢ It can be encased as a sealed unit like the dry cell because gassing will not occur during

nominal discharging or recharging.

33
➢ They possess a longer design life. It can be extended upto 30 years or more if

maintained.

➢ They exhibit good performance ability at low temperatures.

➢ They can be used to produce large instantaneous currents as high as 1000-8000 A for one

second.

Disadvantages:

➢ It poses an environmental pollution hazard due to careless disposal by consumers and

produces health problems (decreases range from asthma to cancer) due to higher toxicity

of metallic cadmium than lead.

➢ Cadmium is a heavy metal and its use increases the weight of batteries, particularly in

larger versions. The energy density is approximately 40 Wh/kg.

➢ Cost of cadmium metal and hence the cost of construction of NiCad batteries is high.

The overall capital cost of these batteries is roughly then higher than that of lead storage

batteries.

➢ The KOH electrolyte used is a corrosive hazardous chemical. It is a poison and if

ingested attacks the throat and stomach linings. Eye contact can result in serve burns and

blindness. Protective clothing and face shields or goggles should be worn while

performing maintenance work.

1.6.5 Lithium ion cells

Lithium metal cannot be used safely in secondary batteries. Hence, various lithium

compounds have been made, which are used in rechargeable batteries, commonly known as

Lithium –Ion Cells. In these type of batteries, a lithiated metal oxide such as LiCoO2,

LiV2O5, LiMn2O4 etc is inserted into the cathode which consists of a layered graphite crystal.

The electrolyte is normally LiPF6, but LiBF4 can also be used as LiPF6 is not corrosion

resistant.

34
Construction:

The anode is a lithium-carbide type intercalate (LixC6). The cathode is a transition metal

oxide MO2 of variable oxidation state (MnO2, CoO2, NiO2) which can intercalate lithium

usually cobalt dioxide, CoO2 is used. The electrolyte is usually inert polar dry ether or

carbonate (diethyl carbonate or propylene carbonate), in which a conductivity salt such as

LiPF6 or LiBF4 is dissolved.

Figure 1.6.5 Schematic diagram of Rechargeable lithium ion battery

Working: Graphite has a layered structure and its electrochemically reduced in an aprotic

organic electrolyte containing lithium salts and lithium in interclated (or doped) between the

layers of graphite to form Lithium-Graphite interclated compound (GIC). Li-GIC undergoes

oxidation leaving an electron.

At anode:

⚫ LixC6 xLi+(solv) + 6C(s) + xe-………………………….(1)

When a negative electrode is discharged, lithium is deinterclated (undoped) from lithiated

graphite and lithium ions dissolve into the elctrolyte. The lithium content in the LiCoO 2

electrode reversibly changes during charge and discharge as indicated in the following

equation:

At cathode:

35
⚫ CoO2(s) + xLi+(solv) + xe- LixCoO2(s)……………….(2)

Net cell reaction:

LixC6(s) + CoO2 Discharge LixCoO2(s) + 6C………………….(3)

Charge
Explanations: It is called as a lithium ion battery to emphasise that it contains no lithium

metal. Both the electrodes are intercalation compounds. The electrode on the left serves as the

anode when the cell discharges. It is a special intercalation compound consisting of a graphite

host into which lithium ions have been electrochemically inserted between the carbon atom

layers. The lithiated graphite is written as LixC6. During the discharge, the lithium ions are

extracted by the half-reaction (1). The electrode that serves as cathode during discharge is

normally cobalt dioxide. The reduction half reaction is cathode during discharge is normally

cobalt dioxide. The reduction half reaction shown in eq.(2), where cobalt undergoes reduction

from IV to III oxidation state. The overall reaction is shown in eq.(3). During discharge the

Li+ ions spontaneously migrate from the lithium graphite anode to the CoO2 cathode

enablingcurrent to flow through the external circuit. When charged, cobalt ions are oxidized

and lithium ions migrate into the graphite, when discharging the battery delivers energy to the

external load and when charging it recieves energy from a d.c. power source. The electrode

that acts as an anode, during discharging becomes a cathode when its charging.

Applications:

• Lithium-ion batteries are most commonly used in applications where one or more of

the advantages (size, weight or energy) outweigh the additional cost, such as mobile

telephones and mobile computing devices.

• Lithium-ion-polymer batteries are used when the battery design matters in a particular

application as different designs are possible (Cylindrical, jelly-roll design, flat

rectangular).

• It is used in current-generation laptops, cellular phones, video-recorders.

36
 • It is also used in portable CD players, televisions and implantable medical devices.

Advantages:

➢ Lithium-ion batteries were designed to overcome the safety problems associated with

the highly reactive properties of Lithium metal.

➢ Long cycle life (400-1200 cycles).

➢ They are smaller, lighter and provide greater energy density than either nickel-

cadmium or nickel-metal-hydride batteries

➢ They can be operated in a wide temperature range and can be recharged before they

are fully charged.

➢ Typically designed to be recharged in the device rather than in an external charger.

➢ The average voltage of a Li-ion battery is equivalent to three Ni-Cd cells.

Disadvantages:

➢ Poor charge retention.

➢ The self discharge rate is about 10% per month.

➢ It prices are high compared to other types of cells commonly used.

1.7 Fuel cells

A fuel cell is a galvanic cell of a special type in which chemical energy contained in a fuel –

oxidant system is converted directly into electrical energy in a continuous electrochemical

process. It is an energy conversion device or electricity producer. The fuel cell has two

electrodes and an electrolyte like a primary cell. The reactants (i.e. fuel + oxidant) are

constantly supplied from outside and the products are removed at the same rate as they are

formed.

Cell: Fuel/ electrode/electrolyte/electrode/oxidant.

Anode: Fuel + oxygen ----------->Oxidation products+ ne-

Cathode: Oxidant + ne- ---------->Reduction products

37
A fuel cell consists of fuel, electrodes, electrolyte, & oxidant. Fuel undergoes oxidation at

the anode and oxidant gets reduced at the cathode. The cell can produce current as long as

the reactants are supplied. Most fuel cells produce low voltages, commonly less than one

volt, So a number of them are connected in series in “fuel batteries.”

Figure 1.7 Fuel cell

Eg:- H2-O2 fuel cell, CH3OH-O2 fuel cell, Solid-oxide fuel cell, Molten carbonate fuel cell

1.7.1 Advantages of fuel cells

• High fuel to electricity conversion efficiency of 70-75 % while a thermal power plant

converts 35-40% chemical energy of coal into electrical energy.

• Fuel cell products do not cause pollution problems such as noise pollution, chemical

pollution and thermal pollution normally associated with conversional power plants.

• Fuel cell power plants can be located near the point of use electricity such as on an

urban location,rather than at a remote place. So transmission and distribution lose

(~30%) could be avoided.

• A fuel cell will produce a steady electric current as long as fresh reactants are

available.

1.7.2 Classification of fuel cells

S. No. Fuel cell type Electrolyte used

38
 1 Polymer electrolyte Polymer membrane

2 Direct methanol Polymer membrane

3. Alkaline Potassium hydroxide

4. Phosphoric acid Phosphoric acid

5. Molten carbonate Lithium/potassium carbonate

6. Solid oxide Yittria stabilized zirconia

1.7.3 Alkaline fuel cell (AFC)

The hydrogen gas is continuously supplied at the anode and pure oxygen gas is continuously

supplied at the cathode form an external reservoir. The cell operates at about 80 oC and the

normal voltage is 1.10 V. At the anode, hydrogen is oxidized to the H+ ions, which are

neutralized by the OH- ions of the electrolyte, forming water and electrons are released. At

the cathode, oxygen and water take electrons to form hydroxide ions. The overall reaction is

equivalent to the combustion of hydrogen. The only product discharge by the cell is water

vapor that escapes through the exhaust point. Note that the gases H2 and O2 diffuse into the

electrode pores and so does the electrolyte solution.

Figure 1.7.3 AFC

Working:

At Anode:

39
 • H2(g) + 2OH-(aq) 2H2O(l) + 2e-

At Cathode:

1
• O2(g) + H2O(l) + 2e- 2OH-(aq)
2

1
Overall: H2 + O2 H2O(l)
2

Advantages: Desirable attributes of the AFC include its excellent performance on hydrogen

(H2) and oxygen (O2) compared to other candidate fuel cells due to its active O2 electrode

kinetics and its flexibility to use a wide range of electro-catalysts.

Disadvantages:

• The sensitivity of the electrolyte to CO2 requires the use of highly pure oxidant and

fuel.

• As a consequence, the use of a reformer would require a highly effective CO and

CO2 removal system.

• If ambient air is used as the oxidant, the CO2 in the air must be removed. While this

is technically not challenging, it has a significant impact on the size and cost of the

system.

Applications: AFC is widely used in US space programs to produce electrical energy and

water onboard spacecraft.

1.7.4 Direct Methanol fuel cell (DMFC)

Construction: Both electrodes are made up of porous nickel plates impregnated with finally-

divided platinum. Methyl alcohol is used as the fuel which is circulated through the anode

chamber. Pure oxygen / air acts as an oxidant and it is passed through the cathode chamber.

Concentrated phosphoric acid, used as electrolyte is placed in the central compartment. The

cell operates at 150-200 oC. At lower temperatures, phosphoric acid is a poor ionic conductor.

At ~200 oC, phosphoric acid polymerizes to pyrophsphoric acid which has higher ionic

40
conductivity. A membrane is inserted adjacent to the cathode on the electrolyte side to

minimize the diffusion of methanol into the cathode. In the absence of a membrane, diffusion

of the dissolved methanol through the electrolyte to cathode takes place and chemical

oxidation of methanol occur forming formaldehyde (CH3OH → HCHO). The emf of the cell

is 1.20 V at 25 oC.

Figure 1.7.4 DEMFC

MeOH is one of the most electro active organic fuels in the low temperature range because (i)

it has a low carbon content (ii) it possesses a readily oxidizable OH group and iii) it is

miscible in all proportions in aqueous electrolytes.

Working:

At anode:

• CH3OH(l) + H2O(l) CO2(g) + 6H+(aq) +6e-

At cathode:

3
• O2 + 6H+(aq) + 6e- 3H2O(l)
2

3
Net reaction: CH3OH(l) + O2(g) CO2(g) + 2H2O(l)
2

Explanation: At the anode methanol from the fuel gas steam is consumed, yielding electrons

to the anode and producing hydrogen ions, which enter the electrolyte. At the cathode,

oxygen combines with electrons (from the cathode) and hydrogen ions (from the electrolyte)

41
to produce water. Water is consumed at the anode and is produced at the cathode. Positive

ions (H+) are transported across the proton exchange membrane to the cathode where they

react with oxygen to produce water. Electrons are transported via an external circuit from

anode to cathode providing power to external devices.The products of the overall reaction

water vapor and carbon dioxide, are removed constantly. The nominal emf of the cell is 1.20

V.

Applications: It is used in military applications and in large scale power production. It has

been used to power television relay stations.

Advantages:

• MeOH can be easily transported stored & dispensed within the current fuel network

because it is a liquid fuel.

• The fuel is very cheap and available in large quantities.

• The only products of combustion are CO2 and H2O which can be removed easily.

• There is no production of NOx gases as the operating temperature is about 150 oC.

• Methanol is stable in contact with the acidic membrane.

Disadvantages:

• The anode reaction has poor electrode kinetics, particularly at lower temperatures.

• The reduction of oxygen at the cathode is also slow.

• The permeability of the current perfluorosulfonic acid membranes to methanol,

allowing a considerable crossover of fuel. This leads to both degradation of

performance, since a mixed potential develops at the cathode and to a deterioration of

the use of fuel.

• Methanol is toxic to humans, causing blindness in low doses and death in larger

amounts.So there are concerns about their proper handling.

42
1.7.5 Proton exchange membrane fuel cell (PEMFC)

Polymer electrolyte membrane fuel cells – also called proton exchange membrane fuel cells –

deliver high power density and offer the advantages of low weight and volume, compared to

other fuel cells. PEM fuel cells use a solid polymer as an electrolyte and porous carbon

electrodes containing a platinum catalyst. They need only hydrogen, oxygen from the air, and

water to operate and do not require corrosive fluids like some fuel cells. Polymer electrolyte

membrane fuel cells operate at relatively low temperatures, around 80 oC (176 oF).

Low temperature operation allows them to start quickly (less warm-up time) and results in

less wear on system components, resulting in better durability. However, it requires that a

noble-metal catalyst (typically platinum) be used to separate the hydrogen’s electrons and

protons, adding to system cost. The platinum catalyst is also extremely sensitive to CO

poisoning, making it necessary to employ an additional reaction to reduce CO in the fuel gas

if the hydrogen is derived from an alcohol or hydrocarbon fuel. This also adds cost.

Developers are currently exploring Pt/Ru catalysts that are more resistant to CO.

Role of Proton conducting membranes:

• The membrane function in two ways: It acts as the electrolyte which provides ionic

communication between the anode and the cathode and also it serves as the separator for

the two-reactant gases.

• Optimized proton and water transport properties of the membrane and proper water

management are crucial for efficient fuel cell operation.

• Dehydration of the membrane reduces the proton conductivity and excess of water can

lead to the flooding of the electrolyte. Both conditions result in poor performance.

• The absence of solution-phase electrolyte in PEF fuel cells, compared to alkaline and

phosphoric acid fuel cells greatly reduces the complexity of the fuel and oxidant flow

controls.

43
• Polymeric electrolyte is carbon dioxide tolerant.

• The most important breakthrough came with the development of perflourinated

membrane by DuPont. From 1966, the membrane requirements were best met by nafion

family of perfluorinated ionomer membranes. Lifetimes over 60,000 hrs have been

achieved at 353 K. Their general formula is

F F F F F F F F F

C C C C C C C C C

F F F F O F F F F

F C F

F C F

F C F

F C F

O=S=O
-
O
+
H

Construction:

Electrolyte:-Ion exchange polymeric membranes. This is an excellent insulator, but an

excellent conductor of H+ ions. The material used, consists of a fluorocarbon polymer

backbone, similar to Teflon, to which sulphonic acid groups are fixed to the polymer and

cannot leak out, but the protons of these groups are free to migrate through the membrane.

Electrodes:-Typical gas diffusion electrodes, made up of porous C impregnated with Pt

catalyst. Noble metal treated carbon fiber paper/cloth which is directly bonded to the polymer

membrane at an elevated temperature and pressure (The catalytic electrode/membrane

configuration is referred to as membrane electrodes assemble, MEA).

Fuel:- Hydrogen

Oxidant:- Air

Catalyst:-Platinum

44
Interconnect:- Carbon or metal

Operating temperature:- 40 – 80 oC.

Charge-carrier:-H+

Electrode:-

Fig.1.7.5.1 schematic of a typical PEMFC electrode, which displays three layers

(i) A Teflonized substrate (typically, carbon cloth)

(ii) A diffusion layer, generally formed by carbon particles of about 0.1 μm size with Teflon.

(iii) An active layer, where Pt catalyst grains are supported on carbon particles (Pt loading is

usually 0.4 mg/cm2or less) with or without Teflon.

Cell reactions and Function of PEMFC:

PEM fuel cells operate at around 80 oC and practical efficiency of 60 %. Power output is in

the range of 5-200 KW. They are ideal for transportation and portable power. Additional

advantages are their high response, small size and low cost. A polymer electrolyte membrane

fuel cell is unusual in that its electrolyte consists of a layer of solid polymer which allows

protons to be transmitted from one fact to the other. Porous carbon is used as the anode and

cathode of the PEMFC, as shown in Fig. It basically requires H2 and O2 as its inputs, though

the oxidant may also be ambient air, and these gases must be humidified. It operates at a low

45
temperature because of the limitations imposed by the thermal properties of the membrane

itself. The operating temperatures are around 90oC and a Pt catalyst is used.

Fig.1.7.5.2 PEMFC

At anode:

• H2(g) 2H+(aq) + 2e-

At cathode

1
• O2(g) + 2H+(aq) + 2e- H2O(l)
2

1
Overall reaction: H2(g) + O(g) H2O(l)
2

Applications:

• PEM fuel cells are used primarily for transportation applications and some stationary

applications.

• Due to their fast startup time, low sensitivity to orientation, and favorable power-to-

weight ratio, PEM fuel cells are particularly suitable for use in passenger vehicles, such as

cars and buses.

Advantages:

The PEMFC has a solid electrolyte which provides excellent resistance to gas crossover.

The PEMFCs low operating temperature allows rapid start-up and, with the absence of

corrosive cell

46
 constituents, the use of the exotic materials required in other fuel cell types, both in

stack construction.

PEMFCs are capable of high current densities of over 2 kW/I and 2 W/cm2.

Disadvantages:

• The low and narrow operating temperature range makes thermal management

difficult, especially at very high current densities, and makes it difficult to use the

rejected heat for cogeneration.

• Optimized proton and water transport properties of the membrane and proper water

management are crucial for efficient fuel cell operation. Dehydration of the membrane

reduces the proton conductivity and excess water can lead to the flooding of the

electrolyte. Both the conditions lead to poor performance.

• Perflourinated membranes have a high cost.

• PEMFCs are quite sensitive to poisoning by trace levels of contaminants including

CO, sulfur species and ammonia.

1.7.6 Differences between the fuel cell and galvanic cell:

Fuel Cell Galvanic Cell

1. They do not store chemical energy They store chemical energy

2. Reactants are fed from outside the cell The reactants from an integral part of its
continuously construction.
3. Need expensive noble metal catalysts & an These special conditions are not required
optimum to an operative for their efficient
functioning.
4. Do not get discharged and no need of Get-discharged when stored – up energy is
charging exhausted.
5. Such cells never become dead as long as Limited life span in use
fresh reactants are available
6. Useful for long-term electricity generation. Useful as portable power services.
7.Reaction products must be continuously No such problem
removed
8. No pollutants are generated (significant Pollutants are generated after their useful
environmental benefits) life
9. Produce power from fuels They cannot generate electricity from fuels
10. Significantly higher power densities Lower power density

47
1.8 Metal finishing

1.8.1 Introduction

Metal objects such as car components, kitchen utensils, juice cans, window frames, railings

and so on which we see in everyday life will have undergone a surface modification, referred

to as finishing. It covers a wide range of processes carried out to modify the surface

properties of a metal. The process involves deposition of a layer of another metal or a

polymer, conversion of a surface layer of atoms into oxide film or any other inorganic

compound film or any process which can finally improve the surface characteristics. Metal

finishing is done by electroplating, electroless plating, grinding wheels and honing, lapping

and burnishing tools to obtain a smooth surface of a component with desired characteristics.

Metal finishing is a process of electro deposition of an adherent metallic film of uniform

thickness on the surface of the substrate for the purpose of modifying its surface properties.

The metal finishing techniques were originally introduced in the industry for improving the

physical appearance of the metal objects by imbibing a decorative appeal. Since then a wide

range of technological developments in the field was taken place for imparting additional

desirable surface properties to the material other than their intrinsic properties to enhance the

utility of the metal. Some of them are

• Improving resistance to corrosion

• Enhancing resistance to chemical attack, abrasion and wear

• Imparting thermal resistance and resistance to impact

• Improving thermal and electrical properties

• Increasing hardness, thermal and optical reflectivity to the surface

• Making the surface resistant for moisture attack

48
1.8.2 Electroplating

The techniques of metal finishing include electroplating of metals and alloys and Electroless

plating of a modified surface. Electroplating is the process by which coating metal is

deposited on the base metal by passing a direct current through an electrolytic solution,

containing the soluble salt of the coating metal. It is primarily used for depositing a layer of

material to bestow a desired property (e.g., abrasion and wear resistance, corrosion protection

and aesthetic qualities) to a surface that otherwise lacks that property and sometimes to build

up thickness on undersized parts. The common metals used for coating purpose are Zn, Cu,

Ni, Cr, Ag, Au and Pt.

1.8.3 Theory of electroplating

Electroplating is the process of coating a metal on a substrate made up of another metal, alloy

or non-metal by the process of electrolysis. The process used in electroplating is called

electrodeposition and the principle is electrolysis. The electroplating device is an electrolytic

cell in which two electrodes (anode and cathode) are dipped in an electrolytic solution. The

part to be plated is the cathode of the circuit. In one technique, the anode is made of the

metal to be plated on the part. Both components are immersed in a solution called an

electrolyte containing one or more dissolved meal salts as well as other ions that permit the

flow of electricity. A rectifier supplies a direct current to the anode, oxidizing the metal

atoms that compromise it and allowing them to dissolve in the solution. At the cathode, the

dissolved metal ions in the electrolyte solution are reduced at the interface between the

solution and the cathode, such that they ‘plate out’ on to the cathode. The rate at which the

anode is dissolved is equal to the rate at which the cathode is plated, ie the current flowing

through the circuit. In this manner, the ions in the electrolyte bath are continuously

replenished by the anode. Other electroplating processes may use an inert anode such as lead

or graphite. In these techniques, ions of the metal to be plated must be periodically

49
replenished to maintain proper coating metal ion concentration in the bath. The device used

for electroplating is an electrolytic cell in the form of a tank having two electrodes immersed

in the electrolyte solution. The schematic representation of various components of the

electroplating unit is shown in Fig. 1.8.3.

Fig. 1.8.3 Schematic of the electroplating bath

Essential components include:

• An electroplating bath containing a conducting salt and the metal to be plated in a soluble

form as well as a buffer and additives.

• The article to be plated - electronically conducting cathode.

• The electronically conducting anode, the coating metal itself, or an inert material of good

electrical conductance like graphite.

• An inert vessel to contain the above mentioned materials made up of either rubber lined

steel, concrete or wood.

Suppose the anode is made of coating metal itself. During electrolysis, the concentration of

the electrolytic bath remains unaltered, since the metal ions deposited from the bath are

replenished continuously by the reaction of free anions with the anode metal. As an example,

if the CuSO4 solution is used as an electrolyte, it ionizes as

CuSO4 → Cu2+ + SO42−

50
On passing current, Cu2+ ions go to the cathode and get deposited there.

• Cu2+ + 2e − → Cu

The free SO42- ions migrate to the copper anode and dissolve an equivalent amount of copper

to form sulfate.

• Cu + SO42- → CuSO4 + 2e

Thus there is a continuous replenishment of electrolytic salt during electrolysis. If however,

the anode is made of some inert material like graphite, then electrolytic salt is added

continuously in order to maintain proper coating metal ion concentration in the bath.

Moreover the process of electroplating goes on nonstop, since the anode is not consumed and

its replacement is not required. The process involves the passage of current and electrolysis

of conducting media. Three important factors governing the electroplating process include

decomposition potential (ED), polarization and overvoltage.

1.8.3.1 Decomposition Potential (ED):

When an electric current is passed through the electrolyte solution the electrolysis starts and

the products formed, gather around the electrodes. Concentration in the vicinity of the

electrodes changes and a back emf sets in. e.g., in the electrolysis of water, if a small voltage

(~ 0.75V) is applied between two platinum electrodes immersed in the 1M sulphuric acid

solution, the electrolysis starts, proceeds to some extent and then decreases rapidly finally to

stop. The reason for this observation is the initial passage of current causing release of a

small amount of hydrogen and oxygen at the cathode and anode respectively. The gases are

adsorbed at the surface of electrodes and the inactive platinum electrode is converted into

active gas electrodes. This produces a back emf of the polarization current, which resists the

emf of the battery or applied voltage. At potential below 1.7V the back emf counterbalance

the effect of applied emf and the process of electrolysis is not sustained. If the applied voltage

is slowly increased, there is a slight increase in the current until the applied voltage just

51
exceeds the back emf (1.7 V), the current suddenly increases appreciably at that point. Thus,

the minimum external potential or voltage, at which the electrolysis current begins to increase

appreciably and continuous electrolysis sets in is known as decomposition potential of the

electrolyte. It is equal to back emf.

Measurement of decomposition potential (ED):

The schematic diagram for the determination of decomposition potential is shown in

Fig.1.8.4.1a The electrolytic cell consists of two platinum electrodes (E1 and E2) dipped in

the electrolytic solution. The applied voltage (V) is measured at different resistance and the

corresponding current is measured with the help of milliammeter (M).

Fig. 1.8.3.1a Setup for measurement of decomposition potential

A series of readings for current passing through the electrolyte cell at corresponding applied

voltage is recorded and a graph is plotted to measure the electrode potential. A graph

between applied emf and the current density is shown in the following Fig.1.8.3.1b

52
Fig. 1.8.3.1b A graph of external voltage applied vs current density

The linear portions of the graph are extended, until they intersect. Voltage corresponding to

the point of intersection is the ED of the electrolyte.

Factors influencing decomposition potential:

Decomposition potentials of different electrolytes are different. Even the ED of an electrolyte

is not a constant. It depends upon the following factors;

• Strength of the current flowing through the cell

• Chemical nature of the electrodes

• Physical nature of the electrodes

• Activity of the electrolyte

• Absolute temperature.

Use of decomposition potential values:

• Knowledge of ED value enables the calculation of actual emf which is required for setting

in continuous electrolytic processes, electroplating and electrorefining.

• It helps in predicting the sequence of discharge process to occur.

• Used in the separation of a mixture of metal ions from a solution by electrolysis.

1.8.3.2 Overvoltage

The decomposition potential of an electrolyte is approximately equal to the emf of the

galvanic cell formed due to the discharge of products at the electrodes. The decomposition of

an electrolyte is therefore expected to start as soon as applied potential reaches the value of

reversible emf of the cell. This is true with respect to metal ions. But when products

discharged at the electrodes are gases, then the actual decomposition potential is invariably

much higher than its theoretical reversible electrode potential. The excess voltage is referred

to as overvoltage (η) of the gas. It may occur at both the electrodes.

53
Overvoltage (η) is the difference between the actual applied emf to bring about continuous

electrolysis and the theoretical emf needed for such electrolysis. For instance, the reversible

potential of oxygen gas with smooth Pt electrode is 1.23 V. But actual gas evolution takes

place at a potential of 1.68 V. The excess 0.45 V is the overvoltage of oxygen on smooth Pt

surface. The following factors influence the overvoltage of an electrolyte;

• Nature of the electrode surface (or material)

• Current density and temperature

• Nature of the electrolyte

Overvoltage is believed to be a surface phenomenon at the electrodes. Of the many steps

involved in gas evolution at electrodes, at least one is rather a slow process and requires

energy. The extra energy is supplied by the applied voltage and this extra energy is related to

overvoltage.

e.g., electrolysis of water

(i) H+ (aq.) + e- H (fast)

(ii) H + H H2 (slow)

The step (ii) being slow, consumes energy and accounts for overvoltage. Hydrogen

overvoltage is the measure of the tendency of hydrogen to be liberated at the cathode. Higher

the value of overvoltage more difficult is the liberation of hydrogen on that metal.

1.8.3.3 Polarization

Since the electrolysis is a non spontaneous process, the minimum energy required to carry out

such a process is equal to the free energy increase accompanying the change. However, in

irreversible conditions, the potential to be applied for electrolysis is higher than the reversible

emf of the cell. A cell that requires excess voltage over the theoretical is said to be polarized

and the phenomenon is referred to as polarization. Electrolytic processes occur at the

electrodes of the cell. Polarization sets in the cell when the electrode processes become slow

54
and irreversible. Thus polarization in the cell is due to polarization at the electrodes.

Magnitude of overpotential is directly proportional to the extent of polarization. The observed

polarizations are of two types.

(a) Concentration polarization (b) Kinetic polarization

Concentration polarization:

An electrochemical reaction occurs only at the surface of the two electrodes. Reactant

concentration decreases in the electrolyte adjacent to the electrode surface. The reactant

species are transported to the electrode surface by processes like diffusion, migration and

convection from the bulk of the solution. When the rate of transport is insufficient to match

the rate of electrode reaction, current flowing through the cell drops. A higher potential than

the theoretical value is required to maintain the current at the necessary level. This

phenomenon is called concentration polarization. The steps involved in electrolytic processes

are

(i) Diffusion of reactant species towards the electrode and

(ii) Diffusion of product away from the electrode, cause concentration polarization.

Concentration polarization can be eliminated or at least minimized by increasing the

convection, by raising the temperature or mechanical agitation of the solution.

Kinetic or Activation polarization:

Activation polarization is caused when steps

i) Adsorption of the reactant on the electrode

ii) Charge transfer across the metal-solution interface and

iii) Desorption of the product from the electrode become slow and need activation

energy.

A higher potential than the theoretical value is to be applied to maintain current at the

necessary level. It is not possible to eliminate or minimize kinetic polarization by any means.

55
Activation polarization is normally very low, when metal deposition or metal dissolution is

the electrode process. When the electrode process is a gas (H2 and O2) evolution, kinetic or

activation polarization is usually very high.

Factors influencing polarization:

• Size and nature of the electrode

• Nature of ions accumulated on electrodes

• Electrolytic concentration

• Temperature

• Conductivity of electrolytic solution

• Stirring of electrolytic solution

• Use of depolarizer

Importance of polarization effect:

An impervious or non-porous film, contributes to the increase of polarization at an electrode.

Considerable polarization effect can also be seen where loosely adhering and even porous

films are formed. Such films either formed naturally (during manufacturing) or artificially

(by the application of special coatings or products of corrosion) are important in determining

the rate of corrosion of a metal or an alloy and also for the protection form corrosion.

1.8.4 Applications of electroplating

• Plating for aesthetic appearance:

• Plating for protection

• For electroforming

• Plating on non-metals

1.8.5 Characteristics of a good deposit

56
 ▪ The deposit should be bright and lustrous

▪ The deposit should be continuous, uniform, non porous and adhesive

▪ It should be hard and ductile

▪ It should be of fine grained nature

1.8.6 Factors influencing the nature of the deposit

There are several factors which affect the nature of an electro deposit.

(a) Current density

Higher the current density, more the deposition rate but will enforce the poor adhesion

and loose and brittle plating quality. There is the possibility of a burnt and spongy deposit.

Whereas low current density takes extra time to finish the job and is uneconomical.

Therefore, optimum moderate current densities should be applied.

(b) Metal ion concentration

As the electroplating involves the discharge of free metal ions, the concentration of free metal

ions plays an important role. If the concentration of metal ion is low the crystal size will be

smaller and a fine adherent film may be coated. Thus the ideal situation is low free metal ion

concentration in a concentrated solution of a metal compound which can be attained by

addition of a compound with a common ion or by the formation of complex compound and

ions. e.g., when copper is deposited from an electroplating bath containing copper sulphate

solution, sulphuric acid is added to increase the concentration of sulphate ion. The

concentration of cupric ions is reduced due to common ion effect.

(c) Temperature:

Generally, the solution to be deposited is used at room temperature. However, warm baths

are used for increasing solubility of electrolyte and current density. The size of the crystals

increases with increasing temperature and renders lower adherence. But on the other hand

57
the solubility and metal dissociation increase at higher temperature leading to the higher

conductance of the solution. Also, the mobility of ions increases at a higher temperature and

decreases the viscosity of the electrolyte solution so that the cathode film is replenished at a

faster rate. This increases the current density for a given voltage and reduces the tendency

towards treeing. There are disadvantages also of using high temperatures. Since, the

possibility of corrosion of equipment, decomposition of the organic addition agent and

evolution of hydrogen gas at cathode would increase at a higher temperature. So the

optimum range of temperature needs to be selected.

(d) pH of the electrolyte

The pH of the electrolyte solution should be properly maintained. The range of the pH varies

for different types of the plating bath. If pH is more towards the acidic side the nature of the

deposit will be affected adversely as the evolution of hydrogen gas is expected at cathode

thereby forming a burnt deposit. If pH is more towards the basic side the plating is delayed,

so uneven and thick deposit is obtained. Suitable buffers may be used for maintaining the

appropriate pH.

(e) Presence of additives:

To obtain electroplate with desire qualities and specifications, additional substances called

additives are added in small quantities to the electrolyte bath. These additives have the

capacity to modify the structure, appearance and characteristics of the deposit. The different

types of additives used are

(i) Complexing agents:

(ii) Brighteners:

(iii) Levellers:

(iv) Wetting agents:

(v) Structure modifiers:

58
(f) Throwing power of the plating bath

Throwing power is defined as the degree of uniformity of metal distribution or evenness of

deposit thickness obtained on a cathode of irregular shape. If the distribution of the deposit is

uniform throughout the surface of the article to be coated, the throwing power is considered

good.

1.8.7 Methods of cleaning the metal surface

It is essential to clean the surface of base metal before the application of the electroplated

coating. The common impurities found on the metal surface are grease, oil, oxide layer and

other extraneous matters. The following methods are employed to clean the metal surfaces.

(iii) Physical (Solvent) cleaning:- Physical cleaning is done with the help of solvents to

make the surface free from oil, grease, superficial dirt, and buffing, polishing and fatty

substances. The commonly used solvents such as chlorinated hydrocarbons, xylene, toluene,

aqueous cleaning agents are used with or without electric current. Solvent cleaning is made

more effective by vapour degreasing. An organic volatile solvent like trichloroethene is

heated and vapours are passed over the metal surface to be cleaned. The vapours condense

on the surface and condensed liquid dissolves and washes away the oil, grease and other

organic matter from the surface. The emulsifying agents are also added to the solvent to

remove organic impurities from the surface of the metal.

(ii) Chemical (Alkali) Cleaning: It is used to remove the minute residue of soil and grease

and for removal of tarnish and oxide film. The commonly used alkali cleaners consist of a

number of alkalies, soap, chelating agents like Na2O3, sodium phosphates, NaOH etc. Alkali

cleaning is made more effective by passing current through a hot alkaline solution, with the

article to be cleaned constituting the cathode. The evolution of H2 at the cathode and O2 at the

anode, metal helps to dislodge the greasy substance. It is followed by thorough rinsing with

59
water and then immersing in a very dilute solution of acids to remove traces of alkali after

cleaning is completed.

(iii) Mechanical Cleaning: Involves removal of the oxide layer (tarnish), loose rust and other

inorganic deposits from the surface to obtain better appearance, protection and optimum

effects. This is done by hand cleaning with bristle brush and some abrasives like sand papers,

polishing tools (grinding with grinding stone), scratch rubbing with chisel, knife, scrapers,

wire brush or a abrasive stone or paper and detergent.

(iv) Pickling: The oxides sometimes cannot be removed by simple alkali or mechanical

cleaning. The extraneous fragments like heavy scales of oxides, scratches and strains can be

removed from the surface by dissolving in the acid solution. The acid pickling involves the

removal of such oxides; rust or tarnish by immersing the material (except Al) in acid like dil.

HCl or dil.H2SO4 or dil. HNO3. Pickling of Al is done in alkaline solution, whereas pickling

of Cu, Ni or brass articles are accomplished in a solution of dil. HNO3 or a mixture of dil.

HNO3 and dil. H2SO4. Pickling is usually followed by polishing and buffing.

(v) Electro polishing :- In this method, the metal to be cleaned is made anode in a suitable

solution. During the process, a surface layer of the metal gets dissolved along with the

impurities. It also helps to remove minor surface irregularities. The most commonly used

baths for electro polishing contain sulphuric acid, phosphoric acid, chromic acid, nitric acid

etc. After the process, the metal is thoroughly rinsed with water, dried and used for

electroplating.

1.8.8 Electroplating of chromium

Chromium plating is a finishing treatment utilizing the electrodeposition of a thin layer of

chromium on a metal object. This layer can be decorative or corrosion protective to the base

surface. The process of chromium plating includes degreasing to remove heavy soiling,

manual cleaning to remove all residual traces of dirt and surface contamination and various

60
pretreatments depending on the objectives of the coating. Different etching solutions such as

hydrochloric, hydrofluoric, sulphuric acid and ferric chloride are used. Further, the treated

base material is placed into the chrome plating bath for electroplating of desired thickness.

• Chromium coatings are generally thinner and have micro pores in it. As the thickness of

the coating increases, cracks develop in the coatings. Hence, chromium coatings are

always plated on nickel/copper undercoates. Ni gives protection and chromium gives a

decorative finish.

• Chromium anodes are not used in electroplating of chromium on account of two

difficulties. These electrodes become passive in acidic medium and they result in a black

deposit.

• Chromium has higher electrode potential and can be easily coated on the iron to protect

from rusting/corrosion

• The anode efficiency is nearly 100 % whereas cathode efficiency is at best around 20 %.

It may be inferred that metal going into the solution is five times of the metal getting

deposited, resulting in building up of excessive chromic acid concentration. This disturbs

the ratio of Cr(III) to Cr(VI) and the conductivity of the bath and dull deposits called

burnt deposits are obtained. To avoid this, inert material is used as anode and chromium

electrolyte in the bath.

Table 1.8.8 Comparison of decorative and hard coating of chromium

Decorative coating Hard coating

Bath Chromic acid (250 g) + Chromic acid (250 g) +
composition H2SO4 (2.5 g) + H2SO4 (2.5 g) +
Trivalent chromium (1g) Trivalent chromium (1
g)
Operating 45 – 55 °C 45 – 55 °C
Temperature
Anode Insoluble anodes like Lead – lead : 6%
Pb – Pb : 6% Sb – Pb: 7%
Sb - Pb--7% Sn
61
 Sn
Cathode Article to be coated Article to be coated
Current density 145--430 A/ft2 290--580 A/ft2
Cathode 10 – 15 17 – 21
efficiency
Applications Decorative applications with Coating of industrial
corrosion resistance finish on components like gauges,
cycles, automobiles, dies, cutting tools,
furniture, household fittings, piston rings and
aircraft, surgical and dental hydraulic rams.
instruments.

1.8.9 Electroless plating

Electroless plating is a method of depositing a metal film on a substrate surface (conductor or

non-conductor) from metal salt solution using a suitable reducing agent without using

electrical energy. The reaction can be depicted as

Metal ions + Reducing agent Metal + Oxidized product

The method involves the deposition of metals such as Cu, Ag, Ni, Au or Pd on the surface of

the base material by means of a reducing agent. Electroless plating results in a fine grained

metal deposit that has similar finishing as that of traditional electrodeposit finishing. In

industries, such process is used for plating on non-conductors like plastic, electroformed dies,

hard memory disks, printed circuit boards (PCBs) or to obtain an extremely uniform plate.

This technique is also used for the prevention of corrosion.

Process of electroless plating: The process of electroless plating involves the following

steps:

(i) Preparation of active surface: This is the most important step and the surface is activated by

any of the following ways.

(a) etching – by acid treatment

62
(b) electroplating with a thin layer of metal or insulators like plastic surfaces followed by heat

treatment

(c) Alternate treatment with SnCl2 and PdCl2 on the plastic surface

SnCl2 + PdCl2 Pd + SnCl4

Pd is coated on plastic.

(ii) Preparation of plating bath:

(a) Metal to be coated in the form of chloride or sulphate solution

(b) Reducing agents like formaldehyde and sodium hypophosphate for reduction of metal ion

to metal

(c) Complexing agents like EDTA, tartrates, citrates to form metal complexes to prevent

excess deposition

(d) Stabilizers like thiourea, calcium ions too prevent decomposition of the bath and to impart

stability to the solution

(e) Exaltants (accelerators) like succinates, glycinates and fluorides to increase the rate of

plating

(f) Brighteners like thiosulphate to give a lustrous appearance

(g) Buffers like boric acid to maintain the pH

(iii) Reduction step: Active surface is dipped in the bath and deposition is carried out. The

plating is carried out in a series of tanks where the object is immersed to plate the desired

metal. The rate of deposition is controlled by the amount of reducing agent present and the

type of chelating agent used. The deposition rate is normally 12.5 – 25 µm, although, it has

been done up to 650 µm in thickness.

Advantages of electroless plating

The following are main advantages of electroless plating

63
 • More uniform coating on the surface of object whatever shape it may have. Even the

objects having irregular shapes, holes, recesses, internal surfaces, valves or threaded

parts get uniform deposit since it has better throwing power than electroplating.

• Electrical power and other accessories are not required.

• Coating is harder than regular plating and better wear resistance.

• Deposits have compatible wettability for oils, inherent lubricity and non-galling

characteristics, unlike electrolytic nickel.

• Deposits are much superior to electroplated nickel and hard chrome, as they are less

porous and provide better corrosion protection to steel substrates.

• Electroless plating of Ni on aluminum substrate enhances the solderability together

with providing a non-magnetic under lay in magnetic components. The deposits are

less porous and possess unique characteristic chemical, mechanical and magnetic

properties.

• Additives or levelers are not required in the process nor the complex filtaration

method requirement.

• It is a simple process, so requires simple equipment.

Disadvantages of electroless plating

The main disadvantages of the process are the following;

• Due to speedy chemical renewal, cost of waste treatment is high.

• The frequency of dumping electroless bath is high as it is sensitive to contamination

• Costs per unit weight of the deposited metal are more.

• It needs pure chemicals.

• Chemical reductants are more expensive than electricity.

• Metal salts and reductant used in electroless plating solutions are thermodynamically

not stable.

64
 • Impurities or dust or colloidal matter (even if present in trace amount) promote the

decomposition of bath components.

1.8.9.1 Electroless plating of Copper

It is an auto-catalytic reaction used to deposit a coating of electroless copper on a substrate

without the use of electrical energy. It is commonly used to plate plastic for decorative

purposes and parts for engineering applications, particularly to render conductivity for

electronic and printed circuit boards.

Reducing agents generally react with the plating bath, resulting in slow, deposition rates and

poor deposit quality. It can be prevented by rejuvenating the bath at regular intervals. The

bath solution undergoes spontaneous decomposition, resulting in an additional waste stream

of copper and etching solution as copper built up on the tanks from the bath solution, must be

stripped with an etchant such as sulphuric acid and hydrogen peroxide.

Electroless plating bath for copper includes;

• Coating solution : CuSO4 soln

• Reducing agent : HCHO

• Buffer: NaOH & Rochelle salt

• Complexing agent: EDTA di sodium salt

• Optimum pH: 11

• Optimum temperature: 25 °C

The reactions involved at two electrodes are

At cathode:

• Cu2+ (aq) + 2e- Cu (S)

At anode:

• 2HCHO + 4OH-(aq.) 2HCOO-(aq.) + 2H2O(l) + H2(g) + 2e-

Overall reaction:

65
 Cu2+(aq.) + 2HCHO + 4OH-(aq.) 2HCOO-(aq.) + 2H2O(l) + H2(g)

Since Cu2+ ions and HCHO are consumed during the redox reaction, these are replenished

periodically. The redox reaction involves consumption of hydroxyl ions and pH of the

solution decreases as the reaction progresses. Hence addition of buffer is essential. Usual

plating rate is 1-5 µmh-1.

Applications of electroless plating:

• Electroless copper plating is widely used for metalizing printed circuit boards (PCBs)

• It is used as a base coating for subsequent conventional electroplating

• It is used for producing through hole connections and for decorative plating on

plastics. When double sided PCBs are fabricated then holes are drilled for making

electrical connections. These holes are plated by electroless plating.

1.8.10 Comparison of electroplating and electroless plating

Table 1.8.9 Comparison of electroplating and electroless plating

Property Electroplating Electroless plating

Driving force Electric current Autocatalytic redox
reaction
Anode reaction
Cathode Article to be plated Article to be plated with a
catalytic surface
Anode Separate anode Article to be plated
Reducing agent Electrons bring about Chemical reagents bring
about reduction reaction
Anode reactant M or H2O R, the reducing agent in
solution
Nature of deposit Pure metal or alloy Usually metal
contaminated with species
derived from the redox
reaction
Thickness limit 1 - 100 1 – 100
(µm)
Applicability Applicable to Can be used for conductors
conductors only and non-conductors

66
Throwing power Less throwing power; More throwing power and
cannot be used for can be used for irregular
irregular shapes and and uneven shaped objects
intricate parts

67
 3: CORROSION AND ITS CONTROL
Introduction, Importance of corrosion study, Corrosion classification, Electro chemical theory
with special reference to rusting of iron. Galvanic series: need, characteristics, advantage. Factors
affecting corrosion: Primary and Secondary factors. Brief account of galvanic corrosion, pitting
corrosion, intergranular corrosion and stress corrosion. Corrosion control by material selection
and proper design. Corrosion control by use of inhibitors, Cathodic protection of metals, Anodic
protection and metal coating, Corrosion control by organic (paint) and inorganic (phosphate)
coatings.
Learning Objectives:
1. Unfold the practical aspects of metal corrosion with real life examples.
2. Be able to describe the mechanism of corrosion by electrochemical theory
3. Describe different forms of corrosion- galvanic, pitting, inter-granular and stress
corrosion
4. Demonstrate an understanding of the importance of the factors affecting corrosion
5. Know about the different established and modern techniques to control corrosion such
as anodic/cathodic protection methods, organic /inorganic coatings
6. Distinguish between dry/wet corrosion, galvanizing/ tinning, electrochemical series/
galvanic series and organic/inorganic coating
1. INTRODUCTION
Various types of metals are used in residential and commercial structures, in bridges, in
automobiles, passenger trains, railroad cars, ships, in pipelines and storage tanks. In addition,
metals are also used in various electronic applications such as printed circuit, computer discs,
connectors and switches. Metals also find use as coins of daily commerce, in jewellery, in
historical landmarks and in objects of arts. Some metals find application in human body as
replacements, as stents, as surgical plates, screws and wires. Whatever be their end use all
common metals tend to react with their environments to different extents and at different rates.
Thus, Corrosion is a natural phenomenon and is the destructive attack of a metal by its
environment so as to cause a deterioration of the properties of the metal.
Corrosion can be defined as spontaneous destruction or deterioration of a metal or alloys
by the surrounding environment because of chemical or electrochemical interaction. Free

1
metals, as such are unstable and whenever favourable situation arises they combine with other
elements like oxygen and form the compounds of minimum energy and maximum stability.
Hence corrosion can be viewed as the reverse process of extractive metallurgy. This
phenomenon is schematically represented in Figure 1

Figure 1: Corrosion as reversal of metallurgy

4Fe(s) + 3O2 (g) →2Fe2O3(s) (rust) , Fe2O3 (s) + 3 CO →2Fe(s) + 3 CO2 (g)
Three most common examples of corrosion include rusting of iron objects forming
reddish brown scale, tarnishing of silver in contact with traces of H2S or SO2 in the atmosphere
or eggs rich in sulfur compounds and formation of green scales on copper vessels. The process
and the products formed in these reactions are described in the following equations.
Rusting of iron 4Fe(s) + 3O2(g) → 2Fe2O3.H2O(s)
Tarnishing of silver 4Ag(s) +2 H2S(g) + O2(g) → 2Ag2S(s) + 2H2O(l)
Scales on copper 2Cu(s) + H2O(l) + O2(g) + CO2(g) →Cu2(OH)2CO3(s)

1.1 Importance of corrosion study

The study of corrosion is an interdisciplinary area embracing chemistry, material science and
mechanics. Four reasons to study corrosion as science and engineering subjects are:
Human life and safety: Loss of life results due to combined effects of stress and corrosion when
structures collapse. Safety issue can be due to the build up of certain toxic product due to
corrosion, sudden failure of equipment may cause fire or explosion.
Cost of corrosion: The annual losses due to corrosion are approximately 3-4% of GDP in many
advanced countries and it is even more in developing countries.
2
Conservation of materials: Corrosion destroys metals by converting them into corrosion
products. Thus corrosion affects the supply of the earth’s meterial resources.
Academic interest: The study of corrosion is in itself a challenging and interesting as corrosion
science is an interdisciplinary area involving chemistry, materials science and mechanics. A
blend of these must be included to understand the various forms of corrosion.
1.2 Economic considerations of corrosion
Corrosion consumes 3-5% of the Gross National Product of that particular nation.
Corrosion costs could be divided into direct and indirect costs. The direct losses include inability
to use otherwise desirable materials, overdesign to allow for corrosion, the cost of repair or
replacement of corroded component, cost of anticorrosive painting or other protection methods.
Indirect losses may be either economic or social. These may include shutdown of power plants
and manufacturing plants, loss of product due to leakage, contamination of product, loss of
production and safety issues. In addition to direct costs in dollars, corrosion is serious problem
because it definitely contributes to the depletion of our natural resources. The rapid
industrialization of many countries indicates that the competition for and the price of metal
resources will increase.
1.3 Corrosion science versus corrosion engineering
Corrosion science is directed towards gaining basic scientific knowledge to understand
corrosion mechanisms. Corrosion engineering involves the use of accumulated scientific
knowledge to corrosion protection and prevention. Corrosion science and corrosion engineering
complement and reinforce each other. Understanding of corrosion mechanisms can lead to
possible new corrosion-resistant alloys, better surface treatments, and improved corrosion control
measures. Understanding of corrosion engineering aspects will trigger the interest in doing
research in finding out actual mechanisms involved in the process.
1.4 Consequences of corrosion
• Maintenance and operating costs: One fourth of the iron produced is used to replace
bridges, buildings and other structures that have been destroyed by corrosion. The
corrosion causes damage to chemical process plants and other equipment.
• Plant shutdowns, loss of production while the plant is inoperable during
repairs/replacement work.

3
 • Contamination and loss of valuable products- Leaking containers, tanks, pipelines results
in significant losses in product, which have a high cost. Soluble corrosion products can
spoil and contaminate chemical preparations.
• Effects on safety- The contaminated products when dumped cause environmental
pollution problems.
• Loss in aesthetic value- Reduced value of goods due to degraded appearance
• Loss of technically important surface properties such as friction, surface reflectivity, heat
transfer and electrical conductivity.
• Loss of efficiency- the corrosion products decreases the heat transfer rate in heat
exchangers
2. 0 CORROSION CLASSIFICATION
Two different types of corrosion are
* Dry or Chemical Corrosion and Wet or Electrochemical Corrosion
2.1 Dry or Chemical corrosion
This type of corrosion occurs by direct chemical reactions between the environment and
the metals and alloys. Presence of an electrolyte/conducting medium is not at all essential for this
type of corrosion to occur. Therefore this kind of corrosion is also known as dry corrosion.
Depending upon the nature of the corrosive environment, dry corrosion may be further classified
into three types.
(i) Oxidation corrosion: It occurs when metals are attacked by dry oxygen (absence of moisture)
at extreme conditions like low or high temperature. The direct oxidation of metals takes place
according to the following reaction scheme:
2M → 2Mn+ + ne−
nO2 + 2ne− → 2nO2−
2M + nO2 → 2Mn+ 2nO2−
In general: Metal + Oxygen→ Metal oxide (corrosion product)
When the oxidation starts, a thin layer of oxide is formed on the metal surface. Nature of this
film decides the further corrosion process. If a stable film is formed, it behaves as protective
coating and, thereby it shields the metal surface from corrosive environment. Consequently,
further oxidation of metal is prevented. eg: Al, Sn, Pb, Cu and Pt. Unstable metal film
decomposes back into the metal and oxygen. Hence oxidation corrosion is not possible in such

4
cases: e.g. Ag, Au, and Pt. In some cases, oxide film layer volatilizes as soon as it is formed,
thereby accelerating the corrosion. e.g: MoO3.
(ii) Corrosion by other gases : It is due to some gases SO2, Cl2, CO2, and H2S, depends mainly on
the chemical affinity between the metal and the gas involved. For example, dry Cl 2 attacks silver
metal and forms AgCl as a thin protective and non-porous layer on the metal. As a result of this
protective layer on the metal surface, the intensity of corrosion decreases.
(iii) Liquid metal corrosion : It occurs when a molten liquid is continuously passed on a solid
metal surface or on alloy. This behaviour may be either due to the dissolution of the molten
liquid or due to penetration of the molten liquid into the metal phase.

2.2 Wet or Electrochemical corrosion

Wet corrosion occurs due to the existence of separate anodic and catholic areas, between
which current flows through the conducting solution. It involves flow of electron current between
the anodic and cathodic areas through electronic conductor. This type of corrosion can be
observed when
(a) A metal is in contact with an acid solution and
(b) Dissimilar metals are dipped partially in a corrosive environment.
2.2.1 Electrochemical theory of corrosion
Corrosion usually occurs not by direct chemical reaction of a metal with its
environment but rather through the operation of coupled electrochemical half-cell reaction.
According to electrochemical theory of corrosion, when a metal is exposed to corrosive
environment, the process of corrosion sets in by the formation of a large number of ‘anodic’ and
the ‘cathodic’ areas on the metal surface (microgalvanic cells). A driving force is necessary for
electrons to flow between the anodic areas to the cathodic areas. This driving force is the
difference in potential between anodic and cathodic areas. This difference exists because
oxidation and reduction reaction has associated with it a potential determined by the tendency of
specific elements for the reaction to take place spontaneously. This electrode potential is a
measure of the tendency of a metal to undergo oxidation or reduction reactions. Corrosion
always occurs at the ‘anodic area’ of the metal due to oxidation process and thus electrons
are liberated.
Anodic reaction:

5
M → Mn+ + ne−
Fe → Fe2+ + 2e−
Al → Al 3+ + 3e−
Cathodic reactions
The electrons set free at the anodic area flow through and are consumed at the cathodic area by
following processes:
i) Hydrogen evolution:
2H+ (aq) + 2e− → H2 (deaerated and acidic medium)
(ii) H2 liberation along with OH− ions formation
2H2O + 2e− → H2 (g) + 2OH− (aq) (deaerated and neutral)
Reduction of oxygen in neutral medium:
(iii) O2 (aq) + 2H2O + 4e− → 4OH−(aq) (aerated and neutral)
In addition to the above mentioned cathodic reactions, following reactions may also occur at
cathodic region.
iv) Metal ion reduction:
Mn+ + (n-1) e−→ M(n – 1)
iv) Metal deposition:
Mn+ + ne− → M
Oxygen reduction is the most common cathode reaction since any aqueous solution in
contact with air contains dissolved oxygen. Hydrogen evolution occurs in acidic media. Metal
ion reduction and metal deposition are rare. Schematic representation of the electrochemical
theory of corrosion is shown in Figure 2.

Figure 2: Schematic representation of electrochemical corrosion.

6
Figure 2 illustrates the four conditions which are necessary for electrochemical corrosion to
occur.
These are: (i) An anodic reaction,
(ii) A cathodic reaction,
(iii) A metallic path of contact between anodic and cathodic sites (electronic
conduction)
(iv) A solution which contains dissolved ions capable of conducting a current
(electrolytic conduction)
From, electrochemical theory, it must be clear that no corrosion take place at the cathodic area
since cathodic reaction does not involve metal dissolution. Corrosion and hence metal dissolution
takes place only at the anodic area. Cathodic area stimulates corrosion of the anodic part by
utilizing the electrons produced at the anodic area.
2.2.2 Mechanism of rusting: Rusting is the name more commonly referred for the corrosion of
iron. When iron is exposed to an atmosphere, in the presence of moisture, it undergoes corrosion.
Depending upon the concentration of oxygen present in the environment different types of
corrosion products are produced. Figure 3 illustrates the rusting process of iron.

Figure 3: Schematic representation of rusting of iron

At anodic area, iron undergoes oxidation and produces Fe2+, by liberating electrons. The
liberated electrons will migrate towards cathode causing corrosion current. The Fe2+ ions formed
at the anode combine with OH− liberated at the cathode to form the corrosion product (ferrous
hydroxide) somewhere between the anode and cathode, after diffusing towards each other
through the conducting medium.
At anodic sites; [Fe → Fe 2+ + 2e−] x 2
At cathodic sites; O2 (g) + 2H2O (l) + 4e− → 4OH−(aq)
Overall reaction; 2Fe + O2 (g) +2H2O (l) → 2Fe2+ (aq)+ 2OH−(aq)

7
Reactions to the formation of hydrated ferric oxide (rust)
Fe2+(aq) + 2OH− (aq) → Fe (OH)2
In the presence of enough oxygen, ferrous hydroxide reacts with moisture and oxygen to give
yellow rust.
4 Fe (OH)2 + 2 H2O + O2 → 2 [ Fe2O3. 3H2O] ( Yellow rust)
If the supply of oxygen is limited, the corrosion product may be black anhydrous magnetite.
6 Fe (OH)2 + O2 → 2 [ Fe3O4. 3H2O] ( Black Rust)
Rust is a brittle substance that easily flakes off the surface to expose more iron atoms, and the
process starts over again. It is too porous to shield the underlying metal from further oxidation.
2.2.3 Differences between dry corrosion and wet corrosion
Dry Corrosion Wet Corrosion
Involves direct attack of atmospheric Occurs due to the existence of separate
gases anodic and cathodic areas between which
current flows through the medium
Do not need a corrosive medium Needs corrosive medium
Types include oxidation corrosion, Types include galvanic, pitting, stress and
liquid metal corrosion and corrosion by intergranular
gases
Less prevailing More common

3 GALVANIC SERIES
The galvanic series is an ordered listing of experimentally measured corrosion potentials of
metals and alloys in natural seawater. They are arranged in the order of their corrosion
tendencies/corrosion resistance.
3.1 Need for galvanic series
1. In the electrochemical (EMF) series a metal high in the series is more anodic and undergoes
corrosion faster than the metal below it. For example, Li corrodes faster than Mg, Zn
corrodes faster than Fe and so on. However, some exceptions to this generalization are
known. In Zn-Al couple, Zn (below Al in the electrochemical series) is corroded; while
aluminum acts as cathodic is protected. These observations, exactly opposite to that
predicted by the EMF series are because metals like Al and Ti develop strongly adhering

8
 oxide layers on their surfaces. The electrochemical series does not take passivity into
account.
2. The electrochemical series does not account for corrosion behavior of alloys. The
electrochemical series lists Eo values of pure metals. But engineering applications involve
many alloys under various circumstances. Consequently, a more practical series called
galvanic series has been prepared by studying corrosion of metals and alloys in like sea
water.
3.3 Characteristics of galvanic series.
• Galvanic series include both metals and alloys.
• Metals and alloys are arranged in the increasing order of their corrosion resistance in
seawater.
• Metals and alloys having almost same corrosion characteristics are grouped within a
square bracket.
• Same metal can occupy two positions in the galvanic series; For example, aluminum
occurs both active and noble region depending upon its active and passive states.
Figure 4 shows the schematic representation of the EMF Series and Galvanic series

9
 Figure 4: The schematic representation of EMF Series and Galvanic series

3.4 Comparison between electrochemical and galvanic series

• In electrochemical series, electrode potentials are measured by dipping pure metals in
their salt solution of 1M concentration without any oxide film on it. The galvanic series
was developed by studying corrosion of metals and alloys in unpolluted sea water,
without their oxide films.
• The position of a given metal in electrochemical series is fixed based on the electrode
potential value. The position of a given metal may shift in galvanic series as it takes
active and passive states, irrespective of its electrode potential.
• Electrochemical series gives no information regarding the position of alloys. Alloys are
included in galvanic series based on their corrosion behavior

10
 • In electrochemical series, metals and non- metals are included. In galvanic series, only
metals and alloys are included.

4. TYPES OF CORROSION
4.1 Galvanic corrosion
Galvanic corrosion occurs when two dissimilar metals are in physical contact in an aqueous
electrolyte. The less resistant metal acts as the anode (metal with lower electrode potential) and
the more resistant metal (metal with higher electrode potential) function as the cathode. Figure 5
depicts galvanic corrosion showing the anodic and cathodic regions and the direction of electron
flow.
Some examples of galvanic corrosion include:
*copper piping connected to steel tanks.
* Zinc coated screws in a sheet of copper,
*A stainless steel screw in contact with cadmium plated steel washer.
* Steel propeller shaft in bronze bearing
The severity of galvanic corrosion depends largely on the amount of the moisture present.
Corrosion is greater in the coastal region than in a dry rural atmosphere. Condensate near a
seashore contains salt and therefore is more conductive (and corrosive) and a better electrolyte
than condensate in an inland location. Accelerated corrosion due to galvanic effects are usually
more pronounced near the junction with attack decreasing with increasing distance from that
point. In the galvanic couple like Zn/Fe, Fe/Sn, Fe/Cu, Zn/Sn, Zn/Cu; the first metal is anodic
with respect to the second metal and hence undergoes corrosion. It is to be noted that nuts, bolts,
and hinges are made up of one single metal or alloy to prevent the galvanic corrosion.

11
 Figure 5: (a) Galvanic Corrosion (b) Effects of Galvanic Corrosion

4.2 Pitting Corrosion

Pitting corrosion is a localized attack that results in extreme cases holes in the metal. Pits
are sometimes isolated or close together that they look like a rough surface. Generally, a pit may
be described as a cavity or hole with the surface diameter about the same length as or less than
the depth. Pitting is localized, and intense form of corrosion and failure often occurs with
extreme suddenness without prior indication. The important reasons for the pitting corrosion
include
* Surface roughness or non- uniform finish.
* Scratches or cut edges.
* Local straining of metal due to non- uniform stress.
*Deposition of extraneous matter such as sand, scale, water drop and dust
Whenever dust particles are deposited, owing to the different amount of oxygen in contact, with
metal, the small part becomes the anodic areas, and the surrounding large parts become the
cathodic area. Intense corrosion starts just underneath the impurity. Examples: peeling of tin
coat on iron, deposition of dust, sand on the steel surface Pitting form of corrosion can be
represented as shown in Figures 6.

Figure 6: (a) Pitting Corrosion (b) Effects of Pitting Corrosion.

Autocatalytic Nature of Pitting

12
 A corrosion pit is a unique type of anodic reaction. It is an autocatalytic process. That
is, the corrosion within a pit produce conditions which are both stimulating and necessary within
a pit produce conditions for the continuing activity of the pit. It is illustrated in Figure 7.

Figure 7: (a) Autocatalytic nature of pits (b) Pitting corrosion in stainless steel
This process is self-stimulating and self-propagating. The gravity effect is a direct result of the
autocatalytic nature of pitting. Since the dense, concentrated solution within a pit is necessary
for continuing its activity pits are more stable when growing in the direction of gravity.
Pitting corrosion rate increases mainly due to chloride ions present in the solution. This is
probably due to an acid-forming tendency of chloride salts and higher strength of HCl. Oxidizing
metal ions with chlorides are aggressive pitters. Pitting is usually associated with stagnant
conditions such as a liquid in a tank or liquid trapped in a low part of an inactive pipe system.
Velocity or increasing velocity often decreases pitting attack. Pitting corrosion is characterized
by small anodic area and large cathodic area, resulting in accelerated corrosion at the anodic
area. It causes equipment to fail because of perforation with only a small percent weight loss of
the entire structure. It is often difficult to detect pits because of their small size and because the
pits are usually covered with corrosion products.

4.3 Inter-granular Corrosion

Grain boundaries are slightly more reactive than the bulk matrix. Under certain conditions,
grain interfaces are very reactive and inter-granular corrosion results. A localized attack at and
adjacent to grain boundaries with relatively little corrosion of grains is inter-granular corrosion.
The alloy disintegrates and or loses its strength. Impurities can cause Inter-granular corrosion at
the grain boundaries, enrichment of one of the alloying elements or depletion of one of these
elements in the grain boundary areas. For, eg, small amounts of iron in aluminum where the
solubility of iron is low, have been shown to segregate in the grain boundaries and cause inter-

13
granular corrosion. It has been observed that based on surface tension consideration the zinc
content of brass is higher at the grain boundaries.
Depletion of chromium in the grain boundary regions results in inter-granular corrosion
of stainless steels. Numerous failures of stainless steels have occurred because of intergranular
corrosion. When these steels are heated in approximately the temperature range 265-419 0C,
they become susceptible to intergranular corrosion. The chromium carbide in the grain
boundary is not attacked. The chromium-depleted zone near the grain boundary is corroded
because it does not contain sufficient corrosion resistance to resist the attack in many corrosive
environments. The standard 18-8 stainless steel contains from .06 to .08 % carbon, so excess
carbon is available for combining with the chromium to precipitate the carbide. This situation
is shown schematically in Figure 8.

Figure 8: Illustration for inter-granular corrosion

Carbon diffuses towards the grain boundary quite readily at sensitizing temperatures,
but chromium is much less mobile. The surface already available at the grain boundary
facilitates the formation of a new surface, namely that of the chromium carbide. Chromium
carbide which precipitates has been described as particles because of small size. This type of
corrosion occurs along grain boundaries and only where the material, especially sensitive to the
corrosive attack exists and corrosive liquid possesses a particular character of attacking only at
the grain boundaries, but leaving the grain interiors untouched or only slightly attacked. This
type of corrosion is because the grain boundaries contain material, which shows electrode
potential, more anodic than that of the grain center in the particular corroding medium. This
may be due to precipitation of specific compounds at the grain boundaries, thereby leaving the
solid material solution (just adjacent to the grain boundary) impoverished (or depleted) in one
constituent. The impoverished solid solution is anodic with respect to the grain centers as well
as to the precipitated compound so that it will be attacked preferentially by the corrosive
environment.

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 Eg. During the welding of stainless steel chromium carbide is precipitated at the grain
boundaries, thereby just adjacent to grain boundaries becomes depleted in chromium
composition and is more anodic with respect to the solid solution within the grain (which is
richer in chromium). For the same reason, it is also anodic to the particles of the chromium
carbide so-precipitated.
4.4 Stress Corrosion: Stress corrosion or cracking refers to cracking caused by the combined
effect of tensile stress (residual, applied or thermal) and a specific corrosive environment.
During stress corrosion/ cracking, the metal or alloy is virtually un-attacked over most of its
surface, while fine cracks progress through it. The two classic cases of stress corrosion cracking
are "season cracking" of brass cartridges (Figure 9) and caustic embrittlement of steel boilers.

Figure 9: Stress cracking of brass

The metal atoms under stress are at higher energy levels compared to those free from stress. The
stressed part of the metal becomes more reactive than the stress-free part. Corrosion cell is
formed with stressed part acting as anode and stress-free part serving as the cathode. The stressed
part undergoes corrosion under specific corrosive environment, initiating the crack. It grows and
propagates through the metal until the metal failure occurs or it may stop after propagating a
finite distance when either the tensile stress or the corrosive environment is eliminated. Thus the
stress corrosion is characterized by three distinct steps of crack initiation, crack propagation and
final failure. In the first step small crack forms at some point of high-stress corrosion. Then crack
propagation takes place as this crack advances incrementally with each stress cycle. The final
failure occurs very rapidly once the advancing crack has reached a critical size. The
caustic embitterment is a typical example of stress corrosion. This is a dangerous form of stress
corrosion observed in the boiler. Water fed into boilers may contain free alkali. Water softened

15
by lime soda process contains sodium carbonate. Under high temperature and pressure prevailing
within boilers, sodium carbonate hydrolyzes to sodium hydroxide and carbon dioxide.
Na2CO3 (aq) + H2O (l) → 2NaOH + CO2(g)
Thus water inside the boiler becomes very dilute NaOH solution. Local stresses exist in metal
sheets of the boiler under rivets. Minute cracks develop on the metal sheets when the stress is
relieved. Dilute NaOH solution flows into these minute hairline cracks. Water evaporates by the
heat of the metal, depositing sodium hydroxide within the cracks. Freshwater flows into them
and evaporates again depositing more NaOH. The concentration of NaOH increases in these
cracks due to the repetition of this process. NaOH concentration cell forms between the stressed
and unstressed part of the metal. The sodium hydroxide attacks the metal forms sodium ferroate
(Na2FeO2) which further undergoes hydrolysis according to the following equation regenerating
NaOH.
Iron / Concentrated, Dilute / Iron
(stressed) NaOH (cracks) NaOH (unstressed) (boiler water)
ANODE CATHODE
3Na2FeO2 + 4 H2O → 6NaOH + Fe3O4 + H2
6Na2FeO2 + 6 H2O + O2 →12NaOH + 2Fe2O4
When iron changes to these oxides metallic properties like malleability and ductility are lost. It
becomes brittle. The brittleness is caused by caustic alkali. Hence it is called caustic
embrittlement. The minute hairline cracks are caused by local stresses under the rivet heads. The
continuation of caustic embrittlement of boiler parts often results in boiler failure, and extreme
cases may lead to the boiler explosion. The following methods can minimize the caustic
embrittlement;
(i) Na2SO4, tannin or lignin is added to water. These substances deposit within the cracks
and prevent the infiltration and accumulation of NaOH.
(ii) The boiler can be constructed by welding the sheets to avoid local stresses.
(iii) Caustic embrittlement is minimized by using demineralized water that does not
contain NaOH and Na2CO3.

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5 FACTORS AFFECTING CORROSION
The rate of corrosion of a material in a given environment is influenced to a varying degree by
several factors. These factors can be classified into two types given below:
A) Primary factors – the factors associated mainly with the metal
B) Secondary factors – the factors which vary mostly with the environment
5.1 Primary factors
Factors related to the corroding metals are known as primary factors.
(a) Nature of metal and relative electrode potentials of metals
In general, the metals with lower electrode potential are more reactive than the metals with
higher electrode potential.. The magnitude of corrosion cell potential is one of the major factors
which decide the corrosion rate. The larger the potential difference between the anode and
cathode of the corrosion cell, higher is the corrosion rate. When two different metals with a large
difference in their electrode potential are in contact with each other, the more reactive metals
undergo corrosion. When the potential difference is more, higher corrosion current is produced.
Example; Corrosion of zinc is faster than iron when in contact with copper in a medium. This is
because the electrode potential difference between Zn and Cu is greater than that of Fe and Cu.
.(b) Relative Cathodic and Anodic area
The rate of corrosion is greatly influenced by the relative areas of the anode and cathode. If a
metal has a small anodic area and large cathodic area, then the corrosion is more intense and
faster. This is shown schematically in Figure 10(a)
At anode oxidation takes place, and electrons are liberated. At the cathode, these electrons are
consumed. When the anode is smaller, and the cathode region is large all the electrons liberated
at the anode are rapidly consumed at the cathode region. The smaller anodic areas can meet the
demand for electrons by the large cathodic areas by undergoing corrosion at a faster rate. This
makes the anodic reactions to take place at its maximum rate thus increasing the corrosion rate.
Example; Small steel pipe fitted in a large copper tank, iron bolt and nuts in copper boilers.
If the cathode is smaller, the consumption of electrons will be slower, and the corrosion reaction
as a whole will be slower as shown schematically in Figure 10(b).

17
 Figure 10. Schematic representation of the effect of the ratio of the anodic and
cathodic area
(c)Hydrogen Overvoltage
The difference between the observed potential at which reduction of H+ ions to H2 gas occurs at a
cathode and the theoretical potential at which it should have occurred is known as hydrogen
overvoltage. The magnitude of hydrogen overvoltage depends upon the nature of the metal used
as the cathode. Increased hydrogen overvoltage at a cathode reduces the corrosion rate when the
reduction of H+ ions is the cathodic process. When the hydrogen evolution reaction on the metal
surface is low, H2 gas is liberated easily, and then the cathodic reaction rate is faster. This makes
the anodic response also faster, thereby promoting overall corrosion reaction.
(d) Nature of corrosion product
The corrosion product is usually an oxide of the metal which may or may not form a protective
layer on the metallic surface. If the corrosion product deposits and is insoluble, stable, uniform
adherent and nonporous, it acts as a protective film preventing the further corrosion of metal.
E.g., formation oxide film on the surface of aluminum, chromium, and titanium.
If the corrosion product is not deposited and is soluble, unstable, non- uniform, non-adherent and
porous, the corrosion continues unabated since in such cases fresh metal surface is continuously
exposed to the corrosion environment, and corrosion of the metal surface takes place
continuously. E.g., Corrosion of iron and zinc.
If the corrosion product is soluble in the corrosion medium or evaporates, then corrosion
proceeds at a faster rate as a fresh metal surface is exposed continuously to the corrosive
environment, and the destruction of the surface occurs continuously. E.g., Molybdenum oxide
If the corrosion product interacts with the medium to form another insoluble product, then
protective film formed on the metal prevents further corrosion.e.g.PbSO4 formed in the case of
Pb in H2SO4.

18
5.2 Secondary factors
Factors related to the environment are known as secondary factors
(a) Concentration and nature of electrolytes
Rapid corrosion takes place at a high ionic concentration of the electrolyte. The conductivity of
deionized water is 1-10 millimhos per meter. Conductivities of tap water and seawater are 10-20
milli-mhos per meter and 5.3 mhos per meter respectively. Therefore, the corrosion rate in
seawater is nearly 500 times as fast as that in tap water and 5000 times as fast as that in
demineralized water. In the marine atmosphere, the presence of sodium and other chlorides leads
to increased conductivity of the liquid layer in contact with the metal surface. So the corrosion
rate is increased. Salt air of coastal cities is very damaging to exposed metal when compared to
that at interior places. In the vicinity of industrial areas, the atmosphere contains corrosive gases
like CO2, SO2, H2S, and fumes of HCl, H2SO4.So the acidity of the liquid adjacent to the metal
surfaces increases and its electrical conductivity also increases. This increases the corrosion
current in the electrochemical cells on the metal surface.
Some electrolyte cause polarization and bring down the corrosion rate. The phosphate ions form
an insoluble, protective phosphate film of metal ions on the surface of a metal and reduce its
corrosion rate. The chloride ions penetrate the protective oxide film of metal increasing the ionic
conductance of the film. Protective action of this film decreases as a result of this and corrosion
rate gets enhanced.
(b) pH of the medium
In general, lower the pH of the corrosion medium, higher is the corrosion rate. The acidic media
provides a more conducive environment than the alkaline or neutral media. The corrosion rate
increases slowly and gradually with decreasing pH and become rapid at pH less than 4. At pH >
10, corrosion of iron practically ceases due to the formation of a protective coating of hydrated
oxides of iron. However, some metals like Al, Zn, and Pb, undergo fast corrosion in highly
alkaline solution.
(c) Temperature
The rate of a chemical reaction in general increases with the rise in temperature. Curve A of
Figure 11 indicates the corrosion of Nickel in HCl. Increase in temperature increases the
conductance of the corrosion medium, which also contributes to the increase in corrosion rate. In
the case of corrosion resistant passive metals, the rise in temperature decreases the passive range

19
and thereby increases the corrosion rate. However, in some cases, initial negligible temperature
effect will be followed by a very rapid in the corrosion rate at a very high temperature. This trend
is reflected in Curve B of Figure 11. An example is the corrosion of stainless steel in HNO3.
This is because increasing the temperature of nitric acid gently increases its oxidizing power. At
low or moderate temperature, stainless steels exposed to the nitric acid are in the passive state
very close to the trans-passive region. Hence at elevated temperature, there will be an increase in
the oxidizing power of the medium which increases the rate of corrosion. However, if the
corrosion medium contains dissolved gases, the solubility of the gases decreases with
temperature. In such a situation corrosion rate also decreases. Presence of too much humidity
also reduces the rate of corrosion

Figure 11. Effect of temperature on the corrosion rate of Ni in HCl and stainless steel in
HNO3
(d) Polarization at the anodic and cathodic region
During electrochemical corrosion both anode and cathode can no longer be at their
reversible equilibrium potentials. The deviation from reversible equilibrium potential of an
electrode when brought in contact with another electrode is called polarization. There is a
variation of electrode potential due to an inadequate supply of species from the bulk of the
solution to the electrode. In the process of corrosion, the polarization of an anode or cathode
decreases the corrosion rate substantially as anode and cathode polarization retards anode and
cathode reactions respectively. Because of anodic polarization (i.e., shifting of potential to more
positive values and the current to lower value), the tendency of the anodic metal surface to
undergo oxidation decreases. It slows down the anodic reaction and thus decreases the overall
corrosion rate. Cathodic polarization retards the cathodic reaction. This can be due to the

20
chemical polarization of the cathode reactant with an electron. The retarded movement of the
cathodic reactant to the cathode surface or retarded removal of the cathodic reaction product
from the surface of the cathode also makes the cathodic reaction slower. For the corrosion to
continue both anodic and cathodic reaction should take place simultaneously. The slow rate of
any one of the reactions makes the corrosion reaction slower.
6. PROTECTION AGAINST CORROSION
Corrosion of metals occurs when they come in electrical contact with a corrosive
environment. Therefore metallic corrosion can be prevented by either changing the metal or
altering the environment or by separating the metal from the environment. Also, corrosion can
also be prevented by changing electrode potential of the metal. The most effective and
economical method; however, is to deal with the corrosion problem at the design stage itself.
Various methods available for corrosion control are listed below;
*Selection of material & design improvement
*Change of metal
*Change of environment
*Use of coatings for separating metal from the environment
6.1 Selection of materials and proper design
Selection of materials:- Planning for corrosion prevention starts with the selection of appropriate
metals and alloys. Therefore one has to take into account the following material selection
principles.
a) Noble metals such as Pt, Au, and Pd do not undergo corrosion. But one cannot use noble
metals because of its prohibitive price. Pure metals show greater resistance to corrosion than
an impure one.
b) The rate of corrosion can be controlled by using an anodic material of larger area and cathodic
material of smaller area.
c) Suitable alloying of metals in some cases improve its corrosion resistivity.
d) Avoid residual stress in fabricated articles by proper heat treatment (annealing)
e) The use of two dissimilar metals having the large difference in their electrode potentials
should be avoided. Under unavoidable circumstances, the metals chosen should be very close
in the galvanic series. Proper insulator fitting may be used in between to prevent direct contact
of metals.

21
Proper design: - A good design minimizes corrosion in metallic structures or equipment. A large
number of corrosion failures are due to improper design and inability to use available knowledge.
Proper designing of the equipment can control corrosion possibilities. Some of the more
important general rules for design which should be observed are described below:
a) Simplify forms: structures having simpler forms can be protected easily and efficiently. A
complicated shape having more angles, corners, edges and internal surfaces will have a larger
surface area exposed to the corrosive environment and will be difficult to protect by painting or
other surface treatment Improvement in design can be achieved through welding the joints as
shown in Figure 12.

Figure 12: Improvement of design by welding the joints

Electrical boxes exposed to the atmosphere should be so designed that water does not collect at
the top or in the crevices. The profile should be so designed that water is drained completely and
moisture retention should be as low as possible.
b) Avoid crevices: Crevices allow moisture and dirt to be trapped which result in increased
corrosion. If crevices are either present in a structural or cannot be avoided they should be filled
by welding or by using filler. (Figure 13)

Figure 13: Improved designs to minimize crevice corrosion

22
c) Avoid residual moisture: The design should be such as to protect the structure from retained
or residual moisture. To avoid residual moisture, ventilation is usually as important as drainage.
Free circulation of air should reduce condensation. (Figure 14)

Figure 14: Improved design to minimize differential aeration corrosion

d) Avoid sharp corners and bends: These are the potential corrosion sites, and round corners
must replace these. Sharp corners result in the thin coating at corners and are not protected
effectively rounding the corners resulting in an even coating. Sharp bends and other areas were
the fluid directions changed rapidly can promote corrosion and should, therefore, be avoided.
(Figure 15)

Figure 15: Improved design with minimum sharp corners

6.2 Cathodic protection

Corrosion of a structure can be controlled if the entire article can be changed into the cathodic
part of a corrosion cell. This is called cathodic protection. Ship's steel hulls, offshore drilling

23
platforms, oil and gas undersea pipelines, containers used to store water and other liquids are
protected by this method.
Two different methods do cathodic protection.
a) Sacrificial anode method b) Impressed current method
a) Sacrificial anode method
A more reactive metal is kept in contact with the metal structure to be protected by this method
as shown in Figure 16. The reactive metal becomes the anodic part, and the structure becomes
cathodic part of the corrosion cell. The anode is sacrificed to protect the structure. Hence this
method is called a sacrificial anode method.

Figure 16: Mg is used as the sacrificial anode for protecting the iron article
Mg is more reactive metals than iron, and hence it is usually used as the anode. It becomes anodic part
in contact with iron. Following reaction takes place when Mg is made to couple with Iron.
Anode: 2Mg(s) → 2Mg2+ (aq) + 4e−
Cathode: O2 (g) + 2H2O (l) + 4e− →
4OH−(aq)
Net reaction: 2Mg (s) + O2 (g) + 2H2O (l) → 2Mg(OH)2
Advantages: * No external power supply is necessary.
* Can be used in remote and difficult to reach areas.
* Low installation cost.
* Minimum maintenance cost.
* Replacement is much cheaper than replacing the tank/oil pipeline
b) Impressed Current Method.

24
 Figure 17: Schematic diagram of an impressed current method
In this method, the metallic structure is made cathode with the use of impressed current by
connecting the negative terminal of the external DC power source to the metallic structure to be
protected and positive to an inert anode. The anode may be made up of steel, graphite and
platinum group metals. The anode may be consumed very slowly or may not be consumed at all
depending on the anode material. The anode is surrounded by backfill consisting of coke breeze,
gypsum to improve electrical contact between the anode and the environment if it is a weak ionic
conductor. Schematic representation of an impressed method to control corrosion is shown in
Figure 17.
Advantages:
* Applicable to large structures and long-term operations.
* Uncoated parts can be protected.
Disadvantages:
* Larger installation cost.
* Higher maintenance cost.
* High energy consumption
* Localized corrosion may occur if the impressed current is not uniform on the entire
surface.
6.3 Anodic protection method
Anodic protection is based on the fact that under specific ranges of potentials a metal
or alloy becomes passive, resulting in the lowering or prevention of corrosion. Anodic protection
may be understood using the potential current density diagram as shown in Figure 18.

25
 Figure 18: Plot of Potential Vs. Corrosion current (corrosion rate).
Certain metals and alloys lose chemical reactivity under certain environmental conditions. This is
a phenomenon of complex nature, and it occurs under specific conditions. This phenomenon is
called passivity of metals. E.g., Al, Ti, Cr, Ni, Mo, and alloys containing a significant amount of
these metals. The curve is obtained by applying a known potential to a metal specimen and
measuring the current changes. As the potential is increased, initially current also increases (AB)
indicating the dissolution of the metal. This trend continues until the current reaches a critical
value (Icrit) and passivation due to the development of an oxide layer sets in. This potential is
called passivating potential (Ep).
Above Ep the current flow decreases and reaches a minimum value called the passivating
current, I passive. The decrease in current is due to the formation of a passive film on the metal.
If the potential is further increased the metal remains unattacked up to a particular potential is
reached (CD).In this range, the corrosion rate of the metal is minimal.
The potential range in which the anodic protection can be achieved is called the passive region.
The optimum potential for anodic protection is midway in the passive region since it permits
slight variations in the controlled potential without affecting the corrosion rate. Beyond the point
D any further increase in potential tends to increase the current due to the dissolution of metal. It
is called trans-passive region.
The mechanism of protection thus lies in the act of applying specific potential range in which no
corrosion takes place. This potential range depends primarily on the relationship between the
metal and reactants resulting in passivity. This technique protects Iron, Nickel, Chromium,
Titanium and their alloys. The anodic protection of a structure is applied by using a device called

26
potentiostat. It is an electronic device that maintains a constant potential with respect to a
reference. The anodic protection of steel tank containing sulphuric acid is shown in Figure 19.
Potentiostat has three terminals. One connected to the storage tank, other to an auxiliary cathode
(Pt) and third to a reference electrode (Calomel).In operation the potentiostat maintains a
constant potential between the tank and the reference electrode, corresponding to the passive
range.

Figure 19: Potentiostat used in anodic protection

The potential is initially increased to Ep for the corrosion to occur, then increased to Ef (fade
potential) when the current decreases to a small value. Now the potential is kept at constant Ep,
and the current is maintained at Ip. Example: Stainless steel containers used for transporting
corrosive chemicals are protected from corrosion by supporting them at proper Ef and Ip.
Advantages:
• Reduced equipment cost-i.e. it is possible to protect two or more vessels with one
controller Cost of anodic protection is generally independent of tank capacity.
• Applicable in extremely corrosive environments
• Low current demand
Disadvantages:
• Cannot be applied in case of corrosive medium containing aggressive anions such as
chloride.
• Needs a continuous supply of electric current

27
 • Applicable only to those metals that show active, passive behavior
• Initial installation cost is high
• It cannot reduce the corrosion rate to zero.
6.4 Use of corrosion inhibitors
The use of corrosion inhibitors is a possible means of corrosion control by altering
the environment. A corrosion inhibitor is any chemical substance which when added to a solution
(usually in small amounts) increases the corrosion resistance. Corrosion inhibitors are used in
various industrial applications, including cooling water systems, automobile engine coolants,
acid pickling solutions, in the surface treatment of metals, in paints and organic coatings. The
mechanisms of corrosion inhibition are different for acidic and neutral solutions. In acid
solutions, natural oxide films initially present on the metal surface are dissolved away so that
inhibitors then interact directly with the metal surface. In neutral solutions, the system is more
complicated because the metal surface is oxide covered and also because dissolved oxygen may
participate in the electrode reaction. Many inhibitors protect against corrosion either by retarding
anodic dissolution process or cathodic reduction process or both the processes. By this property,
inhibitors can also be classified either as anodic or cathodic inhibitors.
a) Anodic Inhibitors: Substances used to stop the anodic reaction are called anodic inhibitors.
They form insoluble compounds with the metal ions formed at the anodic part due to its
initial corrosion. These insoluble compounds form a protective film on the anode surface.
This film isolates the anode from the electrolyte medium and stops its corrosion. The anions
such as chromate, tungstate, molybdate, and phosphate are used to arrest anodic processes.
Anodic inhibitors are found to be effective provided they are added above their critical
concentrations. If the added inhibitor is insufficient, it cannot plug all the anodic sites. This
leads to severe pitting corrosion.
b) Cathodic Inhibitors: Substances used to stop cathodic reaction are called cathodic
inhibitors. They form a protective film on the cathodic surface and isolate it from the
electrolyte medium. Cathodic reaction stops as a result of this.
There are two major reactions taking place on the cathodic surface depending on the nature of the
corrosive environment. They are: 1) Hydrogen evolution type 2) Oxygen absorption type
1) Hydrogen evolution type inhibitors:- 2H+ (aq)+ 2e- -------->H2(g) (acid medium)

28
The evolution of hydrogen gas over the cathode can be prevented either by retarding the
diffusion of H+ ions to the cathode or by increasing the hydrogen overvoltage. The diffusion of
H+ to the cathode is retarded by the addition of certain organic compounds which contain N or S.
Urea, thiourea, mercaptans and heterocyclic nitrogen compounds are widely used as cathodic
inhibitors. Such substances are adsorbed on the cathodic sites forming a protective film that
suppresses cathodic reaction. Even the use of insufficient concentration of these substances does
not have any adverse effect.
Increasing overvoltage of hydrogen can also prevent the evolution of H2 at the cathode. This is
achieved by the addition of oxides of Arsenic, Antimony or salts like sodium meta-arsenite. They
deposit as an adherent metallic film on the cathode areas thereby prevents the evolution of H2
since hydrogen overvoltage for those metals is quite high.
2) Oxygen absorption type inhibitors:- O2(g) + 2H2O (l) + 4e− → 4OH−(aq) (in neutral or
slightly alkaline medium)
This cathodic reaction can be easily controlled either by removing the oxygen from the corrosive
media or by decreasing the diffusion rate of oxygen to the cathode. Reducing agents such as
N2H4 and Na2SO3 remove oxygen from the corroding environment by combining with it.
N2H4 + O2 → N2 + 2H2O
Decreasing the diffusion rate of oxygen is achieved by adding salts such as ZnSO4, MgSO4,
NiSO4 to the aqueous environment. They undergo hydrolysis and form a deposit of their
insoluble hydroxide on the cathodic sites.
Zn2+ (aq) + 2OH− (aq) → Zn(OH)2.
The protective film being impermeable to oxygen prevents its further diffusion to cathodic sites.
6.5 Surface Coating
A protective coating on the metals and alloys isolates them from electrolyte medium, and hence
corrosion cells do not work. This prevents corrosion.
Metallic Coating: Coating of a metal on a substrate metal requiring protection against corrosion
is metallic coating. There are two types of metallic coating. They are
* Anodic metal coating – coating the substrate metal with a more anodic metal, eg. galvanizing
* Cathodic metal coating - coating the substrate metal with a more cathodic metal, eg. tinning
Galvanization: Giving a Zn metal coating on iron and mild steel is known as galvanization.

29
When the coating covers the entire surface of the substrate metal, the coating isolates it from the
environment and protects it against corrosion. When the coating breaks or cracks zinc act as the
anode, and the substrate iron and mild steel acts as the cathode. Thus zinc becomes the sacrificial
anode and provides protection to iron, and mild steel sheets, pipes, wires are usually galvanized.

Figure 17. Galvanization process

Pretreatment: The metal surface is cleaned to remove organic matter like grease/oil by washing
with organic solvents. The rust and other deposits are removed by washing with dilute sulfuric
acid, and the surface is finally washed with water and air dried.
Process: Galvanization is done by hot dipping processes. The melting point of Zn is 419o C. Zn
is melted and kept at 425-430o C. Ammonium chloride flux is spread over it to prevent its
oxidation by air. Iron and mild steel objects are degreased, pickled and cleaned. They are then
dipped in molten Zn bath. Pair of hot rollers wipes out the excess of zinc coating to produce a
thin uniform coating on the objects which are then cooled. It is shown schematically in Figure
17. Galvanized sheets cannot be used to prepare tins or cans for storing food materials, because
zinc salts are toxic.
Applications: Used in the manufacture of fencing wire, roofing sheets, buckets, bolts, nuts, nails,
and screws.
Tinning: A process involving a coating of tin on iron and mild steel is called tinning. Tinning
protects the article until the coating covers the surface thoroughly, by isolating it from the
environment. When the coating cracks or breaks severe or pitting corrosion of the articles at the
exposed region occurs, because tin is cathodic with iron and small anodic areas are in contact
with the large cathodic area.

30
 Pretreatment: Steel sheet is washed with organic solvents to remove grease/oil deposits. It is
then treated with dilute sulfuric acid to remove rust deposits and finally washed with water and
air dried.
Process: Tinning is done by hot dipping. The melting point of Sn is 232 o C. Tin is melted and
kept at 250o C. It is covered with ZnCl2 and NH4Cl flux to protect liquid tin from oxidation by
air. It is dipped in the molten tin, and the passed through rollers kept in palm oil to squeeze out
excess tin from it. The sheet is cooled, rolled and stored. It is shown in Figure 20.

Figure 20: Tinning Process

Applications:
Used for coating steel, copper, and brass,
Used in the manufacture of containers for storing foodstuffs
For making cooking utensils and refrigeration equipment.
Comparison of Galvanizing and tinning
Galvanizing Tinning
A process of coating Zn over iron/ steel to A process of coating Sn over iron to
prevent it from rusting (anode metal prevent it from corrosion (cathode
coating) metal coating)
Hot rollers used to wipe excess coat are not Hot rollers are immersed in oil
immersed in oil
Galvanized containers cannot be used to Tin coated containers can be used to store
store acidic foodstuffs because zinc reacts foodstuffs because tin is nontoxic and does
with food acids forming highly toxic zinc not react to cause any food poisoning
compounds.
Zinc protects the underlying iron by Tin protects the base metal iron due to its
sacrificial action noble nature.

31
 Zinc continues to protect iron by sacrificial Tin protects the iron until the coating is
action in the event of puncture/break in perfect and any break causes rapid
coating corrosion of iron

6.6 Organic Coating:

Organic coatings are inert barriers like paints, varnishes, lacquers, and enamels applied on a
metallic surface for both corrosion protection and decoration. These involve a relatively thin
barrier between the substrate material and the environment. As a rule, these coatings should not be
used where the environment would rapidly attack the substrate material. The protective value of
such a coating depends on (i) its chemical inertness to the corrosive environment, (ii) its good
surface adhesion, (iii) its impermeability to water, salts and gases and its proper application
method.
6.7 Inorganic coating: They are also known as chemical conversion coatings. These are
inorganic
barrier produced by chemical or electrochemical reactions, brought at the surface of the base
metal. Phosphate coating is produced by the chemical reaction of base metal with an aqueous
solution of phosphoric acid and phosphates of iron, zinc, manganese along with copper salts as
accelerators. Such coatings are usually applied to iron, steel, and zinc by either immersion or
spraying or brushing. The chemical reaction between the phosphating solution and the base metal
results in the formation of a surface film, consisting of crystalline zinc-iron or manganese- iron
phosphates.
7. SUMMARY
Corrosion is one of the problems often encountered in industrialized society, and its study is
important from the point of an engineering. Enormous breadths of engineering systems depend
upon corrosion protection for their reliability, performance, and safety. These corrosion problems
are typically complex phenomena, affected by many variables and not necessarily restricted to one
form of corrosion. The different types of corrosion include galvanic, pitting, inter-granular and
stress corrosion. Certain factors can tend to accelerate the action of a corrosion cell, and these
include nature of the metal and their relative environment, cathode and anode areas, nature of
corrosion products, hydrogen overvoltage pH of the medium, temperature, and polarization
Various measures are taken in almost all industries to control the corrosion rate. Corrosion control

32
techniques include the selection of materials and proper design, cathodic and anodic protection
methods, surface coating and the use of corrosion inhibitors.
8. Review questions
1. Explain the meaning, importance, and consequences of corrosion in the industry and our
day-to-day lives.
2. Describe mechanism of rusting of iron.
3. Comment on the following statements, which can be either true or false.
(i) Al2O3 is corrosion resistant, but Fe2O3 promotes corrosion
(ii) A scratch formed on iron sheets coated with tin results in severe corrosion but the
case is the reverse when it is coated with zinc.
4. Explain the following terms as they apply to the corrosion; (a) Cathodic protection (b)
anodic protection.
5. Distinguish between dry and wet corrosion.
6. Explain the electrochemical theory of corrosion.
7. What are corrosion inhibitors? Explain the types of inhibitors used to control corrosion
with examples.
8. Distinguish between the following; i) Electrochemical series and galvanic series ii)
Galvanizing and tinning.
9. Discuss the different factors affecting the corrosion process.
10. List the various methods used to control corrosion.
********

33
 MODERN METHODS OF CHEMICAL ANALYSIS

Introduction, general methods of quantitative analysis, advantages and disadvantages of the

methods, principles of classical methods and instrumental methods, spectroscopic methods of
analysis – properties of EMR, EM spectrum, interaction of EMR with matter and its phenomenon,
various types of spectra, laws of spectrophotometry – Beer Lambert’s law, its derivation,
deviations of Beer Lambert’s law, Applications of Beer Lambert’s law in qualitative and
quantitative analysis, numerical problems. (4)

Introduction:
A qualitative method gives information about the identity of atomic or molecular or ionic
species or the functional groups present in the sample. A quantitative method provides numerical
information of the constituents i.e., the relative amounts of one or more of the constituents of the
sample. The quantitative methods are often classified as either classical or instrumental/modern.
The classical methods are also called as wet-chemical methods.

Classical and modern/instrumental methods of analysis:

In the early years of chemistry, most analyses (which were being analyzed) were carried
out by separating the components of interest by precipitation, extraction or distillation. For
qualitative analysis, the separated components were then treated with reagents that yielded
products that could be identified by their colors, boiling or melting points, solubilities in a series
of solvents, odors, optical activities or their refractive indices. These are the classical quantitative
methods, which are the volumetry and gravimetry.

The phenomena other than those used for classical methods were exploited for solving the
analytical problems in early twentieth century. The measurement of physical properties of analyte
such as conductivity, electrode potential, light absorption or emission, mass-to-charge ratio,
fluorescence etc. were used for quantitative analysis. The techniques like distillation, extraction
and precipitation etc. were replaced by high efficient chromatography and electrophoretic
techniques for separation of components of complex mixtures. These newer methods for
separation and determination of chemical species are collectively known as instrumental methods
of analysis.
Volumetry:
In volumetric analyses, the volume or mass of a standard reagent required to react completely
with the analyte will be determined by carrying out the titrations. The titration is a process used
to determine the volume of a standard reagent (known concentration) required to react completely
with the analyte. The analyte is also called as titrand and the standard reagent used in the process
is called as titrant. Equivalence point is the point at which the volume of the standard reagent added
is chemically equivalent to the analyte with which it reacts. In volumetric analyses, the volume of
the standard reagent reacted stoichiometrically with the analyte is a measuring parameter. The
stoichiometric point or equivalence point may be detected by use of a visual indicator, which
exhibit different colours or forms the precipitate in different media. There are four types of
volumetric methods of analyses, based on the type of reaction between the standard reagent and
the analyte. They are

(i) Acid-Base titrations

(ii) Complexometric titrations
(iii) Precipitation titrations
(iv) Redox titrations
Based on the relative nature of the acid and bases, the acid-base titrations are further
classified as strong acid vs strong base, strong acid vs weak base, weak acid vs strong base and
weak acid vs weak base titrations. For a particular volumetric analysis method, an appropriate
(specific/selective) indicator is to be used. Some examples of indicators used in various types of
volumetric analyses methods are given in the following table-1 along with the phenomena
(between the standard reagent and analyte) occurred during the titration.

Table-1: Types of volumetric methods and suitable indicators

Sl. No. Type of volumetric Phenomena Suitable Examples
method Indicators
1 Acid – Base titrations:
strong acid vs strong base Phenolphthalein HCl vs. NaOH
weak acid vs strong base Phenolphthalein CH3COOH vs
Neutralization NaOH
strong acid vs weak base Methyl orange HCl vs. NH4OH
weak acid vs weak base No suitable CH3COOH vs
indicator NH4OH
2 Complexometric titrations Complex EBT Zn (or Ca) vs.
formation EDTA disodium
salt
 3 Precipitation titrations Precipitation Potassium Cl- vs. AgNO3
chromate
4 Redox titrations Reduction and Diphenylamine Fe2+ vs. Cr6+
oxidation
reactions

The essential conditions for any volumetric method of analysis are:

(i) The reaction must proceed to completion rapidly
(ii) The reaction should not be complicated by additional or side reactions
(iii) There should be a detectable change (such as a sharp change in colour or formation of
a precipitate) in the solution undergoing titration at the stoichiometric end point
(iv) A suitable indicator must be available for detecting the end point.

Gravimetry:
In gravimetric analyses, the mass of the analyte or some compound produced from the
analyte after treating it with appropriate reagent was determined. Gravimetric methods are based
on the measurement of mass of the analyte or the substance derived from the analyte using an
analytical balance. Gravimetric methods are broadly classified as volatilization methods and
precipitation methods. Volatilization methods involve the drying or heating of a sample to
determine by weight of the content of volatile and or non-volatile components. Precipitation
methods involve the formation of a precipitate through an appropriate reaction and weighing the
precipitate. The precipitation methods generally proceed through four steps.

(i) Precipitation: conversion of analyte into a precipitate by an appropriate chemical using

a selective reagent
(ii) Digestion: allow the precipitate to be in contact with its mother liquor and heat it on a
steam bath during which recrystallization occurs and pure crystals/product is formed.
(iii) Filtration: the digested precipitate will be filtered using an appropriate Whatman filter
papers or sintered glass crucibles, which are to be selected based on the type of
precipitate and the residue forming.
(iv) Washing, drying and weighing: the filtered precipitate is to be washed with very dilute
solution of its mother liquor then dried or ignited followed by weighing and drying till
it gives a constant weight.
Instrumental methods of analysis:
The instrumental methods of analysis are based on the measurement of various physical
and or chemical properties of the analytes. These methods require the sensing probes or electronic
gadgets to measure and quantify the physical/chemical property. The following table-2 shows
some of the methods and the corresponding measuring characteristic properties.

Table-2: List of modern methods of analysis

Sl. No. Instrumental method Characteristic property
1 Kinetic methods Rate of reaction
2 Conductometry Electrical resistance
3 Potentiometry Electrical potential
4 Polarimetry Rotation of radiation
5 Refractometry Refraction of radiation
6 Spectrophotometry and photometry Absorption of radiation
(X-ray, UV, Visible, IR)
7 Emission spectroscopy Emission of radiation
8 Raman spectroscopy Scattering of radiation

There is a group of instrumental procedures that are used for separation and resolution of
closely related compounds. Most of these procedures are based on chromatography, solvent
extraction or electrophoresis. One of the characteristics listed in the above table is usually used to
complete the analysis following the chromatographic separations.

Some instrumental techniques are more sensitive than classical techniques. With certain
combinations of elements or compounds, an instrumental method may be more selective, but with
others, a gravimetric or volumetric approach may have less interference. The instrumental
procedures employ is more sophisticated or costlier apparatus.

Spectroscopic methods of analysis:

Spectrometric methods are a large group of analytical methods that are based on atomic
and molecular spectroscopy. Spectroscopy is a general term for the science that deals with the
interactions of various types of radiation with matter. The interactions of interest were between
electromagnetic radiation and matter. But now, spectroscopy has been broadened to include
interactions between matter and other forms of energy such as acoustic waves, beams of particles
like ions, electrons etc. Spectrometry and spectrometric methods refer to the measurement of the
intensity of radiation with a photoelectric transducer or with any other type of electronic device.
 If the intensity of absorption of radiation is measured, then it is called Absorption
spectroscopy. If the intensity of emission of radiation is measured, it is called Emission
spectroscopy.
The most widely used spectrometric methods are based on electromagnetic radiation (the
energy is mainly in the form of light and radiant heat). The other forms of energy viz., gamma
rays, X-rays, U.V., microwave and radio frequency are less in usage.

General properties of electromagnetic radiation (EMR):

Many of the properties of electromagnetic radiation can be described by a classical
sinusoidal wave model, which describes the parameters like wave length, frequency, velocity and
amplitude. Unlike the other wave phenomena such as sound, electromagnetic radiation requires
no supporting medium for its transmission. So it readily passes through a vacuum.
The wave model fails to account for phenomena associated with the absorption and
emission of radiant energy. To understand these processes, it is necessary to consider the particle
model of electromagnetic radiation in which the EM radiation is viewed as a stream of discrete
packets or wave packets of energy called photons. The energy associated with the photons is
proportional to the frequency of the radiation.
Electromagnetic radiation can be represented as electric and magnetic fields that undergo
in-phase, sinusoidal oscillations at right angles to each other and to the direction of propagation as
shown in the following figure-1.

Figure-1: Various components of electromagnetic radiation

The above figure represents a single ray of plane-polarized electromagnetic radiation. The
electric field strength is a vector; whose length is proportional to its magnitude. As electric field
is responsible for most of the phenomena, such as transmission, reflection, refraction and
absorption, only the electric component of radiation will be considered. However, the magnetic
component of electromagnetic radiation is responsible for absorption of radio-frequency waves in
nuclear magnetic resonance.

Figure-2: Representation of wavelength and amplitude

The maximum length of the electric vector is known as amplitude as shown in figure-2.
The time required for the passage of successive maxima or minima through a fixed point in space
is called a period (p) of the radiation. The frequency (υ) is the number of oscillations (p) of the
field per second and is equal to 1/p.

υ = 1/p
Wave length (λ) is the linear distance between any two equivalent points on successive
waves. Multiplication of the frequency (in cycles per second) by the wave length (in meters per
cycles) gives the velocity of propagation.

V=υλ
The frequency of a beam of radiation is determined by the source and remains constant.
But the velocity of the radiation depends upon the composition of the medium through which it
passes. Therefore, the above equation implies that the wave length of radiation is also dependent
upon the medium.
In vacuum, the velocity of radiation is independent of wavelength and is at its maximum.
This velocity is given by ‘c’ and is equal to 2.99×108 m/sec.
c=υλ
υ=c/λ
 In any medium containing matter, propagation of radiation is slowed by the interaction
between the electromagnetic field of the radiation and the bound electrons in the matter. Since the
radiant frequency is invariant and fixed by the source, the wavelength must decrease as radiation
passes from a vacuum to another medium.
~
The wave number (  ) is defined as the reciprocal of the wavelength in cm. and is another
way of describing electromagnetic radiation. The unit for it is cm-1. This is widely used in IR
spectroscopy. The wave number is frequently used, because it is directly proportional to the
frequency and thus energy of the radiation.
~ = 1/ λ = υ/c
The Power of radiation is the energy of the beam that reaches a given area per second. The
Intensity of the radiation is the power per unit solid angle. These two quantities related to square
of the amplitude and which are often used in spectroscopy.
The phenomena of refraction, reflection, constructive and destructive interference are
examples of wave properties. But the wave nature of EMR fails to explain some phenomena like
photoelectric effect etc., In order to explain such phenomena, it is assumed that the EMR consists
of a stream of descrete packets (particles) of pure energy, called photons or quanta. These have
definite energy and travel in the direction of propagation of the radiation beam with the velocity
equal to that of the light. The energy of the photon is proportional to the frequency of radiation
and is given by the following relationship.
E=hυ
Where E is the energy of the photon in J s, υ is the frequency of the EMR in cycles per sec., and h
is called Planck’s constant (6.624×10-34 J-sec.). The intensity of a beam of radiation is proportional
to the number of photons per second that are propagated in the beam. But the intensity is
independent of the energy of each photon.
The connection between the wave and particle characteristics of radiation was suggested
by Planck. According to him, if a transition occurs between the energy states of a system such that
a photon of energy E is emitted or absorbed, the frequency of the emitted or absorbed radiation is
given by
~
E = h υ = hc 
= hc/ λ
 With the help of this equation, a particular wavelength or wave number of frequency can
be converted into desired units.
Electromagnetic spectrum:
Electromagnetic spectrum (figure-3) encompasses an enormous range of wavelengths and
frequencies (and thus energies). In fact, the range is so great that a logarithmic scale is required.
The major characteristics of various regions of spectrum are outlined as follows.

(a) γ-ray region:

υ = 3 EHz to 300 EHz (1 exa Hz = 1018 HZ)
λ = 100 pm to 1 pm
This region corresponds to the energy range of 1 to 100 GJ/mole. The γ-rays have sufficient
energy to bring about nuclear transformations. The γ-ray resonance spectroscopy is known as
Mossbauer Spectroscopy.
(b) X-ray region:
υ = 30 PHz to 3 EHz (1 Pet Hz = 1015HZ)
λ = 10 nm to 100 pm
This region corresponds to the energy range of 10MJ/mole to 1 GJ/mole. The energy of X-
rays is sufficient to cause the transitions of core electrons of atoms and molecules. X-ray
spectroscopy and X-ray photoelectron spectroscopy (XPS) are associated with the X-ray region.
(c) Visible and Ultraviolet region: These are further made up of the following regions.
Vacuum ultraviolet : 1 – 800 nm
Ultraviolet : 180 – 400 nm
Visible : 400 – 750 nm
(d) Infrared region: This region has been further divided into the following sub-regions.
Infrared (near) : 0.7 – 2.5 
Infrared : 2.5 – 15 
Far infrared : 15 – 200 
(e) Microwave region: (0.1 mm to 1 cm wave length) This region corresponds to changes in
the rotation of molecules. Separations between the rotational levels of molecules are of the
order of hundreds of joules per mole.
(f) Radio frequency region: (10 m – 1 cm wave length) The energy change involved in this
region arises due to the reversal of a spin of nucleus or electron. This is of the order 0.001
– 10 J/mole.
 Figure-3: Electromagnetic spectrum
Interaction of EMR with matter:
When EMR passes through matter, a variety of phenomena may occur. Some of these are
as follows.

If the photons of radiation possess the appropriate energies, they may be absorbed by the
matter and result in electronic transitions, vibrational changes or rotational changes or combination
of these. After absorption, atoms or molecules become excited. They give out energy quickly
either by losing energy in the form of heat or by re-emitting EMR.

It is not necessarily that the radiation passing through the matter may be absorbed
completely. The portion of EMR which passes into matter, instead of being absorbed, may
undergo scattering or reflection or may be re-emitted at the same wavelength or a different
wavelength.

When EMR is neither absorbed nor scattered, it may undergo changes in orientation or
polarization.

In some cases, the molecules after absorbing radiation become excited but they do not lose
energy very quickly but with some delay. In such cases the energy is re-emitted as radiation
usually of longer wavelength than was originally absorbed. This phenomenon is called as
fluorescence. If there is a detectable time delay (in some cases) in re-emission, the phenomena are
termed as phosphorescence.
Molecular spectroscopy:
In molecular spectroscopy, the spectra arise from three types of transitions viz., rotational,
vibrational and electronic transitions. Broadly speaking, the total energy of a molecule is given
by the following equation according to Born-Oppenheimer approximation,

Etotal = Etranslational + Erotational + Evibrational + Eelectronic

The molecular energy is the sum of translational energy, rotational energy, vibrational
energy and electronic energy. The translational energy is not quantized and furthermore,

Eelectronic >> Evibrational >> Erotational >> Etranslational

Since the translational energy is negligibly small, we can write the Born-Oppenheimer
approximation as

Etotal = Erotational + Evibrational + Eelectronic

Let us illustrate these energies with reference to a diatomic molecule. Rotational energy
arises when the molecule rotates about an axis perpendicular to the internuclear axis and passing
through the centre of gravity of the molecule. Vibrational energy is associated with the to and fro
motion of the nuclei of the molecule such that the centre of gravity does not change. Electronic
energy is associated with the transition of an electron from the ground energy level to an excited
state energy level of the molecule due to the absorption of a photon of suitable frequency.

Each electronic energy level (designated with E) is associated with a series of vibrational
energy levels (designated with the vibrational quantum number, v) and each vibrational energy
level is associated with a series of rotational energy levels (designated with R) as shown in the
following figure-4.
 Figure-4: Different energy levels of a molecule with possible transitions
The rotational spectra of a molecule are observed in the microwave region, the vibrational
spectra in the infrared (IR) region and the electronic spectra in the ultraviolet (UV) and or visible
regions of the electromagnetic spectrum.

The various types of spectra given by a molecule, the regions in which these spectra lie and
the energy that take place in the molecule on absorption of radiation are listed below.

Rotational (Microwave) spectra: These spectra result from transitions between the rotational
energy levels of a gaseous molecule on the absorption of radiations falling in the microwave
region. These spectra are shown by the molecules which possess a permanent dipole moment,
e.g., HCl, CO, H2O vapour, NO etc. Homo nuclear diatomic molecules like H2, Cl2, etc., and
linear polyatomic molecules such as CO2 which do not possess a dipole moment, do not show
microwave spectra. Microwave spectra occur in the spectral range of 1 – 100 cm-1. From the
microwave spectrum of a molecule, the equilibrium internuclear distance between two atoms,
rotational constant, moment of inertia, the shape of the molecule etc. can be determined. A typical
microwave spectrum of CO molecule (considering it as a rigid rotator) is shown in the following
figure-5.

Figure-5: Typical microwave spectrum of rigid rotating CO

Vibrational and vibration-rotation (Infrared) spectra: These spectra originate from transitions
induced between the vibrational energy levels of a molecule on the absorption of radiations
belonging to the infrared region. IR spectra are shown by molecules when vibrational motion is
accompanied by a change in the dipole moment of the molecule. These spectra occur in the
spectral range of 400 – 4000 cm-1. The presence or absence of functional groups, the extent of
hydrogen bond (HB) interactions (intra and inter) in/between molecules, force constants of various
types of bonds etc. can be determined from the IR spectrum of a molecule. A typical IR spectrum
(vibration-rotation) of a butyraldehyde is given in the following figure-6.
 Figure-6: Typical IR spectrum of butyraldehyde

Electronic spectra: Electronic spectra arise from electronic transition in a molecule by absorption
of radiations falling in the visible and ultraviolet regions. While electronic spectra in the visible
region span 12,500 – 25000 cm-1, those in the ultraviolet region span 25000 – 70000 cm-1. Since
electronic transitions in a molecule are invariably accompanied by vibrational and rotational
transitions, the electronic spectra of molecules are highly complex. A typical electronic spectrum
of a green food coloring agent is given the following figure-7.

Figure-7: Typical electronic spectrum of a green food color

Spectrophotometry:
Beer and Lambert’s law and its derivation:
Lambert’s Law:
When a monochromatic light passes through a transparent medium, the rate of decrease in intensity
with the thickness of the medium is proportional to the intensity of the light. This is equivalent to
stating that the intensity of the emitted light decreases exponentially as the thickness of the
absorbing medium increases arithmetically.
We can write it as
𝑑𝐼
− = 𝑘𝐼 (1)
𝑑𝑡

Where I = intensity of the incident light of wave length, λ

t = thickness of the medium
k = proportionality constant
Integrating eq. 1, and putting I = I0 when t = 0
𝑑𝐼
−∫ = ∫ 𝑘𝐼
𝑑𝑡
𝑑𝐼
−∫ = 𝑘 ∫ 𝑑𝑡
𝐼
𝐼0
ln = 𝑘𝑡
𝐼𝑡
It = I0 e-kt (2)
Where I0 = intensity of the incident light falling upon the absorbing medium of thickness, t
It = intensity of the transmitted light
k = constant for the wavelength and the absorbing medium
we can write the eq. 2 as
𝐼𝑡
= 𝑒 −𝑘𝑡
𝐼0
−𝑘
= 102.3036𝑡
= 10−0.4343𝑘𝑡
It = I0 10−𝐾𝑡 (3)
Where ‘K’ is called as absorption coefficient.
The absorption coefficient (K) is generally defined as the reciprocal of the thickness (t, cm)
required to reduce the light to 1/10th of its intensity.
𝐼𝑡
i.e., in eq. 3, = 0.1
𝐼0

= 10−𝐾𝑡
or Kt = 1 and K = 1/t
 𝐼𝑡
The ratio, is the fraction of the incident light transmitted by a thickness ‘t’ of the medium and
𝐼0
𝐼𝑜
is termed as the transmittance (T). The reciprocal of transmittance i.e., is opacity. The
𝐼𝑡
absorbance (A) of the medium is given by
𝐼
A = log ( 𝐼0) (4)
𝑡

Beer’s Law:
“The intensity of a beam of monochromatic light decreases exponentially as the concentration of
the absorbing substance increases arithmetically”
This can be written as

It = I0 e-k'C
= I0 10−0.4343𝑘`𝐶
= I0 10−𝐾𝐶 (5)
Where ‘C’ is the concentration, k` and K` are constants.
Combining eq. (3) and eq. (5),
𝐼𝑡
= 10−𝑎𝐶𝑡
𝐼0
𝐼𝑡
log ( ) = 𝑎𝐶𝑡 (6)
𝐼0

This (eq. 6) is the mathematical expression for Beer-Lambert’s law.

The value ‘a’ depend upon the method of expression of the concentration of the solution. If ‘C’ is
expressed in mol/l and ‘t’ in cm; then ‘a’ is given the symbol, ε and is called the molar absorption
coefficient or molar absorptivity.
It is clear that, there is a relationship between the absorbance (A), the transmittance (T) and the
molar absorption coefficient.
𝐼
A = log ( 𝐼0) = log(1/T) = - log T (7)
𝑡

⸫ A = -log(T)
A = εCt
The scales of spectrophotometers are often calibrated to read directly in absorbance and frequently
in % transmittance also.
A = εCt
ε = A/Ct
If C = 1 mol/dm3, t = 1 cm; then ε = A
i.e., the molar absorption coefficient is the specific absorption coefficient. Specific absorption
coefficient is defined as the absorption per unit thickness and unit concentration.

Limitations of Beer-Lambert law

The linearity of the Beer-Lambert law is limited by chemical and instrumental factors. The
probable causes of nonlinearity are:

1. Deviations in absorptivity coefficients at high concentrations (>0.01M) due to electrostatic

interactions between molecules in close proximity
2. Scattering of light due to particulates in the sample
3. Fluoresecence or phosphorescence of the sample
4. Changes in refractive index at high analyte concentration
5. Shifts in chemical equilibria as a function of concentration
6. Non-monochromatic radiation, deviations can be minimized by using a relatively flat part
of the absorption spectrum such as the maximum of an absorption band
7. Stray light

Applications of Beer Lambert’s law in qualitative and quantitative analysis:

Estimation of Iron:

Iron is one of the many minerals required by the human body. It is biologically relevant as
oxygen-carrying proteins, haemoglobin and myoglobin. A deficiency of iron in the body can leave
a person feeling tired and can lead to a disorder called anemia. Many of the foods we eat contain
small quantities of iron. The trace quantity of iron also may be present in water sources. Other
application of iron is in industrial metallurgy. So, a simple method to estimate iron at very low
concentrations is desired using colorimetric analysis.

Method:

In this analysis the iron present in the samples (like an iron tablet or a sample of food is
extracted to form a solution containing Fe3+ (ferric) ions. To make the presence of these ions in
solution visible, thiocyanate ions (SCN−) are added. These react with the Fe3+ ions to form a
blood-red colored complex as given below.
 Fe3+(aq) + SCN−(aq) → [FeSCN]2+(aq)

By comparing the intensity of the colour of this solution with the colours of a series of
standard solutions, with known Fe3+ concentrations, the concentration of iron in the tablet, food or
any other sample may be determined. A plot of absorbance vs solution of known concentration
and the by comparison of the absorbance of the unknown solution, one can quantitatively estimate
the amount of iron present.

Numerical:

The molar extinction coefficient of phenanthroline complex of iron (II) is 1200 dm3 mol-1 cm-1 and
the minimum detectable absorbance is 0.01. Calculate the minimum concentration of the complex
that can be detected in the experiment if the path length is 1.00 cm.

A = εbc

c = A/εb = 0.01 / 1.00 * 1200

= 8.33 x 10-6 M

***
4. CHEMICAL FUELS
Introduction, Classification, Gross Calorific value and Net Calorific value. Solid fuel (coal) –
proximate & ultimate analysis. Liquid fuels: Petroleum-Refining, Cracking and reforming.
Synthetic Petrol: Methods of production. Gaseous fuels: bio-gas production and uses.
Learning objectives
• Define calorific value and describe the classification of fuels
• Understand the terms NCV and GCV
• To know about the petroleum refining, cracking and reforming techniques
• Understand about Synthetic fuels, production process
• To know about the production of bio-gas and their uses
4.1 Introduction
Chemical fuel is a carbonaceous material which on proper combustion in air releases a
large amount of heat which can be used for both domestic and industrial purposes
economically. Eg. Wood, charcoal, coal, kerosene, petrol, diesel, producer gas, water
gas, natural gas, etc. The main elements invariably present in chemical fuels are C, and
H. During combustion, C and H of the chemical fuel combine with the oxygen from the
air to form CO2 and H2O respectively. Chemical fuels release heat during combustion
as the heat content of combustion products (CO2 & H2O) are lower than that of the
reactants (C, H of the fuel). The combustion process can be explained in terms of the
three components - temperature, time and turbulence.
Temperature – To have good combustion, the temperature must be high enough to
ignite the fuel constituents and all the gases that are released during the process.
Time – The time (reaction period) must be sufficient to complete the combustion process.
Turbulence – There should be sufficient turbulence to allow complete mixing of
combustible elements, fuel, and oxygen. The sustainability of fire depends upon a
favorable fuel-oxidant ratio and the maintenance of temperature above ignition
temperature. The three components of fire involved in a fuel such as wood, kerosene or
gas, energy sufficient to support combustion and an oxidizing agent like air.
4.2 Classification of fuels
Fuels may generally be classified in two ways as follows;
a) Based on occurrence – Primary (natural) and secondary (derived/man-made/synthetic)
fuels.
b) Based on the physical state – Solid, liquid and gaseous fuels.

4.3 Calorific value

The calorific value is the amount of heat or energy produced when the substance is allowed to
undergo combustion. It is an important property of fuel and is defined as “the amount of heat
liberated when unit mass (or unit volume in gaseous fuel) of fuel is completely burnt with pure
oxygen”. In the case of solid or liquid fuels, the weight sufficiently defines the quantity of the fuel
present. However, in the case of gaseous fuels, it is necessary to specify both temperature and
pressure to define this quantity. The calorific value is generally expressed in calorie per gram
(cal/g), kilocalorie per kilogram (kcal/kg) or joule per kilogram (J/kg) in case of solid and liquid
fuels. In case of gaseous fuels, the units used are kilocalorie per cubic meter (kcal/m3) or joules
per cubic meter (J/m3). It is measured either as gross or net calorific value; the difference is given
by the latent heat of condensation of the water vapor produced during the combustion process.
Gross or Higher calorific value (GCV /HCV)
The Gross or Higher calorific value is defined as “the amount of heat liberated when unit
mass/volume of the fuel is burnt completely in oxygen, and the products of combustion are cooled
to room temperature”. When a fuel containing carbon and hydrogen is burnt, C and H are converted
into CO2 and water vapor. Latent heat of steam is released, and water vapor condenses to form
water when the combustion products are cooled to room temperature. GCV is higher than NCV as
it includes latent heat of condensation of steam.
Net or Lower calorific value (NCV / LCV)
Net or Lower calorific value is defined as “the amount of heat produced when unit mass/volume
of fuel is completely burnt in air, and the products of combustion are allowed to escape into the
atmosphere”. In actual practice, the combustion products (steam) are not cooled to room
temperature but simply let off into the atmosphere. Hence, a lesser amount of heat is available.
Since this calorific value does not include the latent heat of condensation of steam, the net calorific
value is always lower than gross calorific value.
NCV = GCV – Latent heat of condensation of steam
= GCV – Mass of hydrogen × 9 × latent heat of steam
= GCV – 9 x % of hydrogen × latent heat of steam
100
NCV = GCV – 0.09 × % H ×587
[Note: Because1g hydrogen gives 9g of water]
If H = Percentage of hydrogen in fuel, then,
Water formed by combustion of 1g of fuel = 18 x H = 0.09H g
2 100
[Latent heat of steam is 587cal/g]

The calorific value of a chemical fuel is determined experimentally using Bomb and Boy’s
calorimeter. The bomb calorimeter is used for the determination of the calorific value of solid and
liquid fuels whereas Boy’s calorimeter is used for gaseous fuels.

4.4. Solid fuels

Solid fuels are primarily classified into two;

Natural fuels- wood & coal
Manufactured fuels- charcoal & coke.
Advantages
(a) Easily transportable.
(b) Conveniently stored without risk of any spontaneous explosion.
(c) Low production cost.
(d) Possess moderate ignition temperature.
Disadvantages
(a) High ash content.
(b) Wastage of large proportion of heat.
(c) Clinker formation when they burn.
 (d) Combustion process cannot be easily controlled.
(e) High handling cost.
The main solid fuels include wood, peat, lignite, coal, and charcoal.

Applications:
Used for many years to create fire.
Coal - a fuel source that aided the industrial revolution
Wood - used to run steam locomotives. Peat and coal – Currently used in the generation of
electricity
Charcoal is prepared by the dry distillation of wood. It is the best fuel since it has no sulfur content.
But it is costly Coke is obtained by destructive distillation of soft coals in closed retorts. Briquetted
coal is obtained by briquetting the dried coal by applying pressure alone. Pulverised coal is
obtained by pulverized the low-grade fuels.
Analysis of coal and its significance
The proximate analysis involves the determination of moisture, volatile matter, ash, and fixed
carbon. This gives quick and valuable information about classification and suitability. The ultimate
analysis involves the determination of carbon, hydrogen, sulfur, nitrogen, oxygen, and ash.
The ultimate analysis is essential for calculating heat balances.
Proximate analysis of coal
(i) Moisture: About 1 g of air-dried finely powdered sample of coal is weighed into a dry silica
crucible and heated for about one hour at 110 0C in an electric hot air-oven. The crucible is cooled
first in the air, then in a desiccator and weighedW. The loss in weight is noted.
% of moisture = Loss in weight X 100
Wt. of coal sample
During the burning of coal, moisture in it evaporates by taking some liberated heat in the form of
latent heat of evaporation, thereby lowering the effective calorific value of coal. Hence, lesser the
moisture content better is the quality of coal as a fuel. But, the presence of up to 10% moisture
creates more uniform fuel-bed and less of “fly-ash”.
(ii) Volatile matter: The dried coal sample left in the crucible in step (i) is then covered with a lid
and placed in a muffle furnace, maintained at 950 ± 200 oC. The crucible is taken out after 7
minutes of heating. It is cooled first in air further in a desiccator and finally weighed.
% of volatile matter = Reduction in weight due to loss of volatile matter X 100
Wt. of coal sample
Higher % of the volatile matter in coal is undesirable as a high proportion of fuel will distill over
as vapor and a large portion of which escapes unburnt. Coal sample with high % volatile matter
burns with a long flame, high smoke and has low calorific value. Coal is ranked good if the volatile
matter is less.
(iii) Ash: The residual coal left in the crucible in step (ii) is heated without the lid in a muffle
furnace at 700-750 oC, until a constant weight of residue is obtained.

The mineral matter originally present in the vegetable material from which the coal was formed,
consists of oxides of K, Mg and Ca and is called intrinsic ash. Non-essential mineral matters such
as clay, gypsum or other inorganic matters, give rise to extrinsic ash. The intrinsic ash content
rarely exceeds 1 to 2% whereas extrinsic ash content is relatively higher.
Ash-forming constituents in coal are undesirable for the following reasons:
(i) The calorific value of the coal is decreased
(ii) Removal and disposal of ash poses problems
(iii) The ash deposited in the fire bars interferes with the circulation of air
(iv) If the ash fuses to form a clinker on the fire bars, it hinders air circulation and also promotes
corrosion of the fire bars. However, some ash is desirable since it serves to protect the grates
from direct contact with incandescent coal, which might lead to oxidation of the grate bars.
(iv) Fixed carbon: It is reported as the difference between 100 and the sum of the percentages of
moisture, volatile matter and ash content of a coal sample.
Calorific value and quality of a coal sample increase with the percentage of fixed carbon. Greater
the percentage of fixed carbon, smaller is the percentage of volatile matter. It is the fixed carbon
which burns in the solid state. Hence information regarding the percentage of fixed carbon helps
in the designing of the furnace and the fire-box.
Significance: Grading of a coal or coke sample to determine moisture, volatile matter, fixed
carbon, and ash are done by proximate analysis which is important to both the suppliers and users
to have a speedy, precise and consistent procedure. It also helps to;
i) Rank coal
ii) Show the quantity of combustible and non-combustible constituents
iii) Provide the basis for buying/selling,
iv) Identify appropriate coal for different purposes.
Ultimate analysis of coal
(i) Carbon and hydrogen: An accurately weighed coal sample (1-2 g) is burnt in a current of
oxygen in a combustion apparatus. As a result, carbon and hydrogen of the coal are converted into
CO2 and H2O respectively. These are absorbed respectively in weighed KOH and CaCl2 tubes.
The rise in the weights of KOH and CaCl2 tubes corresponds to the amount of CO2 and H2O formed
respectively.

Fig. Schematic diagram of % C & % H analysis

C + O2 → CO2 H2 + ½ O2 → H2O
12 44 2 18
2 KOH + CO2 → K2CO3 + H2O CaCl2 + 7 H2O → CaCl2 .7 H2O
% of carbon = Increase in weight of KOH tube X 12 X 100
Wt. of coal taken X 44
% of hydrogen = Increase in weight of CaCl2 tube X 2 X 100
Wt. of coal taken X 18
Carbon and hydrogen in coal directly contribute towards the calorific value of the coal. Greater
the percentage of C and H, better is the coal quality and higher is its calorific value.
ii) Nitrogen: The percentage of nitrogen is determined by digesting a known quantity (1 g) of
powdered air-dried coal sample with Conc. H2SO4 and HgSO4 in a Kjeldahl’s flask using K2SO4
as a catalyst. After the solution becomes clear, excess NaOH is added and the ammonia liberated
is distilled into a known volume of acid solution of known strength. The volume of unused acid is
determined by back titration using standard NaOH solution. The percentage of nitrogen is
calculated from the volume of acid neutralized by ammonia liberated, The Kjeldahl’s apparatus is
shown in Fig.
Nitrogen in the coal does not contribute any useful value to the coal, and since it is generally
present in small quantities (~ 1%), its presence is not of much significance. However, the nitrogen
content is less in good quality coal.

Fig. Schematic diagram of Kjeldahl apparatus

% of nitrogen = Weight of nitrogen X 100

Wt. of coal taken
Where, Weight of nitrogen = Volume of acid used X Normality of acid X 14
1000
Thus, % of nitrogen = Vacid X Nacid X 1.4
Wt. of coal taken
(iii) Sulfur: Weighed coal sample is allowed to undergo complete combustion in a bomb
calorimeter by which sulfur present in coal is oxidized to sulfates. The ash left after combustion
from the bomb calorimeter is extracted with dil. HCl. Barium chloride solution is added to the acid
extract barium sulfate, which is then filtered, washed, ignited and weighed. From the weight of
barium sulfate obtained the sulfur present in the coal is calculated.
% of sulfur = Wt. of BaSO4 obtained X 32 X 100
Wt. of coal taken X 233
Sulfur present in coal adds to the calorific value of the coal, but its combustion products (SO2 and
SO3) have corrosive effects on equipment, particularly in the presence of moisture. Further, the
oxides of sulfur are undesirable from the atmospheric point of view. Sulfur-containing coal is not
suitable for the preparation of metallurgical coke as it adversely affects the properties of the metal.
(iv) Ash: The ash content of the coal sample is determined as described under proximate analysis.
(v) Oxygen: The oxygen content is calculated by difference as follows:
Percentage of oxygen = 100 – Percentage of (C + H + N + S + Ash)
The oxygen content of coal is generally associated with moisture. The lower the oxygen content,
the more is the maturity of coal, and greater is its calorific value. As the oxygen content increases,
the capacity of the coal to hold moisture increases and the coking power decreases.
Significance
To evaluate the chemical composition of coal in terms of various elements present (C, H, O, N,
S) and ash
To predict the suitability of coal for the purpose of heating
For combustion calculations
To determine the composition of flue gases

Numerical problems
1. About 0.6 g of a coal sample was allowed to undergo combustion in a bomb calorimeter. The
calorific value of the sample was found to be 8600 cal/g. The ash formed was extracted with acid,
and this was heated with BaCl2 solution. The weight of dried barium sulfate obtained was found to be
0.05 g. Calculate the % of S in the coal sample.

2. About 1.6 g of coal sample was kjeldahlised and NH3 gas thus evolved was absorbed in 50 mL
of 0.1 N sulphuric acid. After absorption, the excess of acid required 6.5 mL of 0.1 N NaOH for
neutralization. Calculate the % of nitrogen in the sample.

4.5. Liquid fuels

Liquid fuels are combustible molecules that can be harnessed to create mechanical energy. They
are predominantly used in industries. Most liquid fuels used currently are made from crude
petroleum. Gasoline is the most widely used liquid fuel. Liquid fuels have the advantage of higher
calorific value per unit mass compared to solid fuels, burn without dust, ash & clinkers and are
easy to transport through pipes. But liquid fuels are costlier than solid fuels and possess greater
fire hazard risks (especially highly inflammable & volatile liquid fuels).
Petroleum

Petroleum was formed in nature by anaerobic decay of marine plant and animal life under high
temperature and pressure millions of years ago. It is a complex mixture of organic crude oil and
natural gas which consists of hydrocarbons like paraffins, cycloparaffins, olefins, and aromatics
with small quantities of nitrogen, oxygen, and sulfur-containing organic compounds and traces of
inorganic compounds. The process of separation of crude oil into different useful fractions on the
basis of their boiling points using an efficient bubble cap type fractionating column is called
petroleum refining.

Cracking
An average grade crude oil on fractionation yields about 20-30 % gasoline, 30-45 % intermediate
oils and 25-50 % residual fuel oils. Cracking of the surplus heavier fractions gives greater yields
of improved gasoline and better engine performance than that obtained from fractional distillation
of crude oil. Cracking is defined as the process of decomposition of hydrocarbons with higher
molecular weight into that of lower molecular weight by breaking C-C and C-H bonds producing
low boiling alkanes and alkenes.
Cracking

C10 H22 C5H12 + C5H10

(Decane) High b.p (pentane) (Pentene) Low b.p
Types of Cracking:

1) Thermal Cracking 2) Catalytic Cracking

Thermal Cracking: In thermal cracking high temperatures and pressures are used to break the large
hydrocarbons into smaller ones. Thermal cracking gives mixtures of products containing high
proportions of hydrocarbons with double bonds- alkenes. •Thermal cracking doesn’t go via ionic
intermediates like catalytic cracking. Instead, carbon-carbon bonds are broken so that each carbon
atom ends up with a single electron. In other words, free radicals are formed
Catalytic Cracking:

• Modern cracking uses Zeolites as the catalyst. These are complex aluminosilicates and are
large lattices of aluminum, silicon and oxygen atoms carrying a negative charge. They are, of
course, associated with positive ions such as sodium ions. You may have come across a zeolite if
you know about ion exchange resins used in water softeners.
• The alkane is brought into contact with the catalyst at a temperature of about 500 oC and
moderately low pressures.
• The zeolites used in catalytic cracking are chosen to give high percentages of hydrocarbons
with between 5 and 10 carbon atoms- particularly useful for petrol. It also produces high
proportions of branched alkanes and aromatic hydrocarbons like benzene.
• The zeolite catalyst has sites which can remove hydrogen from an alkane together with the two
electrons which bound it to the carbon. That leaves the carbon atom with a positive charge. Ions
like this are called carbonium ions. The reorganization of these leads to various products of the
reaction.

The main advantages of catalytic cracking are as follows

• The octane number and yield of gasoline produced is high.
• The process can be better controlled.
• There is a saving in production costs as high temperatures, and high pressures are not required.
• External fuel is not required. The necessary heat is obtained by burning off the coke deposited
on the catalyst itself, during the regeneration process.
• Catalysts are selective in their action, and therefore, they permit cracking of only high boiling
hydrocarbons.
Catalytic Reforming: Process of upgrading gasoline by increasing its octane number in the
presence of a catalyst. The main reactions taking place during catalytic reforming process are:
i) Isomerisation: Conversion of straight chain hydrocarbons into branched chain hydrocarbons.

ii) Dehydrogenation: Dehydrogenation of cycloalkanes to produce aromatic compounds.

iii) Cyclisation and dehydrogenation: Straight chain hydrocarbons undergo cyclisation followed
by dehydrogenation to produce aromatic hydrocarbons

iv) Hydrocracking: n-Paraffins undergo cracking in the presence of hydrogen and catalyst to
produce light gases that are removed from gasoline fraction.

Synthetic Petrol

Synthetic fuel or Synfuel is a liquid fuel obtained from coal, natural gas, oil shale, or biomass. It
may also refer to fuels to fuels derived from other solids such as plastic or rubber waste. It may
also refer to gaseous fuels produced similarly. A common use of the term synthetic fuel is to
describe fuels manufactured via Fischer Tropsch conversion, methanol to gasoline conversion or
direct coal liquefaction.

Method of producing Synthetic Petrol:

1. Polymerisation
2. Fischer-Tropsch method
3. Bergius process

Fischer- Tropsch Process: The Fischer-Tropsch process is a collection of chemical reactions

that convert a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. The process, a
key component of gas to liquids technology, produces a synthetic lubrication oil and synthetic fuel,
typically from coal, natural gas or biomass. The F-T process has received intermittent attention as
a source of low sulfur diesel fuel and to address the supply or cost of petroleum-derived
hydrocarbon. The water gas is varied with hydrogen, and the combination is purified by transitory
from side to side Fe2O3 and then into a mixture of Fe2O3+Na2CO3. The cleanse gas is dense to 5
to 25 atm and then led from side to side a converter, which is preserved at a temperature of 200-
300 oC. The converter is provided with a catalyst bed consisting of a mixture of 1000 parts cobalt,
5 parts thoria, 8 parts magnesia and 200 parts keiselghur earth.

nCO + 2nH2 = CnH2n+ nH2O

nCO +(2n+1)H2 = CnH2n+2 + nH2O

The outcoming gaseous mixture is led to a condenser, where the liquid crude oil is obtained, The
crude oil is fractionated to yield gasoline and heavy oil. The heavy oil is used for cracking to get
more gasoline.

Fig. Schematic diagram of Fischer- Tropsch Process

4.6 Gaseous fuels
Biogas
Biogas is a type of biofuel that is naturally produced by the decomposition of organic waste. When
organic matter, such as food scraps and animal waste, break down in an anaerobic environment
(an environment absent of oxygen) they release a blend of gases, primarily methane and carbon
dioxide. Because this decomposition happens in an anaerobic environment, the process of
producing biogas is also known as anaerobic digestion

Biogas digesters receive organic matter, which decomposes in a digestion chamber. The digestion
chamber is fully submerged in water, making it an anaerobic (oxygen-free) environment. The
anaerobic environment allows for microorganisms to break down the organic material, and convert
it into biogas. Biogas is a renewable energy source.

Bio gas composition

Compound Formula %

Methane CH4 50–75

Carbon dioxide CO2 25–50

Nitrogen N2 0–10

Hydrogen H2 0–1

Hydrogen sulfide H2S 0.1 –0.5

Oxygen O2 0–0.5
Applications
Biogas can be used for electricity production, cooking, space heating, water heating and process
heating. If compressed, it can replace compressed natural gas for use in vehicles, where it can fuel
an internal combustion engine or fuel cells.

4.7 Summary
In this chapter, the types of fuels based on their origin and physical state and their characteristics
are discussed. Chemical fuel is a material that stores chemical energy in forms that can be
practically released and used as thermal energy. The calorific value of a substance is the amount
of heat released when its specific amount undergoes combustion. Crude petroleum is processed
and refined into more useful fractions such as gasoline, diesel fuel, kerosene and liquefied
petroleum gas. Quality of gasoline is upgraded through reforming and cracking processes.
Synthetic petrol and their production methods are studied. Production of bio-gases and their
applications are discussed.
Questions:

1. What is reforming? Explain the vinous reforming processes with relevant reactions.

2. How is percentage of sulphur estimated in a coal sample?

 Materials Science and Engineering

Introduction and basic principles

Everything around us is made up of materials, and they are basic substances that have
mass and occupy space. The air we breathe, the water we drink and the food we eat and so on.
They can be natural or human-made. Natural materials are materials that come from animals,
plants and rocks and manufactured materials are those obtained from natural materials through
chemical processes. A wide range of materials in nature form an essential part of the ecosystem
in multiple ways. The materials that are used not only in the field of engineering, but on a day
to day basis because of their properties are called engineering materials. Material engineers
develop and test new materials for different specific applications. A wide range of new products
like computer chips, recreational equipment (golf clubs, bicycles), and building materials for
houses, bridges, cars, and aircraft will be created. Advanced materials refer to all new materials
and modifications to existing materials to obtain superior performance in one or more
functional features that are critical for the application under consideration. The functional
materials perform specific functions within a system. Some recent advances include shape
memory alloys and nanomaterials. Supermaterials of the future include aerogel, carbon
nanotube, transparent alumina, e-textiles, metamaterials, nano-diamond and amorphous metal.
Graphene is the thinnest material ever invented-only one atom thick yet stronger than steel.
Every material has a set of physical and chemical properties that define it. The physical
properties include melting point, boiling point, color, hardness, density and so forth. The
chemical properties include reactivity with water, oxygen, acids, bases, and others.
Traditionally, materials were developed keeping in mind a particular set of properties and were
mainly used for making components and structures. With the advancement of materials
science, they are expected to perform the role of an ‘intelligent’ structure. An excellent example
of this would be applications of shape memory alloys, and they can be used to make deployable
antennas. These materials enable people to explore the design and use of new products to
improve the quality of life. Modern materials are employed in the primary production or
manufacturing of a good, and there are about 3,00,000 different known materials. These include
specialty and bulk chemicals, beverages and food products, metal products and alloys, wood
and paper products, rubber and plastic products, textile and consumer goods, and those used in
mining and metallurgy, and printing and publishing industries.

1
 The kind of questions that a student in materials science would like answers to include
the following; What is the densest crystal packing that can be achieved? How do intermolecular
attractions arise? Why is glass transparent and brittle while copper opaque and ductile? Why
is a diamond an efficient thermal conductor, but electrical insulator? Why is it easier to bend
the Al rod as compared to the steel rod? Why is a wire of copper conducting, while a piece of
dry wood non-conducting? How can we change properties like hardness, flexibility,
biocompatibility in a material? Why does the electrical conductivity of Ag decrease on heating,
while that of Si increases? Why does naphthalene (para-dichlorobenzene) solid evaporate?
How can we explain the fact that good thermal conductors are also good electrical conductors?
How can one understand the observations that when we release the load on a rubber
band/spring, it comes back to its original shape while a bent aluminum rod would not come
back? Why is it essential for some objects being transparent? Why is glass transparent to visible
light, but opaque to UV light? Why can aluminum oxide exist as a transparent, translucent or
opaque a material? What are the reasons for the viscosity of honey, mercury and paraffin oil?
Why are composites used instead of metals, ceramics, or polymers? What is the mechanism
behind functional smart materials? What does material science offer to society? Who can deny
the role of materials in human existence? The answers to such questions could lead the learner
to take the subject to higher levels of understanding, an understanding of the complex structure-
property relationships, molecular mechanisms of material transformations, the development of
an active system, to arrive at practical science-based solutions, and finally better materials
management solutions.

Materials technology includes a range of materials used for manufacturing products,

machines, and structures. For example, plastics are used in solid form as synthetic fibers for
textiles, a film for packaging and in composites like fiberglass. Metals like iron or aluminum
continue to be essential for building machines and structures. Concrete is the prime material
for building civil structures such as bridges. Some building materials like steel, concrete, and
bricks are structural while others, such as ceramics and glass are mainly decorative.
Appropriate technology serves local needs using local resources such as stone and wood.
Rubber is used for the soles of shoes and motor tires because of its resilience and elasticity. It
is also used in rubber gloves and rainwear due to its flexibility and waterproof property. Plaster
of Paris (POP) has the distinct feature of setting into a hard mass on wetting with water. It is
used to make castings for statues, toys and decorative materials, for setting broken or fractured
bones in the right position and as a fireproofing material. Thin-film materials are used

2
extensively in sensor applications. Thin film solar cells like amorphous silicon, cadmium
telluride, copper indium gallium selenide and dye-sensitized solar cells are other examples of
important novel materials. The nano-scale effects on sterical and biological properties include
increased selectivity for specific drug transportation and controlled release, increased
permeability through membranes, and improved biocompatibility. The role of materials science
research, technology and innovations extend to almost all fields of human activity, and this
particular domain has a transformational effect on the development in many areas which
include healthcare, food processing, housing, energy, metals and minerals, and aerospace. The
future of materials engineering is to obtain optimal performance by combining material design
innovation with advances in technology involving several smart features.

Some materials are hard; others are soft. Some are strong; others are weak. Different
materials have various properties because they contain different elements (atomic structure)
and various combinations of ingredients, contain different types of chemical bonds (bonding
between atoms and molecules, have different sizes of units (crystalline structures). The solid-
state structure (microstructure + macrostructure) may include different types of assemblies,
e.g., molecular packing arrangement may be different, or the geometry of linkage in an
extended 3D structure may vary. Physical properties include mechanical and thermal properties
(hardness, tensile strength, influence of coating, velocity of sound, thermal data and
thermodynamic properties, thermal conductivity), electrical and magnetic properties (electron
paramagnetic resonance, nuclear magnetic resonance, electrical conductivity, switching effect,
thermoelectric power, magnetic susceptibility, magnetoresistance, optical and spectroscopic
properties (index of refraction, dielectric constant, infrared spectra, Raman spectra, absorption
in UV and visible range (EMR), photoconductivity, color dichroism, photoluminescence, The
chemical properties include reactions of atoms, adsorption of gases, reactions with
hydrogen/halogens, and reactions with main group/transition metals. The following factors put
together determines the properties of the material; composition, phases present and their
distribution, defect structure (in the phases and between the phases) and residual stress. The
properties of materials also depend on the properties of individual components, the relative
amount of particles, their size, shape, distribution, orientation and the degree of bonding. The
goal of materials science and engineering is to design materials with a predetermined set of
properties using suitable processing techniques, which gives them a particular microstructure
and desired performance. The role of engineers has become very important for meeting the
complex and specific challenges of making materials with desired functional characteristics

3
and solve technical issues with a specialized skill set and knowledge. The specific objective of
this chapter is to provide students the vast subject in a structured and useful manner to equip
them with a basic familiarity with materials science and engineering. It is a learning journey
through the fundamental principles underlying the materials science and engineering and
provides the essential vocabulary of these engineering sciences through inspirations,
experiences, practices, and evolutions.

Classification of Materials

All materials used for engineering application can be put into six broad categories;
pure substances (Cu, Ni, Fe), alloys (brass, NiAl), polymers (polyethene, polyvinyl chloride,
polypropylene) ceramics (alumina, glass, zirconia), composites (wood, golf club shaft, bricks),
and miscellaneous materials (lime, gypsum, tiles). The common types of engineering materials
can be classified into different categories based on various parameters. Based on phase (state
of matter) a given material can be divided into gases, liquids or solids. The solid state is a rigid
state, the particles of liquids can move with greater freedom and gas particles have total
freedom of motion. What distinguishes the crystalline state from the liquid and gaseous states
is the nearly perfect positional order of the particles in crystals. Based on the structure of
particles (arrangement of atoms/molecules/ions) materials can be classified into crystalline
(quartz), quasicrystalline (Al-Pd-Mn alloy) or amorphous (glass). Liquid crystals and solid
electrolytes have the properties in between liquids and crystals. Supercritical fluids have
properties in between liquids and gases. Homogeneous materials include pure substances and
solutions that have fixed, specific features. Heterogeneous materials can be separated into their
components by purely mechanical means such as filtration, decantation, extraction,
centrifuging and so on. Based on the size of the particles in question we can find nanocrystals,
nano-quasicrystals, and bulk materials. Materials can be divided into paramagnetic,
diamagnetic, ferromagnetic, ferrimagnetic, and antiferromagnetic materials based on the
magnetic states of matter. Based on electrical conduction, we can categorize the materials into
conductors (Cu, Al, Ag), semiconductors (Ge, Si, GaAs) and insulators (Al2O3, -(CH2-CH2-)n).
Based on ductility, we can have two categories- ductile (metals, alloys) and brittle (ceramics,
glasses). Materials can be acoustic conductors (bronze) or acoustic insulators (cotton fiber)
based on the capacity to transmit sounds. Materials can be classified based on the behavior
when light strikes as transparent (clear glass windows, clear plastic food wrap), translucent
(frosted glass, wax paper) and opaque materials (aluminum foil, wood). Based on the bonding,

4
solids can be classified into ionic (table salt, calcium chloride) molecular (ice, solid carbon
dioxide) covalent network (diamond, quartz), and metallic solids (iron, silver). There are other
categories of materials such as raw materials, in-process materials, finished products, bulk
materials, value-added products, and packaging materials. Further classification of chemicals
includes bulk chemicals (sulfuric acid), fine chemicals (ibuprofen) and specialty chemicals
(adhesives).

Metals can be further classified into ferrous (steel, stainless steel, cast iron) and non-
ferrous (aluminum, copper, tungsten) metals. Plastics can be further subdivided into
thermoplastics (polyethene, polyvinyl chloride, teflon), thermosets (bakelite, melamine,
vulcanized rubber) and elastomers (natural rubber, silicones, styrene-butadiene rubber) based
on the response to heat. They can be classified into linear, branched, cross-linked (based on
molecular structure), natural, semisynthetic, synthetic (based on origin), addition and
condensation (based on the method of formation), plastics, elastomers, fibers and resins (based
on applications). Ceramic materials can be categorized into glasses, clay products, refractories
(acid, neutral, basic) abrasive materials, cement and advanced ceramics by an application.
Composites are classified according to the matrix material into ceramic, metal, and polymer
matrix materials, and based on reinforcement geometry into particulate-reinforced, fiber-
reinforced and structural composites. Liquid crystalline materials can be subcategorized into
calamitic, discotic, polycatenar, and bent-core types based on the shapes, and thermotropic and
lyotropic liquid crystals based on the response to temperature or concentration. The
classification of smart materials includes piezoelectric, electrostrictive, magnetostrictive,
thermoelectric, shape memory alloys, photochromic and thermochromic materials. The
classification of biomaterials based on the materials used include polymeric, metallic, ceramic
and composite categories. Nanomaterials could be of natural or synthetic based on origin and
zero, one, two and three-dimensional based on dimension. Electronic materials are classified
into conductors, superconductors, semiconductors, and dielectrics. Based on their behavior in
an applied field, superconductors are classified into two types; Type-I – soft and Type-II -hard.
There are nine classes of hazardous materials; explosives, flammable gases, combustible
liquids, flammable solids, oxidizers, toxic, radioactive, corrosive and miscellaneous materials.

The research and development of various kinds of materials have been exponential, and
in the future, these types of materials will be used more extensively to meet the needs of the
society. Material design is of vital importance in the development of different functional
engineering systems, and it depends on multiple factors, including certain microscopic

5
structural features, texture, sizes, shapes, and density. Understanding how structural patterns
are controlled and how that affects the properties gives engineers greater insight into the
preparation of materials with predetermined properties. The materials have conveniently been
grouped into various classes, and a combination of these materials will give a variety of other
new materials. Apart from the standard categories of materials, future materials include smart
materials, nanomaterials and advanced materials for specialized applications. There is a need
for well-planned effort to synthesize and explore materials with unique property and use. This
overview of the topic should make us think about the identity, composition, structure of
materials in question and study the structure-property relationships, mechanism of change and
its control, and finally the question about benefits, costs, and risks involved. We also have to
take into consideration the ecological properties related to the impact they have on the
environment and the function of biological systems can be exploited to find meaningful
solutions to engineering problems. The qualities of successful material design include material
quality, desired characteristics, ease of use, precision, attractiveness, cost of manufacture,
development cost, development time, and enhanced development capacity. A multi-step
investigation by researchers, exploration of eco-friendly approaches, preparation of semi-
synthetic materials, and preference to use of local materials would go a long way in promoting
sustainable and responsible discovery of novel materials and the development of new
technological methods. We can achieve success in offering world-class materials through our
expertise and experience by doing exceptional and result-oriented, hard work involving
systematic and target-based planning with predictable outcomes. The quality of materials and
their performance in processes and systems is probably the surest guide to the quality of
research in materials science and engineering. These multiple perspectives might help the right-
thinking people ask the right questions on the topic and to create future ideas, innovations and
stable, sustainable, smart and high-quality materials that power the world through the scientific
transformation and paves the way for severe developmental changes.

Effect of Bonding on Properties

The two important contributing factors to the properties of materials are the atomic
structure and the nature of bonding. The properties of solids depend both on the arrangements
of particles and on the attractive forces between them. A chemical bond is defined as a force
that acts between two or more atoms to hold them together in a stable arrangement. Bonding
in materials could involve strong interactions such as ionic, covalent and metallic bonds and
weak interactions like van der Waals forces and hydrogen bond. Solids can be classified

6
according to the nature of the bonding between their atomic or molecular components into ionic
solids, covalent network solids, molecular solids and metallic solids. Typical examples of these
classes have distinctive electron distributions and binding energies, and thermodynamic,
electronic, and mechanical properties. We have to note that this is not a rigid classification
scheme and bonding in solids can be of mixed or intermediate kinds.
Ionic bond: A net electrostatic attraction between the positive (cation) and negative (anion)
ions formed by transfer of electrons from metal to a non-metal atom constitutes an ionic bond
(electrovalent bond). There are no rigid, directional bonds in an ionic material and the strong
ionic bonding continues throughout the solid crystal resulting in giant structure. Some
examples of ionic compounds include MgCl2, CaO, ZnS, Al2O3. The characteristic properties
of ionic compounds are the following; They are solids at room temperature. The crystals of
ionic solids are hard and brittle. They possess high melting and boiling points. They do not
conduct electricity in the solid state but are good conductors of electricity in the molten state
or aqueous solution. They are soluble in polar solvents, but insoluble in nonpolar solvents.
They do not exhibit isomerism. More common structures are the Rock salt structure which has
a face-centered cubic (f.c.c.) unit cell and the Cesium chloride structure, which has a body-
centered cubic (b.c.c.) unit cell. Less common structures include the Zincblende structure,
Wurtzite, Fluorite, and Rutile structures. An ionic solid consist of cation and anions arranged
in such a way that each ion is surrounded by as many nearest neighbours of opposite charge as
possible and there is local neutralization of charge. There could be partial ionic character in
predominantly ionic bonds in compounds with large anions, small cations, high charge on one
of either ion, and non-noble gas electron configuration of the cation.

Covalent bond: Covalent bonds are formed by an overlap of atomic orbitals and mutual
sharing of electrons. A covalent bond is typically formed by two non-metals having similar
electronegativities and each bonded atom may contribute one electron to the shared electron
pair or one atom may contribute both electrons. Covalently bonded compounds usually form
molecular structures. Molecular solids are collections of distinct molecules held together by
intermolecular forces such as dispersion forces, dipole-dipole forces, and hydrogen bonds.
Typical examples of covalent molecular crystals include the noble gases, oxygen, nitrogen, the
halogens, CO2, H2O, C12H22O11, I2, and the vast majority of organic compounds. Depending on
the number of shared electrons covalent bonds can be single (F2), double (O2) or triple bond
(N2) types. The common spatial arrangements of atoms in covalent molecular solids include
linear, angular, trigonal plane, trigonal pyramid, tetrahedron, square plane and octahedral

7
structures. A covalent network solid has atoms at the crystal lattice sites that are linked together
by covalent bonds into a three-dimensional array, e.g. C (diamond), SiO2 (quartz). These solids
are hard and high melting. Silica is the most abundant covalent solid in nature and carborundum
(SiC) is the most common synthetic solids. The characteristic properties of covalent molecular
compounds are the following; they are gases, liquids or solids at room temperature. Covalent
solids are soft and easily deformed. They have low melting and boiling points. They are soluble
in organic solvents. They are rigid and directional and can cause stereoisomerism. They do not
conduct electricity in any state.
Metallic bond: The bonding which holds the metal atoms firmly together by force of attraction
between metal ions and the mobile electrons is called metallic bond. Typical examples of
metals include Na, Fe, Cu, Mg and Al. A metallic solid has metal atoms that occupy the crystal
lattice sites in hexagonal close-packed (h.c.p.), cubic-close-packed (c.c.p.) or body-centered
cubic (b.c.c.) structures. If many metal atoms are brought together, the outer electrons of each
can merge together and overlap. These valence electrons are shared by nuclei of all the atoms
that make up the solid (giant structure). These electrons have become delocalized and hence
more stable. A block of metal can be thought of as an array of positive ions immersed in a sea
of delocalized electrons. The great cohesive forces resulting from the delocalization is
responsible for the great strength noted in metals. The type of bonding found in metals involves
the manifold of closely spaced sublevels that can be regarded as a band. Using the band theory
of metals, we can explain the properties of metals. The characteristic properties of metals
include the following; they have bright metallic lustre. Metals are malleable and ductile. They
have high electrical and thermal conductivity. The melting points vary according to the
efficiency of metallic bonding and highest melting elemental metal, tungsten melts at 3410 oC.
Those elements with intermediate electronegativity, exist as solids on the border between
metallic and covalent, called metalloids. Silicon and germanium are semiconductors, with
electrical conductivities significantly lower than those of metals, but far higher than those of
true insulators like a diamond.
Intermolecular forces: To explain the properties of different materials, it is necessary to
consider several types of intermolecular forces. These bonds are weaker than the intramolecular
covalent bonds (for example, it takes only 1.2 kJ to overcome a mole of Ar-Ar interatomic
attractions but it takes 239 kJ to break a mole of Cl-Cl covalent bonds). Intermolecular forces
are much less directional than covalent bonds and they operate at longer range than covalent
bonds. It is useful to distinguish types of forces based on their strength, directionality, and
range. It exists in the inert gases, and between molecules in covalent molecular solids that arise
8
from atomic or molecular dipoles. All inert gas materials are gaseous at high temperatures as
the high kinetic energy of the molecules disrupts all possible attractions. At lower temperatures,
where materials are in the liquid state, molecules are close together and details of the
intermolecular potential energy determine the properties of materials. The physical properties
of molecular solids and liquids are because of intermolecular forces. The boiling and melting
points of different substances reflect the strengths of the intermolecular forces. The stronger
the intermolecular attractive forces, the higher is the boiling point of the liquid and the melting
points of solids increase as the strengths of the intermolecular forces increase. The types of
intermolecular forces include hydrogen-bonding forces, London dispersion forces, dipole-
dipole interactions, and ion-dipole forces. The first three types are also known as van der Waals
forces and all are electrostatic in nature.
Hydrogen bond: The electrostatic attraction between an H-atom covalently bonded to a highly
electronegative atom X such as nitrogen, oxygen or fluorine and a lone pair of electrons on X
in another molecule is called hydrogen bonding. The compounds like H2O, NH3, and HF have
abnormally high boiling points because of hydrogen bonding. Water has a high melting point,
a high specific heat and a high heat of vaporization because of the abnormally strong
intermolecular forces between water molecules. The hydrogen-bond attraction can occur
between molecules (intermolecular) or within different parts of a single molecule
(intramolecular). The examples of intermolecular hydrogen bonding include (HF)n, (H2O)n,
(NH3)n and (CH3COOH)2. The examples of intramolecular hydrogen bonding include o-
nitrophenol, 2-nitrobenzoic acid and o-fluorophenol. Though the H-bonds are weak forces,
they are strong enough to influence physical properties such as boiling points, solubility,
viscosity, and crystal structure. The energy associated with hydrogen bonding lies in between
15 to 40 kJ/mole, and they are much weaker than ordinary chemical bonds. These bonds help
stabilize the structure of proteins and DNA in biological systems. Ice floats on the top of the
water when a lake freezes in winter because of its lower density compared to liquid water,
thereby insulating the water below and protecting most of the aquatic life. Hydrogen bonds
tend to be the strongest type of intermolecular force.
Ion-dipole forces: This type of force exists between an ion and the partial charge on the end
of a polar molecule, e.g. KBr/NaCl in water. The negative ions are attracted to the positive end
of a dipole, and positive ions are attracted to the negative end. These are important for solutions
of ionic substances in polar solvents.
Dipole-dipole bonds: The strongest secondary bonding type exists between adjacent polar
molecules. The associated binding energies are significantly higher than for bonds involving
9
induced dipoles and they are weaker than ion-dipole forces. HCl, H2S, and CH3Cl are some
examples of polar molecules. For molecules of approximately equal mass and size, the
strengths of intermolecular attractions increase with increasing polarity. The positive end of
one dipole attracts the negative end of the other. There is the overall effect of net attraction
between the polar molecules because two molecules that are drawing each other spend more
time near each other than do those that are repelling each other. Generally, such attractions are
about 1 % as strong as a covalent bond. The boiling point increases as the dipole moment
increases. They are sufficiently strong to influence melting points, and molecular orientations
in solids.
Dipole-induced dipole bonds: Permanent dipole moments exist in some molecules by an
asymmetrical arrangement of positively and negatively charged regions. The polar molecules
will induce a dipole in adjacent nonpolar molecules, and a bond will form as a result of
attractive forces between the dipole and induced dipole. The magnitude of this interaction
depends on the magnitude of the dipole moment of the polar molecule and the polarizability of
the non-polar molecule. Eg. Solution of polar solutes in nonpolar solvents.
London forces: A dipole may be created or induced in an atom or molecule that is normally
electrically symmetric; that is, the overall spatial distribution of the electrons is symmetric with
respect to the positively charged nucleus. All atoms are experiencing constant vibrational
motion that can cause instantaneous and short-lived distortions of this electrical symmetry for
some of the atoms or molecules and the creation of small electric dipoles. One of these dipoles
can, in turn, produce a displacement of the electron distribution of an adjacent molecule or
atom, which induces the second one also to become a dipole that is then weakly attracted or
bonded to the first. The momentary attraction between the molecules of a liquid caused by the
instant dipole and induced dipole are called London Forces. These attractive forces may exist
between large numbers of atoms or molecules, which forces are temporary and fluctuate with
time. Liquefaction [e.g.Ar(l)] and, in some cases, the solidification of the inert gases and other
electrically neutral and symmetric molecules such as H2, I2 (s) and Cl2 are realized because of
this types of bonding. Melting and boiling temperatures are extremely low in materials for
which induced dipole bonding predominates; of all possible intermolecular bonds, these are
the weakest. Dispersion forces operate between all polar and non-polar molecules. Polar
molecules experience dipole-dipole interactions in addition to dispersion forces. The dispersion
forces are approximately equal when the molecules have comparable molecular weights and
shapes. The strength increases with increasing molecular weight, though molecular shape is
also an important factor.
10
The Road Ahead
It is essential to study the effect of several environmental conditions such as heat,
radiation, carbon dioxide, oxygen, water and various pollutants in finer detail to obtain the full
picture. The study may reveal the number of critical molecules that can be exploited for both
creating new materials and functional purposes. Finally, better technology using the finest
ingredients and expert techniques to create innovative materials with practical utility and
responsible sourcing becomes critical in this age of specialized domain expertise. Long-term
stability and safety standards for new materials matters in some applications. The microscopic
details make all the difference in the material world that turn ideas, dreams and the future into
reality. Innovating in finding new ways of adding value to unique products makes the complex
systems more efficient and make a positive transformation of society. Advanced material
characterization remains a challenge because of several factors, including structure related
(molecular geometry, 2D structure, perovskite structure), bonding pertaining (bond length,
angle, strength, order), and condition/treatment-related (pressure, temperature, radiation)
factors. Regular follow up of processes is essential from three perspectives. First, to understand
if the method is working and what is the progress of material formation. Second, it helps to
modify the method or alter treatment conditions based on the improvement. Lastly, if there are
undesired events, necessary actions can be taken to prevent those. The sophisticated techniques
such as wide angle X-ray diffraction, field emission scanning electron microscopy (FE-SEM),
tensile strength tester, simultaneous TG-DTA/DSC apparatus, and acoustic material testing
with impedance tube are used for characterization of final stable material. It remains to be seen
that a multipronged approach to preparing modern materials soon could lead to better systems
to enable sustainable development and the material progress of human beings.

11
 Polymers
The word polymer is derived from two Greek words, poly and meros, where poly means many
and meros means parts. Polymers are giant molecules formed by the combination of several
simple molecules having two or more binding sites linked through covalent bonding.
H H
H H
Polymerisation
n C C C C
H H n
H H
Ethene Polythene

The simple molecules which are repeating units of the polymer, are called monomers.
Eg: Polythene is formed by the combination of several ethene (ethylene) molecules.
Degree of polymerization (DP): Degree of polymerization is the number which expresses the
total number of repeating units (n) in the polymer chain. Polymers with large number of
repeating units are called high polymers and those with lower number of repeating units are
called oligomers.
DP is used to determine the molecular weight of the polymer by multiplying the number of
repeating units (n) with the molecular weight of repeated unit.
Functionality: The total number of functional groups, bonding sites or reactive sites present in
the monomer is called the functionality of the monomer. The reactive functional groups can be
–OH, -COOH, -NH2, -SH , –NCO etc.
Eg: In CH3CH2OH one reactive - OH group is present, hence functionality is one (
monofunctional)
HO- CH2 -CH2 – OH has two – OH groups hence bifunctional
HOOC CH2 CH (COOH) CH2 COOH has three -COOH groups, hence trifunctional
The presence of double or triple bonds in the molecule imparts polyfunctionality to the
molecules.
Eg: Ethylene - due to the presence of a double bond, it can take on two atoms of hydrogen or
halogens. Depending upon the functionality of the monomers used linear, branched or three
dimensional cross-linked polymers are formed.
Classification of polymers
Polymers can be classified in several ways, based on their
➢ origin
➢ structure
➢ methods of formation
➢ response to heat and crystallinity
➢ properties (or applications)
Based on their origin, polymers are broadly classified as
(a) Natural polymers (b) synthetic polymers.
Natural polymers are those which are obtained naturally. Eg: Cellulose, Silk, Starch
Synthetic polymers are those which are man-made. Eg: polythene, PVC, polyster, etc.
Semi-synthetic polymers are chemically modified natural polymers. Eg: cellulose acetate,
cellulose nitrate, halogenated rubbers etc.
Based on their molecular structure, the polymers can be classified as
(a) Linear (b) Branched (c) Cross-linked
If all the monomeric units are identical and combine linearly with each other to form a polymer,
it is called a linear homopolymer.
Eg. - M – M – M – M – M – M – M - …………
If the monomeric units are not identical, it is called a linear co-polymer.
Eg: -M – M1 – M – M1 – M – M1 – M - …………
If the linear co-polymers in which the units of each type form fairly long continuous sequences
(blocks) are called block co-polymers.
Eg., ………..- M – M – M – M - M1 – M1 - M1 - M1 - M – M – M – M – …………
If the linear polymer branches out, then it is called a branch polymer.
The polymers can be classified as follows, on the basis of their method of formation
(a) Addition polymers (b) condensation polymers
Addition polymers are formed by a process of self-addition of monomers without the elimination
of any byproducts. Eg: Polyethylene & synthetic rubbers.
Condensation polymers are formed by condensation reaction i.e., reaction between two or more
monomer molecules with the elimination of simple molecules like water, ammonia, HCl etc.,
Eg: Urea-formaldehyde resins, phenol-formaldehyde resins & polyesters.
The polymers can be classified on the basis of their response to heat as follows.
(a) Thermo softening (b) Thermosetting
The polymers, which soften on heating and can be converted into any shape, which they can
retain on cooling, are called as thermo softening or thermoplastic polymers. The process of
heating, reshaping and retaining the same on cooling can be repeated several times. Eg:
polyethylene, nylons , sealing wax.
The polymers which undergo some chemical change on heating and convert themselves into an
infusible mass are called as thermosetting polymers. Eg: bakelite, egg yolk.
Based on their application and properties polymers are classified as follows.
(a) Plastics (b) Elastomers (c) Fibers (d) Resins
Plastics are the polymers, which are soft enough at some temperature to be moulded into a
desired shape and hardened on cooling so that they can retain that shape. Eg: polystyrene,
polyvinyl chloride , poly methyl methacrylate.
Elastomers are polymers in which the structural units are either zig zag or helical chains. They
undergo elastic changes when subjected to an external force, but readily regain their original
shape when the force is withdrawn. Eg: natural rubber, silicone rubbers.
Fibres are characterized by their molecular chains arranged parallel to each other in a spiral or
helical pattern which do not undergo stretching or deformation and the molecular length is at
least 100 times its diameter. Eg: nylons, terylene.
Resins are much lower molecular weight polymers either in liquid or solid form used as
adhesives or moulding powders. It has a glossy appearance. Resins constitute the major essential
part of the plastics. Eg: Polysulphide sealants,epoxy adhesives.
Polymerization
Polymerization is defined as the process by which the monomer molecules are linked to form a
big polymer molecule .
Types of Polymerization:
Polymerization occurs basically in two different modes.
1. Addition (chain growth) polymerization
2. Condensation (step growth) polymerization
Addition polymerization: The reaction in which self-addition of several olefinic monomers to
each other takes place without elimination of by products is known as addition polymerization.
The addition polymerization must be initiated by using heat or light or pressure or catalyst for the
breakage of the double bonds of monomers.

Condensation Polymerization: The reaction in which monomers containing two or more

reactive functional groups (hydroxyl, carboxyl, amino) condensing with each other.

Distinguishing features of addition and condensation polymerisation

Addition polymerisation Condensation polymerisation

➢ Monomers undergo self ➢ Monomers undergo intermolecular

addition to eah other without condensation with continuous
loss of by products elimination of by products such as
H2O, NH3, HCl, etc.,

➢ It follows free radical

➢ It follows step mechanism
mechanism (Chain
mechanism)
➢ Monomers containing the functional
 ➢ Unsaturated vinyl compounds groups(-OH,-COOH,-NH2) undergo
undergo addition this polymerization
polymeristion ➢ Covalent linkages are through their
functional groups
➢ Monomers are linked together
through C – C covalent ➢ The reaction is slow and the polymer
linkages molecular weight increases steadily
➢ High polymers are formed fast throughout the reaction
➢ Linear or cross linked polymers are
produced
➢ Linear polymers are produced ➢ Examples: nylons, terylene, PF
with or without branching resins, etc.
➢ Examples: polystryrene,
plexiglass, PVC, etc.

Stereo regular polymers (Tacticity in polymers)

This classification is based on the position of the substituent groups in the polymer chain.
Depending on the position and regularity of the repeating substituent groups, three different
arrangements can be visualized- isotactic, syndiotactic and atactic.
Structure and properties of polymers
The structure of a polymer has profound influence on some of the properties of polymers .The
properties such as crystallinity, tensile strength, elasticity, resistance to chemicals and plasticity
depend mostly on the polymer structure and are discussed below.
Strength: This property is discussed based on forces of attraction and slipping power.
Based on forces of attraction: Strength of the polymer is mainly determined by the magnitude
and distribution of attraction forces between the polymer chains. These attractive forces are of
two different types viz., primary or covalent bond and secondary or intermolecular forces.
In case of straight chain and branched chain polymers, the individual chains are held together by
weak intermolecular force of attraction. But in these polymers, strength increases with increase
in chain length (increase in molecular weight) i.e., attains mechanical strength if the chain length
is greater than 150 – 200 carbon atoms in the chain. Less than these numbers, the polymers will
be soft and gummy, but brittle at low temperature. Intermolecular forces can be increased by
introducing polar groups like carbonyl & hydroxyl.

In cross-linked polymers, monomeric units are held together only by means of covalent forces.
Hence possess greater strength than straight and branched chain.

Based on slipping power: Slipping power is defined as movement of molecules one over the
other. Eg: polyethylene molecule is simple and uniform, hence movement of molecule one over
other is possible, i.e., slipping power is high. Hence it has lesser strength. But in case of
polyvinyl chloride (PVC), bulky chlorine atoms are present along the chain length hence,
movement is restricted, i.e., slipping power is less. Hence it has higher strength compared to
polyethylene. But in case of cross-linked polymer, movement is totally restricted because of the
presence of covalent bond. Hence these products are strong, rigid and tough.
Plastic deformation: When a polymer is subjected to some stress in the form of heat or pressure
or both, permanent deformation in shape takes place, which is known as plastic deformation.
This property actually helps in moulding of plastics. Slippage is more in case of linear molecules
than branched and cross-linked, because of the presence of weak intermolecular forces and hence
they show greatest degree of plastic deformation. At high pressure and temperature the vander
Waal‘s forces acting between molecules become more and more weak. No slippage occurs in
case of cross-linked polymers, because only strong covalent bonds are present throughout the
entire structure. However, when considerable external force or temperature exceeding the
stability of material is applied, it will result in total destruction.
Crystallinity: Based on the relative arrangement of polymer chains with respect to each other,
polymer can exhibit amorphous and crystalline nature. An amorphous state is characterized by
completely random arrangement of molecules and crystalline form by regular arrangement of
molecules. The crystallization tendency of a polymer depends on the ease with which the chains
can be aligned in an orderly arrangement. Crystalline regions of a polymer are formed when the
individual chains are linear (without branching), contain no bulky substituents and are closely
arranged parallel to each other. The chains of polymer may be held together by vander Waal‘s
forces, hydrogen bonding or polar interactions. A polymer with high degree of crystallinity will
have high tensile strength, impact and wear resistance, high density and high fusion temperature.
Polymers with a long repeating unit or with low degree of symmetry do not crystallize easily,
hence forms amorphous structure e.g., polystyrene. Crystallization imparts denser packing of
molecules due to increase of intermolecular forces of attraction. Such type of polymers will have
sharp softening point, greater strength and rigidity. e.g PVC, Polypropylene. Polymers are in
general, amorphous with some degree of crystallinity.
Chemical Resistance: Chemical resistance of polymer depends upon the chemical nature of
monomers and their molecular arrangement. A polymer is more soluble in structurally similar
solvent. For example, polymers containing polar groups like – OH, - COOH, usually dissolve in
polar solvents like water, alcohol etc but are chemically resistant to non-polar solvents. Similarly
non-polar compounds like hydrocarbons dissolve only in non-polar solvents like benzene &
toluene.
As a general rule, the tendency of solubility in a particular solvent decreases with increase in
molecular weight of the polymer- (i) high molecular weight polymer on dissolving yield
solutions of high viscosities (ii) crystalline polymers exhibit higher resistance than less
crystalline polymers of similar chemical character (iii) greater the degree of crystallinity, lesser is
its solubility.
Today several drugs and essential oils are stored in plastic bottles for long shelf life. If they
disintegrate or change in their chemical composition they may render the drug ineffective or
may cause it to react adversely when used, leading to specific disorder. Therefore, chemical
resistance of plastic bottles is important to prevent drug polymer interactions.
Elasticity: Elastic nature in polymers results due to the uncoiling and recoiling of the molecular
chains on the application of force. In an upstretched elastomer we can observe a peculiar
configuration of irregularly coiled and entangled snarls in a random fashion, indicating the
amorphous state. In a stretched state snarls disentangle and straighten out in a proper chain
orientation, indicating the crystalline state. The crystallinity in a stretched rubber band can be
observed from its opaqueness and warmth it produces when touched by lips. The main criteria
for a polymer to show elastic nature is that , the individual chains should not break even after
prolonged stretching. This can be done by introducing suitable crosslinking in the chains, by
allowing nonpolar groups or side groups in the repeating unit.
Glass transition temperature Tg
Amorphous polymers do not have sharp melting points. They possess softening point. At low
temperature, polymers exist as glassy substances. Since the molecular chains cannot move at all
easily in this state, the solid tends to shatter, if it is hit. If the solid polymer is heated, eventually
it softens and becomes flexible. This softness and flexibility is obtained at the glass transition
temperature. After this temperature, crystalline and amorphous thermoplastic polymers behave
differently. Heating has little effect on thermosetting polymers and at a high temperature, they
are destroyed.
So the glass transition temperature can be defined as the temperature below which an
amorphous polymer is brittle, hard and glassy and above the temperature it becomes flexible, soft
and rubbery.
Glassy state rubber state
(Hard brittle plastic) (soft flexible)

In the glassy state of the polymer, there is neither molecular motion nor segmental motion.
When all chain motions are not possible, the rigid solid results. On heating beyond Tg segmental
motion becomes possible but molecular mobility is disallowed. Hence flexible,
Factors affecting glass transition Temperature
Glass transition temperature of a polymer depends on parameters such as chain geometry, chain
flexibility, molecular aggregates, hydrogen bond between polymer chains, presence of
plasticizers and presence of substrates in the polymer chains.
A polymer having regular chain geometry show high glass transition temperature, the bulky
groups on chain increases the Tg of the polymer. E.g., polyethylene has Tg -110 oC. The Tg is
quite low because there are no strong intermolecular forces and no bulky side groups are present,
the side chain is only hydrogen atom. But nylon 6 has Tg 50 oC because of the presence of large
number of polar groups in the molecule leading to strong intermolecular hydrogen bonding.
The Tg of a polymer is influenced by its molecular weight. However, it is not significantly
affected if molecular weight is around 20000. With increase in molecular mass, the temperature
(Tg ) will be higher.
In crystalline polymers the polymer chains are arranged in a regular parallel fashion. Each chain
is bound to the other by strong forces like H-bonding. Hence crystalline polymers have higher
Tg than amorphous polymers.
The added plasticizers reduce the Tg of the polymer by reducing the cohesive forces of attraction
between the polymers. e.g., dibutyl phthalate, diacetyl phthalate etc.,
The glass transition temperature is an important parameter of polymeric material. This helps in
choosing the right processing temperature. It is a measure of flexibility of a polymer and also
gives the idea of the thermal expansion, heat capacity, electrical and mechanical properties of the
polymer.
Molecular weight of polymers
A polymer comprises of molecules of different molecular weights and hence, its molecular
weight is expressed in terms of an ‘average’ value. Eg. In ethylene gas each of its molecules has
the same chemical structure and hence, a fixed molecular weight of 28. But upon
polymerization, it forms polyethylene and we encounter an indefinite chemical structure of --(-
CH2 – CH2 -)n—where ‘n’ can change its value from one polyethylene molecule to another
present in the same polymer sample.
When ethylene is polymerized to form polyethylene, a number of polymer chains start growing
at any instant, but all of them do not get terminated after growing to the same size. The chain
termination is a random process and hence, each polymer molecule formed can have a different
number of monomer units and thus different molecular weights.So a sample polymer can be
thought of as a mixture of molecules of the same chemical type, but of different molecular
weights.
In this situation, the molecular weight of the polymer can only be viewed statistically and
expressed as some average of the molecular weights contributed by the individual molecules that
make the sample.
So the molecular weight of a polymer can be expressed by two most and experimentally
verifiable methods of averaging - (i) Number – average and (ii) weight – average.
Number – average molecular weight: Number average molecular mass of a polymer can be
defined as the total mass of all the molecules in a polymer sample divided by the total number of
molecules present.
Weight – average molecular weight: The sum of the fractional masses that each molecule
contributes to the average according to the ratio of its mass to that of the whole sample.
White foam cups, clear plastic cups and ultrathin fishing line are made of polystyrene with
different average molar masses while styrofoam cups are made from beads of polystyrene with
an average mass of approximately 15000 g/mol. Clear plastic cups are made by melting
polystyrene with average mass of approximately 250000 g/ mol. Ultrathin fishing lines are
composed of polystyrene with an average mass of 1000000 g/ mol.

Application of Average molecular mass (AMM)

It is used to characterize a polymer. Samples of the polymer prepared under different conditions
may have different AMM. It affects the mechanical, solution & melt properties of the polymer.
Chain length is related to the ease of processing of the polymer. The longer the chain, the more
difficult the melt is to process. The polymer chain becomes more entangled as the molecules get
larger and offer more resistance to flow at the molecular level. In most applications, the polymer
must be able to flow so that it can be flattened into sheets, moulded into bottles and so on.
Numerical Problems
1) Calculate the number average & weight average molecular weight of a polymer sample in
which 40 % molecules have molecular mass of 25000, 20 % have molecular mass of
30000 & rest have molecular mass of 55000.
2) A polymer sample contains 1, 2, 3 & 4 molecules having molecular weight 105, 2x 105 ,
3x 105 and 4x 105 respectively. Calculate the number average & weight average
molecular weight of the polymer.
6.3 Liquid crystals
Liquid Crystals (LC) possess properties of both the conventional liquids and solid crystals. They
find application in the areas of science and engineering, particularly in display systems of modern
electronic gadgets. Devices using liquid crystal displays have the advantage of low power
consumption and hence are widely used in display devices of mobile communication appliances,
aircraft cockpit, laptops and other electronic equipments.
In a crystalline state, the molecules (or atoms) are having a definite position and orientation in
space in a regular repeated manner in a rigid arrangement and are immobile. They tend to orient
in a preferred direction i.e., the molecules in solids have a positional and orientational order. In
the liquid state, the molecules neither occupy specific positions nor remain oriented in a particular
manner. The molecules are somewhat free to move at random and collide with one another,
abruptly change their positions. The liquids have neither positional order nor orientational order.
A liquid crystal (LC) is a state of matter exists between solids and liquids with both the properties.
Normally when a low molar mass solid melts, it forms an ordinary liquid and is isotropic. Organic
substances which are geometrically anisotropic i.e., long and relatively narrow molecular shape
exhibits this intermediate state of order between solid crystals and isotropic liquids. They undergo
more than a single transition in passing from solid to liquid through different intermediate states
on heating. These intermediate states with different molecular ordering are also known as
mesophases, derived from a Greek word, mesos meaning middle. In mesophase state either the
individual molecules align with respect to each other or exhibit some regular position with respect
to each other. The molecular arrangement in solids, liquid crystals and liquids can be represented
as below.

In a liquid crystal, the molecules possess orientational order, i.e., the molecules tend to remain
oriented in a particular direction. The direction of preferred orientation in a liquid crystal is called
the director ( n ) and may be imagined to be directed towards the top or bottom of the page. Since
the molecules are in constant motion, in liquid crystal phase they spend more time pointing along
the director than along any other direction. The extent of orientational order can be described by
taking an average. An average of 0° indicates perfect orientation and can be expected in solids.
An average of greater than 45° indicates no orientational order and found in liquids. However, in
liquid crystals, a smaller average angle with the director is observed which indicates orientational
order.
The quality of any device using LCs depends mainly upon the physical properties of the LC
molecules. To achieve a high performance of the LC device, it is essential to select the most
appropriate LC material according to the specific requirements of the desired device. In general,
the LCs must satisfy the following characteristic properties
a. Liquid crystalline nature should be at room temperature and the entire temperature
range of the device operation
b. Chemically, electrochemically, photochemically and thermally stable
c. Permanent electric dipole
d. Should possess easily polarizable substituents

6.3.1 Classification of Liquid Crystals

Based on the response to temperature or concentration, Liquid Crystals are broadly
classified as
❖ Thermotropic LCs
❖ Lyotropic LCs
The liquid crystalline substances which undergo transitions by variation in temperature are
called thermotropic LCs. Eg. p-azoxyanisole. The liquid crystalline substances which undergo
transitions by the influence of solvents are called lyotropic LCs. Eg. sodium stearate. Both these
systems can be characterized by anisotropic viscous, electrical, optical and mechanical properties.
Organic molecules, which are able to form thermotropic as well as lyotropic mesophases, are
termed as amphotropic LCs.
Thermotropic Liquid Crystals: Based on the mesophase, the TLCs are further classified as
a. nematics
b. smectics
c. columnar
d. cubic
Nematic: The properties of this phase are very close to liquid or they possess most liquid-like
structure. The molecular axes are oriented parallel to one another, resulting in a long
range of an orientational order. They do not possess positional order.
Smectic: The properties of this phase are very close to solid. They possess layered structures with
many possibilities of the state of order inside the layers. They show long-range
orientational as well as partial positional order.
Columnar: Structures with columns consisting of parallel arranged disc-like molecules.
Cubic: Structures with micellar lattice units or complicated interwoven networks.
Based on the shape of the constituting molecules, the thermotropic LCs can be further classified
as
(i) Calamitic LCs
(ii) Discotic LCs
(iii) Polycatenar LCs
(iv) Bent (Banana ) LCs
Calamitic Liquid Crystals: The LC compounds possessing rod-like molecular shape belong to
this category. The general molecular structure of a calamitic LC is as given below.

Rʹ A L B L C L D Rʺ
Where A, B, C, and D are called the rigid cores (containing a phenyl, biphenyl, naphthyl,
cyclohexyl or five/six-membered heterocycles) of the molecule. In a Liquid crystal, there should
be at least one rigid core.
‘L’ is the linking group (an imine, azo, azoxy, ester, thioester, C=C, and C≡C)
Rʹ or Rʺ is the end group/chain (a halo group, cyano, nitro, alkyl or alkoxy groups)
Some examples of the calamitic LCs are given below.

C10F21

(perfluorodecyl)-decane
Discotic Liquid Crystals: Discotic compounds consist of flat and disc-like rigid cores which are
surrounded by flexible chains such as alkyl, alkyloxy or alkanoyloxy. These discotic molecules
can be stacked one over another in many ways so as to obtained different columnar structures like
hexagonal, rectangular or oblique symmetry. Within the columns, the molecules can have a certain
order or disorder. The general structure of discotic LCs can be represented with the following
cartoon picture.

In discotic liquid crystals, the molecular diameter (d) is much greater than the disc thickness (t) to
form anisotropy. A typical molecular structure of a discotic molecule is shown below.
 R R

R R

R R

where R=alkyl chain

Polycatenar Liquid crystals: Polycatenar mesogens are considered as a hybrid class of

thermotropic LCs, as its molecular features lie intermediate between classical rod-like and disc-
like mesogens. Schematically the central core of polycatenar LCs comprises a calamitic region,
with half-discs on the extremities. This hybrid molecular structure allows them to exhibit both
calamitic (nematics/smectic) and discotic (columnar) phases, depending on the specific molecular
structure of the components. E.g., the tetracatenar mesogens (shown below), at shorter chain
lengths exhibit nematic and/or smectic-C phases, while at longer chain lengths exhibit columnar
phases. The numbers of the flexible end chains of the core can be indicated by using the term,
m,n–polycatenary mesogen. The different polycatenar LCs can be represented with the following
schematic diagrams.

2,2-polycatenary mesogen 3,1-polycatenarymesogen

Bent (Banana) Liquid Crystals: Bent (Banana) shaped liquid crystals are constituted of two
mesogenic groups linked through a rigid core in such a way that the molecule is not a linear (as
shown in the following figure). The central rigid core (Z) may be a phenyl or biphenyl or naphthyl
group. The mesogenic groups attached to the central core are mostly the calamitic molecules
consisting of two (or more) aromatic rings with different linking groups (A, B, X, Aʹ, Bʹ, Xʹ) and
a terminal chain/a substituent in para position to the linking group of the aromatic rings. The angle
between the two calamitic wings (bending angle) is around 120°. In case of a benzene central
core, the mesogens are connected in 1 and 3 positions (i.e., meta position to each other). If the
central core is a naphthyl, the two calamitic wings are connected in 2 and 7 positions.

Z
X
X'

A
A'

B
H3 C
n B'
CH3
m

Lyotropic Liquid Crystals: Lyotropic liquid crystals are formanisotropic aggregates when
combined with a solvent, like water. The phase behavior is dependent on the concentration and
polarity of solvent and also on the temperature. Molecules which form lyotropic phases are usually
amphiphilic, having non-polar, hydrophobic "tails" at one end with a polar, hydrophilic "head" at
the other end. Some examples are sodium stearate (soap) and phospholipids. The concentration of
material in the solvent and the response of the amphiphile to the solvent environment dictate the
type of lyotropic phase formed. For example, in a polar solvent like water, micelles are formed in
which the hydrophobic tails assemble together and the hydrophilic heads groups are presented to
the solvent. When combined with a non-polar solvent such as hexane, an inverse micelle is formed
where the hydrophobic tails shield the hydrophilic head groups from the non-polar environment.
Under certain conditions, these micelles further aggregate to form more complicated assemblies,
such as lamellar and hexagonal Phases, which generate lyotropic liquid crystal phases. Lamellar
phases are particularly significant as they form the structural basis for biological membranes
Examples of Lyotropic liquid crystals and their phase structures

Sodium Sterate Phospholipid

Micellar aggregates and phase structures formed by Lyotropic liquid crystals are shown below.
6.3.2 Applications of liquid crystals:
Liquid crystal displays operate at low voltages (a few volts) and consume less power as
compared to other displays and hence are used in:
1. Liquid crystal displays: Used in display devices such as watches, calculators, mobile
telephones, laptop computers, and clocks.
2. Liquid crystal thermometers: Chiral nematic LCs reflect light and the color which is
reflected is temperature dependent.

6.3.3 Liquid Crystals in Display systems

The electro-optic effect of liquid crystals controls the brightness/darkness of the light emerging
from its elements and this is used in information displays. Information is passed on to the user
using LCs which control the brightness/darkness of the parts of a display. Liquid Crystal Displays
are available in many sizes and can be used to display numeric, alphanumeric and graphic images.
The numeric display has seven segments whereas alphabets are displayed using fourteen segments.
More complex graphic images are formed using pixels (picture elements) which are closely packed
array of dots in two dimensions.
A numeric display consists of seven segments for each digit. Light from the area of each of the
seven segments is controlled independently and is used to create any one of the ten digits. When
an electric field is applied to a segment, the liquid crystal in that segment undergoes deformation
(is activated) and when polarized light is incident, the light is modulated depending on the
deformation in that segment.
In twisted nematic displays (TND), the nematic LC is sandwiched between two ITO coated glass
plates with parallel (homogeneous) alignment of its molecular director with the glass walls.
However, the two glass plates are twisted by 90° relative to each other (as shown in the following
figures).

Electric field off Electric field on

In such geometry, the LC is forced to perform a 90° twist of the director resulting in a helical
structure. The distance between the plates, hence the thickness of the LC film, is typically 6–10
µm. To complete the TND unit, a pair of crossed polarizers is placed on the outer side of the glass
plates. In the absence of an external electric field, when linearly polarized light enters the device,
the LC film rotates the polarization of the light by 90°. Thus, the light reaches the second polarizer
with its polarization plane parallel to the polarizer axis and is transmitted. In this configuration,
the display appears bright (off-state). However, when an electric field is applied (on-state), the
90o twist in the cell is lost and the LC molecules reorient in order to align the molecular director
with the external electric field, causing the helical arrangement to be unwound. As a consequence,
the light passing through the LC film is not guided through 90° and is not able to pass through the
second polarizer. The display looks dark and the observer can see the black character on a silver
gray background.
Ceramics
The term “ceramic” comes from (Gk. Keramos- burnt matter) indicating that desirable properties of
these materials are generally achieved through a high-temperature heat treatment process called
firing. Ceramics consist of a combination of non –metallic substances, mostly silicates and metal
oxides. It is used to indicate refractories, glass, enamels, porcelain, bricks and abrasive materials. For
example, some of the typical ceramic materials include aluminum oxide, silicon dioxide, silicon
carbide, silicon nitride and, also, the traditional ceramics are those composed of clay minerals as well
as cement and glass. The chemical combination of different metallic and non-metallic elements gives
rise to ceramic materials with a variety of properties. They could withstand a temperature of 1500 to
2000C, but a particular application may require the metals to withstand the temperature up to
5000C.

For mechanical behavior, ceramic materials are relatively stiff and strong, very hard, brittle, highly
susceptible to fracture, higher stability, and higher melting points. Most of these are insulators like
other covalent materials. Some of the refractory materials are quite stable and are thus used as
structural materials in structures where resistance to high temperature and oxidation are essential, as
in furnaces for steel making and as glass making. About optical characteristics, Ceramics may be
transparent, translucent, or opaque, and some of the oxide ceramics (e.g.,Fe3O4) exhibit magnetic
behavior. These new materials affect our lives; electronic, computer, communication, aerospace and
a host of other industries rely on their use.

Classification of ceramic materials based on application

1. Glasses - products of fusion rapidly cooled to a rigid condition without crystallization.
They are noncrystalline silicates that contain other oxides. Optical transparency is the most desirable
properties of these materials. The most common uses for these materials are as ovenware, tableware,
oven windows because of their strength and excellent resistance to thermal shock. They also serve as
electrical insulators and as substrates for printed circuit boards and heat exchangers and regenerators.

2. Clay products- structural clay products, whitewares

Clay is the principal component of the whitewares and structural clay products. Structural clay
products include building bricks, tiles-applications in which structural integrity is essential. In the
whiteware ceramics group are porcelain, pottery, china and sanitary ware. Feldspar and quartz may
be added which influence the changes that occur during firing. Fireclays are hydrated aluminosilicates
of composition Al2O3.2SiO2.2H2O.

3. Refractories – fire clay, silica, basic, special materials :

These are the materials that are employed at elevated temperatures and often in reactive environments.
By composition and application, the four main subdivisions are fireclay, silica, basic and special.
Typical applications include furnace linings for metal refining, glass manufacturing, metallurgical
heat treatment and power generation.

3a. Acid refractories

They consist of mostly acidic materials like alumina (Al2O3) and silica (SiO2). They are not attacked
or affected by acidic materials, but easily affected by basic materials. They include substances such
as silica, alumina, and fire clay brick refractories. Fireclay bricks are used in furnace construction to
confine hot atmosphere and to insulate structures from excessive temperatures thermally.
3b. Neutral refractories
These are used in areas where slags and atmosphere are either acidic or basic and are chemically
stable to both acids and bases. The principal raw materials belong to but are not confined to, the M2O3
group. The typical examples of these materials are alumina (Al2O3), chromia (Cr2O3) and carbon.

3c. Basic refractories

The refractories that are rich in periclase, or magnesia (MgO) are termed basic; they may also contain
calcium, chromium, and iron compounds. These are used in areas where slags and atmosphere are
basic; they are stable to alkaline materials but could react with acids. The steelmaking process used
artificial periclase (roasted magnesite) as a lining material for the furnace.

4. Abrasive materials – metal oxides and nitrides:

The abrasives being hard and tough are used to cut, grind and polish other softer materials. Diamond,
SiC, Tungsten carbide are typical examples. The abrasives may be employed in the form of loose
grains, bonded to an abrasive wheel or coated on paper or fabric, used for sharpening knives and
polishing wooden surfaces.

5. Cement – Portland cement:

When mixed with water, inorganic cement forms a paste that is capable of assuming just about any
desired shape. The subsequent setting is a result of chemical reactions involving the cement particles
and occurs at the ambient temperature. For Portland cement is the most common hydraulic cement,
the chemical reaction is one of hydration. The produced mixture hardens into a solid mass on reacting
with water and provides the water-resistant product.

6. Advanced ceramics - composite materials, engine rotors:

Many of our modern technologies use advanced ceramics because of their unique mechanical,
chemical, electrical magnetic and optical properties and property combinations. Examples: ceramic
ball bearings, piezoelectric ceramics.

Properties to be considered:
1. Glass-ceramic materials have relatively high mechanical strength; low coefficient of thermal
expansion (to avoid a thermal shock) and high-temperature capabilities, excellent dielectric properties
and good biological compatibility, ease of fabrication. They serve as electrical insulators and as a
substrate for printed circuit boards.
2. In refractories, porosity must be controlled. Strength, load bearing capacity and resistance to attack
by corrosive materials all increase with porosity reduction. Any residual porosity will have a
damaging influence on both elastic properties and strength.

Mechanical properties of ceramics:

Mechanical properties of ceramics are inferior to Metals.
Energy absorption is low. Strength and melting temperature vary linearly. At low temperature,
ceramics are brittle while close to its melting temperature, non-crystalline ceramics becomes ductile.

The processing method of ceramics decides the strength and are usually strong in compression than
in tension. Ceramics have limited energy absorption, load carrying capacity.
Brittle fracture
When the tensile load is applied on crystalline or non-crystalline ceramics, fracture takes place, before
any deformation sets-in. Brittle ceramic strength is lower than expected. Compressive strength is
higher than tensile strength. Flaws in the ceramics behaves like stress magnifiers and forms the cracks.
Fractures in ceramics sequentially take place. Fracture toughness is the ability of the ceramics to resist
the fracture is directly proportional to applied stress and length of the crack.

Stress-strain behavior
As ceramics are brittle, they tend to fracture before it reaches the plastic deformation state. As
materials under consideration have diverse shapes, their tensile strength measurement is difficult.
Instead, three-point bending apparatus to measure stress-strain behavior.
Flexural or fracture strength fs is the stress at fracture, directly proportional to load at fracture and
indirectly proportional to the thickness of the material.

Elastic behavior:
Elastic deformation is reversible deformation, while plastic deformation is permanent deformation.
In reversible deformation, the material comes to its original configuration, (shape and size), when
load/force is released. Elastic deformation can be due to tension / compression / shear force. Metals
and ceramics usually have linear elastic behavior. The elastic modulus, like fracture strength, is
directly proportional to load at fracture and indirectly proportional to the thickness of the material.

Composite materials
A composite material is a material system composed of two or more macro constituents that differ in
shape and chemical composition. Many modern technologies require materials with proper
combinations of properties that cannot be met by conventional metal alloys, ceramics, and polymeric
materials. This is especially true for structural materials that have low densities are strong, stiff and
abrasion resistant and are needed for aerospace, underwater and transport applications. Other
applications of these materials involve automotive, home appliance and sporting goods, industries.

Material property combinations and ranges have been extended by the development of composite
materials. A composite is composed of two (or more) individual materials which come from the
categories, namely metals, ceramics, and polymers. Thus Composites are artificially produced
multiphase materials having a desirable combination of the best properties of the constituent
phases. Usually, one phase (the matrix) is continuous and surrounds the other (the dispersed phase).
The properties of composites are a function of the properties of the constituent phases, their relative
amounts and the geometry of the dispersed phase.
Some composites occur in nature. For example, wood consists of strong and flexible cellulose fibers
surrounded and held together by a stiffer material called lignin. However, most are synthetic
composites. One of the most common and familiar composites is fiberglass, in which small glass
fibers are embedded within a polymeric material (epoxy or polyester). The glass fibers are relatively
strong and stiff (but also brittle), whereas the polymer is ductile. The plastic matrix holds the glass
fibers together and also protects them from damage by sharing out the forces acting on them. It is still
widely used today for boat hulls, sports equipment, building panels and many car bodies.

An optimum combination of properties is usually sought rather than one particular property, in
selecting a composite material. For example, wings of an aircraft must be lightweight and be strong,
stiff and sturdy. Several fiber-reinforced polymers possess this combination of properties. Adding
significant amounts of carbon black to natural rubber increases its strength drastically.

Properties of composite materials are determined by three factors.

i) The materials used as component phases in the composite
ii) The geometric shapes of the constituents
iii) The manner in which the phases interact with one another.

Classification of composites
Composites are classified into various types based on different parameters. One such classification is
based on the matrix material, and the reinforcement geometry (particles, fibers, layers) and the simple
scheme of such classification are shown below consisting of three main divisions.

I. Particle reinforced - Properties are isotropic

• Large particle
• Dispersion strengthened
II. Fiber reinforced - Properties can be isotropic or anisotropic
• Continuous (aligned)
• Discontinuous(short) – Aligned and Randomly oriented
III. Structural - Based on the build-up of sandwiches in layered form
• Laminates
• Sandwich panels

Particle reinforced:
The dispersed phase for particle reinforced composites is equiaxed (i.e., particle dimensions are
approximately the same in all directions). Large particle and dispersion –strengthened composites fall
within this category. The distinction between these is based upon reinforcement or strengthening
mechanism.

For most of the large particle reinforced composites, the particulate phase is harder and stiffer than
the matrix. In essence, the matrix transfers some of the applied stress to the particles, which bear the
friction of the load.
For dispersion-strengthened composites, particles usually are much smaller. In this the matrix bears
the major portion of an applied load, the small dispersed particles hinder the motion of dislocations.
Thus plastic deformation is restricted such that yield and tensile strengths, as well as hardness
improve.

Fiber reinforced:
The essential composites are those in which the dispersed phase is in the form of a fiber. The dispersed
phase has the geometry of a fiber (large length to diameter ratio). Design goals of fiber reinforced
composites often include high strength and /or stiffness on a weight basis. With these composites, an
applied load is transmitted to and distributed among the fibers via the matrix phase. Based on
diameter, fiber reinforcements are classified as whiskers, fibers, or wires.

Fiber orientation and concentration have a significant influence on the strength and other properties
of fiber reinforced composites. With respect to orientation, two extremes are possible;

i) a parallel alignment of the longitudinal axis of the fibers in a single direction and
ii) a random alignment. Continuous fibers are generally aligned, whereas discontinuous fibers may
be aligned randomly oriented or partially oriented. Better overall composite properties are realized
when the fiber distribution is uniform.

Structural:
Structural composites are combinations of composites and homogeneous materials, the properties of
which depend not only on the properties of the constituent materials but also on the geometrical design
of the various structural elements. Laminar composites and sandwich panels are two of the most
common structural composites.

The properties of laminar composites are virtually isotropic in a 2-D plane. This is made possible
with several sheets of a highly anisotropic composite, which are cemented onto one another such that
the high strength direction is varied with each successive layer.

Sandwich panels consist of two strong and stiff faces that are separated by a core material or structure.
These structures combine relatively high strengths and stiffnesses with low densities.
Influence of length, orientation, concentration, and elastic behavior of fibers
Influence of fiber length
The mechanical characteristics of a fiber-reinforced composite depend not only on the properties of
the fiber but also on the degree to which an applied load is transmitted to the fibers by the matrix
phase, which in most cases is at least moderately ductile. Significant reinforcement is possible only
if the matrix – fiber bond is strong. Based on diameter, fiber reinforcements are classified as whiskers,
fibers, or wires. Since reinforcement discontinues at the fiber extremities, reinforcement efficiency
depends on fiber length. For each fiber – matrix combination, there exists some critical length; the
length of continuous fibers dramatically exceeds this critical value, whereas shorter fibers are
discontinuous.

For some glass and carbon fiber–matrix combinations, this critical length is on the order of 1 mm,
which ranges between 20 and 150 times the fiber diameter.

Influence of fiber orientation and concentration

The arrangement or orientation of the fibers relative to one another, the fiber concentration, and the
distribution all have a significant influence on the strength and other properties of fiber-reinforced
composites. Concerning orientation, two extremes are possible: (1) a parallel alignment of the
longitudinal axis of the fibers in a single direction, and (2) a random alignment. Continuous fibers are
normally aligned (Figure 6a), whereas discontinuous fibers may be aligned (Figure 6b), randomly
oriented (Figure 6c), or partially oriented. Better overall composite properties are realized when the
fiber distribution is uniform.

Figure 6a b c
Fiber arrangements are also crucial relative to composite characteristics. The mechanical properties
of continuous and aligned fiber composites are highly anisotropic. In the alignment direction,
reinforcement and strength are a maximum; perpendicular to the alignment they are minimum.

For short and discontinuous fibrous composites, the fibers may be either aligned or randomly oriented.
Significant strengths and stiffness are possible for aligned short-fiber composites in the longitudinal
direction. Despite some limitations on reinforcement efficiency, the properties of randomly oriented
short fiber composites are isotropic.

Elastic Behavior—Longitudinal Loading

When the load is applied on the composite in the direction of the orientation of continuous fiber, then
its modulus of elasticity is equal to the summation of the products of the modulus of elasticity (E) and
volume fraction (V) of the respective phases.

i.e., Modulus of elasticity of composite, E = (EV)matrix + (EV)fiber

When the load is applied on the composite perpendicular to the orientation of continuous fiber, the
inverse of the modulus of elasticity is equal to the summation of the ratio of volume fraction (V) and
modulus of elasticity (E) of the respective phases.

i.e., 1/E = (EV)matrix + (EV)fiber

𝟏 𝑽 𝑽
=( ) +( )
𝑬 𝑬 𝒎𝒂𝒕𝒓𝒊𝒙 𝑬 𝒇𝒊𝒃𝒆𝒓

Polymer – Matrix Composites

Polymer-matrix composites (PMCs) consist of a polymer resin as the matrix, with fibers as the
reinforcement medium. These materials are used in diverse composite applications, as well as in the
largest quantities, due to their room-temperature properties, ease of fabrication, and cost.

Polymer matrix materials:

The matrix materials used in composites are polyesters, vinyl esters, epoxies, polyetheretherketone
(PEEK), polyphenylene sulfide (PPS), and polyetherimide (PEI). PEEK, PPS and PEI are the
polymeric resins with potential aerospace applications.

The fibers, which are the reinforcing materials generally used are - Glass fibers, carbon fibers or
aromatic polyamides (or aramids). Accordingly, they are classified into three categories.
i) Glass Fiber-Reinforced Polymer (GFRP) Composites,
ii) Carbon Fiber-Reinforced Polymer (CFRP) Composites, and
iii) Aramid Fiber-Reinforced Polymer Composites.

The fiber is embedded in the matrix to make the matrix stronger. Fibre reinforced composites impart
two important properties: (i) often stronger than steel (ii) less weight. This means that composites can
be used to make automobiles lighter, and thus making them more fuel efficient.
Advantages of polymer composites: Polymer composite materials are preferred to conventional
metals and materials for the following advantageous properties;
- Lightweight.
- High strength to weight ratio.
- More durable than conventional materials like steel and aluminum.
- Good corrosion resistance.
- High fatigue strength.
- High-temperature resistance.

Applications:
- Composites of phenolic resins and nylon are used in heat shields for space crafts.
- Automotive and railway applications.
- As the structural material in construction industries.

i) Glass Fibre Reinforced Plastic (GFRP):

Glass Fibre Reinforced Plastic is a typical polymer composite in which the reinforcing material is
fiberglass. Its matrix is made by reacting a polyester with carbon-carbon double bonds in its
backbone and styrene - a mix of the styrene and polyester over a mass of glass fibers.

The styrene and double bonds in the polyester react by free radical polymerization to form a cross-
linked resin. The glass fiber is trapped inside, where they act as a reinforcement. The matrix adds
toughness to the composite, while fibers have good tensile strength. The matrix gives compressional
strength to the composite. Fiber reinforced composites are used in applications like car engine
components, airplane parts.

ii) Carbon Fiber Reinforced Polymer (CFRP) Composite:

Carbon is a high-performance fiber material that is most commonly used reinforcement in advanced
polymer matrix composites. The reasons for this are as follows:
1. Carbon fibers have the highest specific modulus and specific strength of all reinforcing fiber
materials.
2. They retain their high tensile modulus and high strength at elevated temperatures; high-temperature
oxidation, however, may be a problem.
3. At room temperature, carbon fibers are not affected by moisture or a wide variety of solvents, acids,
and bases.
4. These fibers exhibit a diversity of physical and mechanical characteristics, allowing composites
incorporating these fibers to have specific engineered properties.
5. Fiber and composite manufacturing processes have been developed that are relatively inexpensive
and cost-effective.

Use of the term “carbon fiber” may seem perplexing since carbon is an element. Carbon fibers are
not totally crystalline, but are composed of both graphitic and noncrystalline regions; these areas of
non-crystallinity are devoid of the three-dimensional ordered arrangement of hexagonal carbon
networks that is characteristic of graphite. Manufacturing techniques for producing carbon fibers are
relatively complex and will not be discussed. However, three different organic precursor materials
are used: rayon, polyacrylonitrile (PAN), and pitch. Processing technique will vary from precursor to
precursor, as will also the resultant fiber characteristics.
Carbon-reinforced polymer composites are currently being utilized extensively in sports and
recreational equipment (fishing rods, golf clubs), filament-wound rocket motor cases, pressure
vessels, and aircraft structural components—both military and commercial, fixed wing and
helicopters (e.g., as a wing, body, stabilizer, and rudder components).

iii) Aramid Fiber-Reinforced Polymer Composite:

Aramid fibers are high-strength, high-modulus materials that were introduced in the early 1970s.
They are especially desirable for their outstanding strength-to-weight ratios, which are superior to
metals. Chemically, this group of materials is known as poly(paraphenylene terephthalamide). There
are some aramid materials; trade names for two of the most common are Kevlar™ and Nomex™.

Kevlar composites:
Kevlar is an aromatic polyimide (or aramid). The chemical composition of Kevlar is poly(para
phenyleneterephthalamide). They belong to the family of nylons. Common nylons, such as nylon-6,6
do not have very good structural properties, so the incorporation of para-aramids improve the
properties. The aramid ring gives Kevlar its thermal stability, while the para structure gives it high
strength and modulus. Kevlar is used as matrix material, whereas many fibers like carbon fiber or
glass fiber are used as the reinforcing agent.

Advantages:
- Lightweight, high strength, Thermally Stable
- Resistant to impact and abrasion damage. It can be used as a protective layer on graphite
laminates.
- Can be mixed with graphite to provide damage resistance and to prevent failure.

Disadvantages:
- Fibers themselves absorb moisture, so Kevlar composites are more sensitive to the
environment than glass or graphite composites.
- Poor compression resistance.
 Biomaterials
Biomaterials is an exciting and rapidly developing interdisciplinary field involving elements of
materials science, engineering, biology, chemistry, and medicine. The biomaterials topic is
designed to provide a broad basis in the fundamentals of biomaterials science and engineering.
Definition
Biomaterial - Any material of natural or synthetic origin that comes in contact with tissue, blood
or biological fluids, and intended for use in prosthetic, diagnostic, therapeutic or storage
application.
Factors that govern biomaterial choice
• Bulk properties: The use of biomaterial in particular applications is often dictated by bulk
properties; Mechanical (Eg. modulus, strength & toughness for load-bearing applications,
wear resistance for articulating surfaces, flexibility & compliance for vascular and soft
tissues.), Chemical (Eg. degradation) and Optical (Eg. whiteness, clarity) matched to those
of natural organs.
• Ability to Process
Requirements of Biomaterials
A biomaterial should broadly satisfy the following requirements;
• Biocompatibility - the ability of a material to perform with an appropriate host response in
a specific application. The biomaterials must neither degrade in its properties within the
body (unless this is wanted), nor biomaterials/devices (and any degradation product) must
cause any adverse reaction within the host´s body. Biocompatibility is strongly determined
by the primary chemical structure of the material.
• Biofunctionality - The material must satisfy its design requirements. Eg: Articulation to
allow movement (e.g. artificial knee joint), load transmission and stress distribution etc.
• Inert or specifically interactive
• Mechanically and chemically stable - tensile strength, yield strength, elastic modulus,
corrosion and fatigue resistance, surface finish, creep, and hardness.
• Processable (for manufacturability) - should be machinable, moldable and extrudable
• Sterilizable
Types of Biomaterials
The biomaterials are divided into four classes: – Metals, Ceramics (including glasses), Composites
and Polymers. The properties and safety of materials must be carefully assessed with respect to
the specific application. Metals are susceptible to degradation by corrosion, a process that can
release by-products that may cause adverse biological responses. Ceramics are attractive as
biological implants for their biocompatibility. The availability of a wide range of polymers
significantly influenced the growth of tissue engineering and controlled drug delivery
technologies. Innovations in the composite material design and fabrication processes are raising
the possibility of realizing implants with improved performance.
1. Metals and alloys
Metals are widely used as biomaterials due to their favorable mechanical properties like strength
and toughness, especially fracture toughness and fatigue strength. The type of bonding (closely
packed crystal structure) in metals and metal alloys render them valuable exclusively for load-
bearing implants, such as hip and knee prostheses and fracture fixation wires, pins, screws, and
plates. Their properties depend on the processing method and purity of the metal. When processed
suitably they contribute high tensile, fatigue and yield strengths; low reactivity and good ductility.
Although pure metals are sometimes used, alloys frequently provide an improvement in material
properties, such as strength and corrosion resistance. The main considerations in selecting metals
and alloys for biomedical applications are their excellent electrical and thermal conductivity,
biocompatibility, appropriate mechanical properties, corrosion resistance, and reasonable cost.
The human body is an aggressive medium for inducing corrosion in metals: water, dissolved
oxygen, proteins, chloride and hydroxide. The biocompatibility of the metallic implant is of
considerable concern because these implants can corrode in an in vivo environment. The corrosion
of the implant material will weaken the implant, and the corrosion products induce a toxic effect
on the surrounding tissues and organs. Hence to avoid corrosion, the composition of the biological
environment (ions, pH, oxygen pressure, etc.) should be considered. Choice of appropriate metals,
avoiding implantation of dissimilar metals and minimizing pits and crevices on the metal surface
can reduce corrosion. Three material groups dominate biomedical metals: Stainless steel, titanium
and titanium alloys and cobalt-chromium-molybdenum alloy.
Stainless steel (most common 316L) used in orthopedics (Eg. Joint replacements, screws) and
dental implants has 60-65% Fe, 17-19% Cr, 12-14% Ni, > 0.030% C and minor amounts of N,
Mn, Mo, P, Si, and S. The low carbon content enables better resistance to in vivo corrosion,
chromium for corrosion resistance by formation of surface oxide and nickel improves strength.
Due to the potential long-term release of Ni2+, Cr3+ and Cr6+ restricted to temporary devices.
Ti alloys due to the combination of its excellent characteristics such as high strength, low density,
lightweight, high specific strength, good resistance to corrosion, complete inertness to body
environment, enhanced biocompatibility, good mechanical properties are a suitable choice for
implantation. TiO2 layer provides good corrosion resistance to stress corrosion cracking and
corrosion fatigue in body fluids. But, titanium has unsatisfactory wear. Eg. heart pacemakers,
artificial heart valves, Bone and Joint Replacements
Co-Cr-Mo alloy- Cobalt-based alloys are highly resistant to corrosion even in chloride
environment due to spontaneous formation of passive oxide layer within the human body
environment. The thermal treatments used to Co-Cr-Mo alloys modify the microstructure of the
alloy alters the electrochemical and mechanical properties of the biomaterial. The corrosion
products of Co-Cr-Mo are more toxic than those of stainless steel 316L.
2. Ceramics
Inorganic polycrystalline compounds that contain metallic and non-metallic elements. High
oxidized state and inter-atomic ionic/covalent bonding in ceramics make them resistant to
oxidation, increasingly stable and non-conducting. Ceramic biomaterials have been used less
extensively than either metals or polymers. The bioceramics are highly chemically inert in the
body, hard, possess excellent corrosion resistance, high wear resistance, high modulus (stiffness)
& compressive strength and fine aesthetic properties (for dental applications), but they are difficult
to fabricate. Ceramics are used in several areas like dentistry, orthopedics, and as medical sensors.
Eg: Alumina, Zirconium, Calcium phosphate, Silica, hydroxyapatite
Bioceramics are of three basic types: bioinert, bioactive and bioresorbable ceramics.
i) Bioinert refers to a material that retains its structure in the body after implantation and does
not induce any immunologic host reactions.
Eg. Alumina (Al2O3) is used in loadbearing hip prostheses and dental implants, because of
its combination of excellent corrosion resistance, good biocompatibility, high wear
resistance and high strength. These properties are attributed to ionic bonding/electrostatic
interactions with the charges on the proteins.
ii) Bioactive refers to materials that form direct chemical bonds with bone or even with the
soft tissue of a living organism.
 Eg. Bioglass and glass-ceramics widely used for filling bone defects permit modification
of the surface that occurs upon implantation. Bonding to bone is due to specific amounts
of ionic network formers: SiO2 and P2O5 and network modifiers: Na2O and CaO. They are
partially soluble in vivo, which facilitates direct chemical bond with bone, which includes
a slight solubility of the glass ceramic and a solid state reaction between the stable apatite
crystals in the glass ceramic and the bone. The porosity of bioglass is beneficial for
resorption and bioactivity.
iii) Bioresorbable refers to materials that degrade by a hydrolytic breakdown in the body,
while they are being replaced by regenerating natural tissue; the chemical byproducts of
the degrading materials are absorbed and released via metabolic processes of the body.
Eg. Calcium phosphate ceramics have ideal pore size similar to that of spongy bone, and
hence bond to living the bone-like apatite layer on their surface.
Ceramics typically fail due to little plastic deformation, and they are sensitive to the presence of
cracks or other defects, has low tensile strength and poor fatigue resistance.
3. Polymers
Polymers are the most widely used materials in biomedical applications. The unique properties of
the polymeric biomaterials compared to metal or ceramic materials are flexibility, ease of
manufacture to produce various shapes (latex, film, sheet and fibers), ease of secondary
processability, surface modification, reasonable cost, resistance to biochemical attack, good
biocompatibility, light weight, availability in a wide variety of compositions with tailorable
physical and mechanical properties. But they are leachable, absorb water and proteins, allows
surface contamination, wear and tear and difficult to sterilize.
Eg: Polymethylmethacrylate (PMMA) is used as intraocular lenses due to its high refractive index,
easily processability, environmental stability (relatively inert) and good mechanical properties.
Surfaces of materials are high-energy regions and thereby facilitate chemical reactions that
influence the performance of biomaterials. Eg. Some biopolymers are susceptible to chemical
reactions that lead to degradation through hydrolysis. However, in some cases, a polymer is
specifically chosen for its ability to degrade in vivo.
Polymer hydrolysis involves the scission of susceptible molecular groups by reaction with H2O,
catalyzed by acid, base or enzyme. Molecular and structural factors influencing hydrolysis are
a) Hydrophobicity: ↑ hydrophobicity ⇒ ↓ hydrolysis
b) MW & architecture: higher MW ⇒ ↓ hydrolysis
c) Morphology: crystallinity ↓ hydrolysis
crystallinity ↓ solubility
porosity ↑ hydrolysis
d) Tg: less mobility ⇒ ↓ hydrolysis
Rates of Hydrolysis: anhydride > ester > amide > ether
Esters: R-COO-R’ + H2O → R-COOH + HO-R’
An amorphous poly(lactide-co-glycolide) with rapid degradation property is used as
bioresorbable sutures, controlled release matrices, tissue engineering scaffolds etc. Whereas,
semicrystalline polyethylene terephthalate (Dacron) with very slow hydrolysis property find
application in vascular grafts, arterial patches, heart pumps etc.
Ethers: R-O-R’ + H2O → R-CH2-OH + HO-CH2-R’
Semicrystalline polyethylene oxide (PEO) used for protein resistant coatings and hydrogels is
flexible, hydrolyzable, water soluble and bioinert. These properties are derived from both
primary and strong secondary H-bonding.
However, some olefins (e.g., Ultrahigh molecular weight polyethylene-UHMWPE: joint cup
liners), halogenated hydrocarbons (e.g., PVC: catheters; PTFE: vascular grafts), siloxanes
(e.g., PDMS: soft tissue prostheses) and sulfones (e.g., PSF: renal dialysis membranes) exhibit
stable polymer chemistry
4. Composites
Natural biocomposites include bone, wood, dentin, cartilage, and skin. Biocomposites are
composite materials composed of a biodegradable matrix and biodegradable natural fibers as
reinforcement in order to obtain properties that improve every one of the components. Composite
materials allow a flexible design since their structure and properties can be optimized and tailored
to specific applications. Eg. fiberglass with a polymeric matrix is used in the current synthetic
casting materials. The use of composite materials for biomedical applications offers many new
options and possibilities for implants design. The implant structure and its interactions with the
surrounding tissues can be optimized by varying the constituents, the type, and distribution of the
reinforcing phase and adding coupling agents. The composite materials and components can be
designed to obtain a wide range of mechanical and biological properties.
Thin films

A thin film in general, refers to films with thickness ranging from 0.1 µm to about 300
µm. Coatings such as paint or varnish are typically much thicker. Thin film coatings have
unique properties and hence make them desirable for a variety of reasons including materials
conservation and design flexibility. A large number of materials which are used for coatings
today range from the naturally occurring oxide layer (which protects the surfaces of many
metals such as aluminum, titanium, and stainless steel), to those with very deliberate and
controlled alloying additions to the surface to produce specific properties as follows;

• Chemically stable in the environment where it is used

• Adhere well to the substrate

• Uniform thickness

• Chemically pure or of controlled chemical composition

• The low density of imperfections

• Optical or magnetic properties, insulator or semiconductor as required for

particular applications

As the film is inherently fragile, the bonding between the thin film and substrate provides
the structural support. The bonding forces may be primary chemical in nature. Eg. The oxide
lattices of the metal oxide and the glass blend at the interface forming a thin zone of intermediate
composition. The bonding energies are in the range of 250 - 400 kJ/mol. In some cases, the bonds
are based on intermolecular van der Waals and electrostatic forces. The energies are in the range
of 50-100 kJ/mol. Eg. Deposition of polymer film on a metal surface

Uses of thin films

They are used as conductors, resistors and capacitors. They are widely used as optical
coatings on lenses to reduce reflection and to protect the softer glass against scratching. Thin
metallic films have been used as protective coatings on metals. Eg. Silver plating, chrome plating.
Metal tool surfaces are coated with ceramic thin films to increase their hardness. The top of the
drill bit is normally coated with a thin film of tungsten carbide to impart hardness and wear
resistance. The films are applied to the glass to reduce scratching and abrasion and to increase
lubricity.
Formation of thin films

The process of applying a thin film to a surface is known as thin-film deposition or

fabrication. It is the technique for depositing a thin film of material onto a substrate or onto
previously deposited layers. Thin films are formed by different techniques such as physical vapor
deposition (PVD) or chemical vapor deposition (CVD). In PVD there is no change in the chemical
nature of the source and coated material whereas in CVD due to chemical reactions occurring, the
chemical identity of the source and the coated thin film materials are different.

Physical vapor deposition

PVD processes are atomistic deposition processes in which material is vaporized to form a solid
or liquid source in the form of atoms or molecules, transported as vapor through a vacuum or low
pressure gaseous (or plasma) environment to the substrate where it condenses. The material to be
deposited is placed in an energetic, entropic environment so that particles of material escape its
surface. Facing this source is a cooler surface which draws energy from these particles as they
arrive, allowing them to form a solid layer. The whole system is kept in a vacuum deposition
chamber, to allow the particles to travel as freely as possible. Since particles tend to follow a
straight path, films deposited by physical means are commonly directional, rather than conformal.

Typically, PVD processes are used to deposit films with thicknesses in the range of a few
nanometers to thousands of nanometers. The substrates can range in size from very small to very
large, in shape from flat to complex geometries. The source-substrate geometry influences the
ultimate film uniformity. Two principal methods for optimizing film uniformity over large areas
involve varying the geometric location of the source and interposing static as well as rotating
shutters between evaporation sources and substrates. The chemical purity of evaporated films
depends on the nature and level of impurities that (1) are initially present in the source, (2)
contaminate the source from the heater, crucible, or support materials, and (3) originate from the
residual gases present in the vacuum system. Typical PVD deposition rates are 10-100 Å/s.

Fig. PVD: Process flow diagram

Vacuum evaporation is one of the important methods for depositing thin films using PVD
technique.

Vacuum deposition: This method is used to form thin films of substances that can be vaporized
without destroying their chemical identities. Eg. Optical lenses are coated with inorganic materials
such as MgF2, Al2O3 and SiO2. During evaporation, a target consisting of the material to be
deposited is bombarded by a high energy source such as a beam of electrons or ions in a high
vacuum chamber with a pressure of 10-5 torr or less. This dislodges atoms from the surface of the
target, ‘vaporizing’ them. Vaporized atoms from the target move in a straight path to the substrate
to be coated. Finally, the metal atoms get deposited on the substrate surface mounted at an
appreciable distance away from the evaporation source. Uniformity is obtained by rotating the
substrate to be coated.

Fig. Schematic diagram of vacuum deposition

The vacuum environment may serve the following purposes by providing low pressure plasma
environment, a means for controlling gas and vapor composition and a means for mass flow
control into the processing chamber. And reducing the particle density of undesirable atoms and
molecules (contaminants) so that the mean free path for collision is long

Advantages:

• PVD coatings are harder and more corrosion resistant than coatings applied by the
electroplating process.
• Most coatings have high temperature and good impact strength, excellent abrasion
resistance
 • More environmentally friendly than traditional coating processes such as electroplating
and painting.

• It is possible to change the target material without disturbing the system so that multilayer
films can be formed.

Disadvantages:

• It is extremely difficult to coat undercuts and similar surface features

• High capital cost
• Some processes operate at high vacuums and temperatures, require skilled operators
• Processes involving a large amount of heat requires appropriate cooling systems
• The rate of coating deposition is usually quite slow

Chemical Vapor Deposition (CVD)

In this method, the surface is coated with a volatile, stable chemical compound at a
temperature below the melting point of the surface. It involves the dissociation and /or chemical
reactions of gaseous reactants in an activated (heat, light, plasma) environment, followed by the
formation of a stable solid product. The deposition involves homogenous gas phase reactions,
which occur in the gas phase, and/or heterogeneous chemical reactions which occur on/near the
vicinity of a heated substrate leading to the formation of powders or films, respectively. It has
been used to produce ultrafine powders and thin films.

In general, the CVD equipment consists of three main components:

(a) Chemical vapor precursor supply system: to generate vapor and deliver to the reactor.

(b) CVD reactor component: consists of a reaction chamber equipped with a load-lock for the
transport and placement of the substrate into the chamber, a substrate holder, and a heating
system with temperature control. The main function is to heat the substrate to the
deposition temperature.

(c) Effluent gas handling system: This component consists of a neutralizing part for the
downstream gases, and /or a vacuum system to provide the required reduced pressure for the
CVD process.

Process principles and deposition mechanism: CVD process involves the following key steps:

1. Generation of active gaseous reactant species

 2. Transport of these gaseous species into the reaction chamber.

3. Gaseous reactants undergo gas phase reactions forming intermediate species.

(a) At a high temperature above the decomposition temperatures of intermediate species

inside the reactor, homogeneous gas phase reaction can occur where the intermediate
species undergo subsequent decomposition and/or chemical reaction.

(b) At temperatures below the dissociation of the intermediate phase,

diffusion/convection of the intermediate species across the heated substrate surface
occur. These intermediate species subsequently undergo steps (4-7)

4. Adsorption of gaseous reactants on to the heated substrate and the heterogeneous reaction
occurs at the gas-solid interface (i.e. heated substrate) which produces the deposit and by-
product species.

5. The deposits will diffuse along the heated substrate surface forming the crystallization
center and growth of the film takes place.

6. Gaseous by-products are removed from the boundary layer through diffusion or
convection.

7. The unreacted gaseous precursors and by-products will be transported away from the
deposition chamber.

Examples: Titanium tetrabromide is evaporated and the gaseous TiBr4 is mixed with hydrogen. The
mixture is then passed over a substrate heated to about 1300 °C, such as silica or alumina. The metal
halide undergoes reaction with hydrogen to form a thin film of titanium metal
TiBr4(g) + 2H2(g) Ti(s) + 4HBr(g)

Films of silicon are formed by decomposing SiCl4 in the presence of H2 at 1200 °C.

SiCl4(g) + 2H2(g) Si(s) + 4HCl(g)

 Fig. Schematic diagram of simplified CVD reactor

Advantages

• Capable of producing highly dense and pure materials without carbon or oxygen
impurities.

• Produces uniform films with good reproducibility and adhesion at reasonably high
deposition rates.

• Has good throwing power and hence can be used to uniformly coat complex shaped
components and deposit films.

• Able to control crystal structure, surface morphology and orientation of the products by
controlling the process parameters.

• Deposition rate can be adjusted readily. The low deposition rate is favored for the growth
of epitaxial thin films for microelectronic applications. The deposition of thick protective
coatings is favored by a high deposition rate.

• Reasonable processing cost using the CVD technique.

• The flexibility of using a wide range of chemical precursors such as nitrides, borides,
organometallics which enable the deposition of a large spectrum of materials including
metal carbides, nitrides, oxides and sulfides.

Drawbacks
• Chemical and safety hazards caused by the use of toxic, corrosive, flammable and/or
 explosive precursor gases.

• Difficult to deposit multicomponent materials with well-controlled stoichiometry using

multisource precursors because different precursors have different vaporization rates.

• The use of more sophisticated reactor and /or vacuum system by CVD variants such as
low pressure or ultrahigh vacuum CVD, plasma-assisted CVD and photo-assisted CVD
tends to increase the cost of fabrication.

Applications:

• Production of high-quality optical fibers suitable for long distance applications.

• Diamond thin films: They are used as heat sinks for microelectronics and optoelectronics,
sensors, microwave devices, coatings for IR windows in nuclear detectors, UV imaging,
cold cathodes. The potential applications of diamond films involve speaker diaphragms
which are coated with thin films of diamond to provide improved acoustic properties.

Comparison between PVD & CVD

Features PVD CVD

Mechanism of Thermal energy Chemical reaction

deposition

Deposition rate High Moderate

Deposited species Atoms & ions Precursor molecules

dissociate into atoms

Energy of deposited Low (0.1-0.5 eV) Low; can be high with

species plasma-assisted CVD

Throwing power Poor Good

Nano-materials

Nanoscience and nanotechnology deal with objects that have dimensions in the range from 1
 nm to about 100 nm. Nano-materials are materials which have at least one of their dimension
in the nanometer (1 nm= 10−9 m) range. The physical and chemical properties of nano-materials
differ significantly from those of their bulk counterparts. The new properties are the result of
an increase in the ratio of surface area to volume. This will change the surface effects such as
those that give rise to catalysis, adsorption, adhesion and photonic effects. The reason for this
is that the electrons in nanomaterials are confined within such a small volume that quantum
effects now dominate optical and electronic behavior. Nano-fibers, nano-wires, nano-scale
particles, Nano-channels and nano-tubes are some of the important nanostructures. The nano-
science field is progressing so rapidly that it is probably hard to find any technical areas that
are not useful.

The most important aspects of this field are connected with four issues;

i) The way in which nanoparticles interact with their neighbors in solid arrays or
with the second phase in composite materials.

ii) Miniaturization of electronic circuits below the micro-scale to pack an

increasing number of features into an integrated array.

iii) Development of methods to produce nano-fibers that are of interest in

geological tissue engineering, advanced textiles and filtration technology.

iv) Use of micelles with diameters in the nano range for controlled drug delivery.

Classification

(a) Based on origin

(i) Natural nanomaterials (ii) Artificial nanomaterials

Natural nanomaterials are those which are obtained naturally. Examples:- Carbon-nanotubes
and fibers. Artificial nanomaterials are those which are synthesized artificially Examples:-
Au/Ag nanoparticles, Polymeric nano-composites.

(b) Based on dimension

This classification is based on the number of dimensions which are not confined to the nanoscale
range (<100nm). They may be amorphous or crystalline, single crystalline or polycrystalline,
made up of one or more elements, metallic, ceramics or polymers.
(i) Zero-dimensional: Materials wherein all the dimensions are within the nanoscale range are
called zero-dimensional nanomaterial. Eg: quantum dots.

(ii) 1 dimensional: Here two dimensions are at the nanoscale range, another dimension is not.
This leads to needle-like nanomaterials. Eg: nanotubes, nanorods, nanowires.

(iii) 2 dimensional: Here one dimension is at the nanoscale range, the other two dimensions
are not. They exhibit plate-like shapes. Eg: nanocoatings, nanofilms

(iv) 3 dimensional: These materials are not confined to the nanoscale in any dimension. These are
characterized by having three arbitrarily dimensions above 100 nm. They are also known as bulk
nanomaterials. 3-D nanomaterials can contain dispersions of nanoparticles, bundles of nano wires/
nanotubes as well as multilayers. Eg: Nanocrystalline materials, nanospheres.

There are other types of classifications based on their field of application, shapes, properties,
structures, manufacturing process and morphologies.

Preparation of nanomaterials:

Nanomaterials can be synthesized by two different approaches. They are “Bottom-up” and “Top-
down methods”. Top-down methods start with micro – or macro scale materials, which are then
broken down chemically or physically to nanoparticles. Methods that are used include ball milling,
chemical etching, electrospinning and the vaporization of metals using plasmas. They are slow, not
cheap, and not suitable for large-scale production. Bottom-up methods involve the assembly of very
small units (atoms, molecules or small nanoparticles) to create larger nanomaterials and systems. The
fabrication is much less expensive.

“Bottom-up” Approach:

Sol-gel method

The sol-gel process is a wet-chemical technique used primarily for the fabrication of materials
starting from a chemical solution which acts as the precursor for the preparation of gel by either
discrete particles or network polymers. The process usually consists of five steps:

1. Preparation of a precursor solution: The desired colloidal particles are dispersed in a

liquid to form a sol. Typical precursors are metal alkoxides, which undergo various forms
of hydrolysis and polycondensation reactions. The formation of a metal oxide involves
connecting the metal centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore
generating metal-oxo or metal-hydroxo polymers in solution.
 2. Deposition of the sol onto a substrate: The sol solution is coated on a substrate by
spraying, dipping or spinning.

3. Formation of gel: The particles in the solid state are polymerized through the removal of
the stabilizing components. This can be done either by heating the sol at a low temperature
or allowing it to stand for a certain duration. This results in the formation of a gel.

4. Drying process: Removal of the remaining liquid (solvent) phase requires a drying
process, which is typically accompanied by a significant amount of shrinkage and
densification.

5. Heat Treatment: After drying, a thermal treatment, or firing process, is often necessary to
favor further poly-condensation reaction and enhance mechanical properties, structural
stability of the gel.

The sol-gel approach is a cheap and low-temperature technique that allows for the fine control of
the product’s chemical composition. Even small quantities of dopants, such as organic dyes and
rare earth elements, can be introduced in the sol and end up uniformly dispersed in the final
product. It can use used as a means of producing very thin films of metal oxides for various
purposes. Examples include Gallium based nano-materials, Dye-doped gel Glasses, Glass
dispersed liquid crystals, Synthesis of glass-metal nano-composite, Metal-silica and Metal oxide-
silica nanocomposites.

“Top Down” Approach:

Ball Milling

In this process, small balls are allowed to rotate around the inside of a drum and drop with gravity
force on to a solid enclosed in the drum. The significant advantage of this method is that it can
be readily implemented commercially. The grinding of ceramics can reduce them to a fine powder
with each individual particle having nanoscale dimensions. It is difficult to avoid contamination
of the nanoparticles by the materials used in the abrasion process and the particle sizes are not
uniform. Polymers cannot be reduced to nanoparticles by grinding because of their molecular
structure and their impact resistance. Ball milling can be used to make a variety of new carbon
types, including carbon nanotubes. It is useful for preparing other types of nanotubes, such as
boron nitride nanotubes and a wide range of elemental and oxide powders. For example, iron
with grain sizes of 13-30 nm can be formed. Ball milling is the preferred method for preparing
metal oxides.

To successfully prepare metal oxides, it is important to keep the crystallites from reacting and to
have an understanding of the kinetic energy transferred during crushing. However, a by-product
can sometimes be useful. In the production of nanocrystalline Zirconia (ZrO2), zirconium chloride
is treated with magnesium oxide during milling to form zirconia and magnesium chloride:
ZrCl4 + 2MgO ZrO2 + 2MgCl2

The by-product, magnesium chloride, acts to prevent the individual nanocrystallites of zirconia
agglomerating. It is washed out at the end of the process.
1
2
Electrochemistry has a vital role in electro refining, battery technology, corrosion
control & metal finishing.

An electrochemical cell consists of two electrodes or metallic conductors, in contact

with an electrolyte, an ionic conductor.
The two electrodes may share the same compartment. If the electrolytes are different,
the two compartments may be joined by a salt bridge.

3
Electrochemical cell consists of two electrodes & an electrolyte in a compartment.
The two electrodes may share the same compartment. If the electrolytes are different,
the two compartments may be joined by a salt bridge, which is a tube containing a
concentrated electrolyte soln. in agar jelly that completes the electrical circuit to
enable the cell to function. An electrochemical cell can act as Galvanic cell or
electrolytic cell.

In a galvanic cell, anode is the site for oxidation & cathode is the site for the
reduction. The -vely charged electrons flow from anode to cathode and e-s are
attracted to the +ve cathode from the –ve anode thru the external circuit.

4
A galvanic cell produces electricity as a result of the spontaneous redox reaction that
occurs.
Galvanic cell generally consists of two electrodes dipped in two electrolyte solns.
which are separated by a porous diaphragm or connected through a salt bridge. It
converts stored up CE in the form of electroactive materials directly into EE. In a
galvanic cell, anode is -ve; and cathode is +ve.
Galvanic cells are used as portable source of electrical energy.

Galvanic cell is represented by as follows:

Anode is written on the LHS & cathode is written on the RHS of cell representation
The anode is represented by writing the metal (or solid phase) first & then the
electrolyte along with the concentration in the bracket. The two are separated by a
vertical line.
Anode representation:
Metal/ Metal ion (concentration) i.e. M/Mn+ (c)
Zn│Zn2+ or Zn; Zn2+ or Zn │ ZnSO4 (1M) or Zn; ZnSO4 (1M)
The cathode is represented by metal ion first & then the metal (or solid phase)
thereafter. The two are separated by a vertical line.
Cathode representation:
Mn+ (c) / M i.e. Metal ion (concentration) / Metal
e.g. Cu2+│Cu or Cu2+; Cu or Cu2+ (1M); Cu or CuSO4 (1M)/Cu
4. A salt bridge is indicated by two vertical lines, separating the two half-cells.

5
e.g. Zn │ ZnSO4 (1M)║ CuSO4(1M)/Cu
Cu(s) / Cu2+ (aq) ║Ag+(aq) / Ag (s)

5
Daniel cell is a typical example for a galvanic cell & it may be represented as:
Zn │ ZnSO4 (1M)║ CuSO4(1M)/Cu
At the anode: Zn → Zn2+ + 2e-
At the cathode: Cu2+ + 2e- → Cu
Net reaction:
Zn(s)+ Cu2+(aq)→ Zn2+(aq)+ Cu(s)

6
An electrolytic cell is an electrochemical cell in which a non-spontaneous redox rxn is
driven by an external source of electrical energy (or a battery) i.e. EC-a single
arrangement of two electrodes in one or two electrolytes where non-spontaneous
redox rxn is forcibly carried out by sending EE into the cell
Electrolytic cell involves conversion of EE into CE.
In an electrolytic cell, anode is +ve (electrode which attracts the anions) & cathode is
–ve (electrode which attracts the cations).
This type of cells have wide ranging applications in purification of metals, in
electrodeposition of a metal on to the surface.

7
.

8
9
The emf cannot be measured accurately using a voltmeter :

As a part of the cell current is drawn thereby causing a change in the emf.

As a part of the emf is used to overcome the internal resistance of the cell.

The E Cell depends on:

the nature of the electrodes.
temperature.
concentration of the electrolyte solutions.

10
11
EMF Measurement: For precise emf measurements potentiometers are used, which
require extremely small current at balance point. In this method, emf of a test cell is
opposed by the impressed emf from an external source of emf, & the length
measurement is made when there is no net flow of current in the circuit. The basic
principle is that the emf of the cell to be measured is exactly balanced by an equal &
opposite known emf so that no current flows in the circuit (null point). Unknown emf
Ex can be calculated as emf of std. cell Es is known.

12
Potential at the junction of the two electrolytes, arising from unequal migration of
cations in one direction & anions in the other.
In a Daniel cell, Cu2+ ions diffuse into ZnSO4 (aq) & Zn2+ ions diffuse into CuSO4
(aq) because Cu2+ ions are slightly more mobile than Zn2+ ions. This produces a small
excess +ve charge on ZnSO4(aq) side of the junction & equal - ve charge on the
CuSO4 (aq) side.
LJPs are of the order of a few millivolts. It can be minimized by SB : KCl, KNO3,
NH4NO3 whose ions have same migration velocities. As ions move almost with equal
speed to anode & cathode compartments  Junction potential almost reduced to zero.

13
1. Prevents any net charge accumulation in the two electrolytes
2. Physically separates the two electrolytes but completes the electrical circuit by
allowing ions carrying charge to move from one half-cell to the other
3. Reduces LJP to a minimum by nearly equal diffusion rates of positive & negative
ions [Diffusion, Migration, Convection]

14
15
16
Construction: It consists of an H-shaped glass vessel with the lower ends of both
arms closed, having platinum wire scaled into the bottom of the each arm. The +ve
electrode contains mercury over which a paste of mercurous sulfate (Hg2SO4) &
mercury is placed. The -ve electrode consists of an amalgam of Cd & Hg, containing
about 12-15 % Cd by weight. Over both electrodes are sprinkled some crystals of
solid CdSO4. 8/3 H2O are added to keep the electrolyte solution sat’d at all
temperatures. The remaining part of the cell is filled with a saturated solution of
cadmium sulphate that acts as an electrolyte. The cupper ends of the tube are closed
with corks & sealing –wax.

Cell representation:
Cd-Hg/Cd2+// Hg2SO4/Hg
Working:
Anode: Cd (s) ↔ Cd2+(aq) + 2e-
Cathode: Hg2SO4(s) + 2e- ↔ 2Hg (l)+ SO42-(aq)
CR: Cd(s) + Hg2SO4(s)  CdSO4(s) + 2Hg(l)
Explanation:-----------
Weston Cadmium Cell :
*The emf of the cell is 1.01807 V at 298 K
*(δE/δT) = 4x10-5 volt/degree
*Emf remains const. for many years
*Reproducible value of emf

17
Application : as a std.cell in accurate emf measurements of other cells

17
Single Electrode potential (E):The potential of single electrode is the difference of
potential between a metal and the solution of its salt. i.e the tendency of an electrode
to lose or gain electrons when in contact with its own ions in the soln.
In a cell, the electrode with lower EP has less tendency to undergo reduction & acts as
anode. The electrode with higher electrode potential has higher tendency to undergo
reduction & acts as cathode.
Example: In case of Zn in ZnSO4 soln. acquires a -ve charge
M(s) → Mn+ + ne -(aq) (1) Dissolution reaction
Metal shows the tendency to go into the solution as metal ion by losing electrons.
Mn+ (aq) + ne -(aq) → M(s) (2) Deposition reaction
Oxidation potential vs Reduction potential
By convention, E.P.  Reduction potential

Standard E.P. (Eo) std.state c = 1 M, P = 1atm.T = 298 K

If the dissolution rxn is faster than deposition …

If the deposition rxn is faster than dissolution …

Formation of Helmholtz double layer/electrical double layer (EDL) at the junction

of the electrode & the soln.
The P.D. across the EDL is the cause for the EP.

18
Absolute EPs cannot be measured i.e. it is impossible to determine absolute half-cell
potential—Why?
All voltage measuring devices differences in potential
Voltmeter-2 knobs (EPs cannot be measured with one wire!)
–one contact – test electrode
--other contact –with the soln in the electrode compartment via another conductor
Second contact  solid/soln interface  acts as second half cell
Redox rxn must occur if charge is to flow & potential is to be measured
Potential is associated with this second rxn
Absolute half-cell potential is not obtained
Difference between the half-cell potential of test electrode & a half cell made up of
the second contact & the soln.
We can only determine the relative value of electrode potential, if we can fix
arbitrarily the potential of any one electrode.
The numerical values of electrode potentials of different electrodes are relative values
w.r.t SHE by arbitrarily fixing its potential as zero.
Therefore, single electrode potentials of electrodes are referred to as potentials on the
hydrogen scale.

19
Sign of EP:
A +ve sign on the EP value indicates that the half cell acts as cathode & acepts
electrons from the hydrogen electrode.
A –ve sign on the electrode potential value indicates that the half cell acts as anode by
releaseing electrons to the hydrogen electrode.

According to latest convention, all single electrode potential values reported represent
reduction potentials.

20
The relation between E & ∆G:
The maximum electrical work as per thermodynamics, chemical reaction can do is
given by the value ∆G for the reaction.
We, max = ∆G-----------------(1)
The net electrical energy & the emf of the cell produced in a cell is the product of the
quantity of electricity that passes through the cell & the emf of the cell.
We = QE Joules. -------(2)
If n moles of electrons are transferred in the cell reactions, the quantity of electricity =
nF
Therefore, electrical energy= nFE, ----------(3)
Electrical energy produced = decrease in free energy for cell reaction i.e. - ∆G = nFE
or ∆G = -nFE Joules-------(4)
A cell in which the overall reaction has not reached chemical equilibrium can do
electrical work as the reaction drives electrons through an external circuit.
The cell does net work at the expense of decrease in free energy. If we know emf E,
∆G can be calculated. The larger the value of CP, the further the reaction is from
eqmThe sign of CP tells us the direction in which rxn. must shift to reach eqm.
Relation between E & ΔH:
From Gibbs–Helmholtz equation: -ΔG = -ΔH - T [δ(ΔG)/ δT]P

ΔG = ΔH + T [δ(ΔG)/ δT]P ------- (5)

-nEF = ΔH + T {δ(-nEF)/δT}p

21
 nFE = -ΔH + TnF(δE/δT)P { as n & F are constants}
ΔH = TnF(δE/δT)P–nFE
Enthalpy Change ΔH = nF[T(δE/δT)P –E] --------(6)
If we know, emf & temp.coeff. of emf, ΔH can be calculated
The heats of reaction calculated from emf measurements is almost equal to values
derived from thermal measurements.
Case-1, If (δ E/ δ T)P =0, nFE = - ΔH .The electrical energy is equal to the heat of
reactions.
Case-2, If (δ E/ δ T)P >0, nFE > - ΔH. The additional energy will come either from
surrounding or the temperature of the cell would fall.
Case-3, If (δ E/ δ T)P <0, nFE < - ΔH. The excess energy will be given either to the
surroundings or the temperature of the cell would rise.
Entropy Change:
We know that ΔG = ΔH -TΔS
-nFE = nF[T(δE/δT)P –E] - T ΔS
Entropy change: ΔS = nF(δE/δT)P ------(6), ΔS can be calculated
Numerical problems-Follows---------- Calculate ΔS, ΔH, ΔG at given T

If we know emf & temperature coefficient of emf, ΔH can be calculated.

Relation between E & ΔS :

(7)
We know that ΔG = ΔH –TΔS, Substituting the values of ΔG & ΔH,
-nFE = nF[T(δE/δT)P –E] - T ΔS

Entropy change: ΔS = nF(δE/δT)P ------(6), ΔS can be calculated

ΔS = ΔH- ΔG  Do not use in the calculations !

T

ΔG= -nFE implies ΔS = nF(∂ɛ/∂T)P

If we know number of electrons involved in the cell reaction & temperature
coefficient of emf, ΔS can be calculated.

21
Solution:1- ∆G: ∆G = - n FE
n = 2 for the cell reaction; F = 96,500 C
E= 1.0181 V at 298 K
∆G = -2 x 96,500 x 1.0181 J = -196.5 KJ
∆H: ∆H = nF [ T (δE /δT)P – E]
(δE/δT)p = 1.0181 – 1.0183 / 298-293
= -0.0002 / 5 = -0.00004VK -1
T = 298 K
∆H = 2 x 96,500 { 298 x (-0.00004) – 1.0181)
= -198. 8 KJ
ΔS: ΔS = nF (δE / δT) P
= 2 x 96,500 x (-0.00004) = -7.72JK -1
Soln. 2. Here n = 2, E = 0.6753 V at 298 K and 0.6915 at 273 K.
∴ (δE/δT)p = (0.6753-0.6915) V/ (298-273) K = - 0.00065 V/K
Now at 298 K, ∆H = nF [ T (δE /δT)P – E]
= 2 mol x 96,500 C mol-1{ [298 K x (- 0.00065 V/K)] –
0.6753 V }
= -167. 7 KJ
∆G at 298 K ; ∆G = - n FE = -2 x 96,500 x 0.6753 = -130.33 KJ
ΔS = nF(δE / δT) P
= 2 x 96,500 x (0-00065) = -125.45 J.K-1

22
Derivation:
Consider a general redox reaction:
Mn+(aq) + ne- → M(s) ----(1)
We know that, ΔG =ΔGo +RT ln K ----(2)
and ΔG =-nFE ----- (3)
ΔG =ΔGo +RT ln[M]/[Mn+]-----(4)
-nFE= -nFEo + RT ln [M]/[Mn+]----(5)
E= E – RT/nF ln 1/[Mn+]------(6)
o

E=Eo- 2.303 RT/nF log 1/[Mn+]---(7)

At 298K,
E= E -0.0592/n log 1/[Mn+]-------(8)
o

E= Electrode potential at some moment in time

E0= Standard electrode potential
R= Universal gas constant ( joules per mol K)
T= Temperature in Kelvin scale
F= Faraday constant (96,500 Coulumbs)
n = Number of electrons transferred in the half reaction/ cell reactions
[Mn+]= Concentration of metal ion at that moment in time (moles per litre).

The Nernst equation for the emf of the cell is

Ecell = Eocell – 2.303RT/nF log [C]c [D]d /[A]a [B]b
At 298 K,

23
Application of the Nernst equation:
It can be used to calculate the potential of a cell that operates under non-standard
conditions.
It can be used to measure the equilibrium constant for a reaction. At eqm. the overall
cell potential for the reaction is zero. i.e. E=0
0 = Eo - RT/nF lnKc
Kc = e nFE0 / RT

23
Solution :1:
Cell reaction: Fe + Cu2+ ↔ Fe2+ + Cu

ECell= E0Cell-0.0592/2 log [Fe2+ ]/[Cu2+]

ECell= 0.78 + 0.0296 log 10/1

=0.8096V

Soln. 2:
Cell representation: Zn/ Zn2+((1M)//Ag+(10M) /Ag

Cell reaction: Zn + 2Ag+ ↔ Zn2+ + 2Ag

ECell= E0Cell-0.0592/2 log [Zn2+ ]/[Ag+]2

ECell= 1.56 + 0.0592 log 10/1.0

=1.6192 V

24
Construction: Pure mercury at the bottom of a tube. Paste of mercurous chloride
(calomel) filled with sat’d soln of KCl. Pt-wire sealed at its end fixed into main tube
(Pt-wire remains dipped into the mercury)
The electrode can be represented as ; Hg (l) /Hg2Cl2 (sat’d)/KCl-(sat’d/xM)
The calomel electrode can act as anode or cathode depending on the nature of other
electrode of the cell.
When it acts anode, the electrode reaction is
2Hg(l) + 2Cl- (aq) → Hg2Cl2 (s)+ 2e-
When it acts as cathode, the electrode reaction is,
Hg2Cl2(s) + 2e- → 2Hg (l) + 2 Cl-(aq)
The net reversible electrode reaction is,
Hg2Cl2(s) + 2e- ⇌ 2 Hg (l) + 2 Cl-(aq)

Electrode potential is given by

E = Eo - 0.0591 log [Cl-] at 298 K
Its electrode potential depends on the concentration of KCl solution.
Uses:
Since the electrode potential is a constant it can be used as a secondary reference
electrode to replace the inconvenient SHE for potential measurements.
The test electrode, Zn(s) /Zn2+(aq) is coupled with a sat’d calomel electrode.
Zn(s)/Zn2+ (aq)││Cl- (sat’d soln.) /Hg2Cl2(s) / Hg (l)
The emf of the so formed cell is determined experimentally by potentiometric method.

25
Then E cell = E cathode – E anode
= 0.2444 – Ezn
Ezn = 0.2444 – E cell

To determine the pH of a solution cell:

H+ /pt,H2 (g)//Hg(l) / Hg2Cl2 (s)

E cell = E cathode – E anode

= 0.2422+ 0.0592 pH
pH = (E cell- 0.2422) /0.0592

25
It is less prone to contamination because the mercury/ mercurous chloride interface
is protected inside a tube not in direct contact with the electrolyte.
If we use the Calomel electrodes above 50o C , the mercurous chloride breaks down,
yielding unstable readings. This is important if substantial temperature changes occur
during a measurement.

26
Construction: The electrode consists of a thin glass membrane, typically about 0.03
to 0.1 mm thick, sealed onto one end of a heavy–walled glass tube. A special variety
of glass (corning 0l5 glass with approximate composition 20 % Na2O, 6 % CaO & 72
% SiO2) is used which has low melting point & high electrical resistance. The glass
bulb is filled with a solution of constant pH (0.1 M HCl). A small volume of saturated
silver chloride is contained in the tube. A silver wire in this solution forms a
silver/silver chloride reference electrode which is connected to one of the terminals of
a potential measuring device. The internal reference electrode is a part of the glass
electrode & it is not the pH sensing element. Only the potential that occurs between
the outer surface of the glass bulb & the test solution responds to pH changes.
Working: The glass is a partially hydrated aluminosilicate containing sodium or
calcium ions. The hydration of a pH sensitive glass membrane involves an ion-
exchange rxn. between singly charged cations in the interstices of the glass lattice &
protons from the solution. The process involves univalent cations exclusively because
divalent cations are too strongly held within the silicate structure to exchange with
ions in the solution & hence immobile. The ion-exchange reaction can be written as

H+ + Na+ ⇌ Na+ + H+
Solution glass solution glass

The Na+ ions on the glass membrane are exchanged for H+ ions in the solution. The

27
potential of the electrode is controlled by the difference between the hydrogen ion
concentration inside & outside the thin glass membrane. Since the H+ ion
concentration inside the electrode is constant, the electrode’s potential varies only
with the concentration of H+ in the solution outside. Thus the potential arises from the
difference in positions of ion-exchange equilibrium on each of the two surfaces. The
surface exposed to the solution having the higher H+ concentration becomes positive
with respect to the other surface. This charge difference or potential serves as the
analytical parameter when the pH of the solution on one side of the membrane is held
constant. Evidently the selectivity of glass electrodes is related both to the ability of
the various monovalent cations to penetrate into the glass membrane and to the degree
of attraction of the cations to the negative sites within the glass.

27
The overall potential of the glass electrode has three components.
1) The boundary potential Eb, which varies with the pH of the analyte soln. It is made
up of two potentials, E1 & E2 which develop at the two surface of the glass membrane
i.e. the potential developed at the inner glass surface & the potential developed at the
outer glass surface.
Eb = E1-E2 _______________________ (1)
Where Eb is the boundary potential
E1 = potential developed at the interface between the exterior of the
glass & the analyte soln.
E2 = Potential developed at the interface between the internal solution
& the interior of the glass. The boundary potential is related to the concentration of
hydrogen ion in each of the solution by the Nernst-like equation.
Eb = E1 – E2 = 0.0592 log Cl / C2 _________________ (2)
For a glass pH electrode the hydrogen ion concentration of the internal solution is held
constant. So eqn. (2) becomes
Eb = K + 0.0592 log C1 __________________(3) (Recall pH= -log [H+]
Asymmetry potential include the following;
(i) Differing conditions of strain in the two glass surfaces during
manufacture
(ii) Mechanical abrasion on the on the outer surface during use
(iii) Chemical etching of the outer surface during use.
The asymmetry potential changes slowly with time.

28
The glass electrode potential can be written in the equation form as
EG = Eb + EAg/ AgCl + E asym __________________ (4)
Substitution of eqn – (3) for Eb, gives
EG = K + 0.0592 log C1 + EAg/AgCl + E asym
= K – 0.0592 log pH + E Ag/AgCl + E asym ___(5)
EG = EoG – 0.0592 pH __________________(6)
where EoG = K + EAg/AgCl + E asym. a combination of three constant terms = constant
To measure the hydrogen ion concentration of the test solution, the glass electrode
(indicator electrode) must be combined with an external reference electrode, which is
required for all kinds of ion-selective electrode determinations.

28
29
30
The glass electrode has an emf that changes with hydrogen ion concentration, i.e the
glass electrode is the most important indicator electrode for hydrogen ion. It is used
for the measurement of pH under many conditions & normally calomel electrode is
used as reference electrode to complete the cell.
E cell = E glass – E calomel where E glass = the E.P. of glass electrode.
E calomel = the E.P. of the SCE
E cell = EoG – 0.0592 pH – 0.2444
The EoG value of a glass electrode can be determined by dipping the glass electrode in
a solution of known pH. Typical fields are the clinical & food analysis, environmental
monitoring (industrial waste acidity of rain) & process control (fermentation, boiler
water, galvanization & precipitation)

31
Soln: Eog= 0.0592pH +Ecell + Ecal.
= 0.0592 x 2.8 + 0.24 + 0.2422
=0.648 V
pH = Eog -Ecell – Ecal./0.0592
= 0.648 -0.26-0.2422/0.0592
= 2.46

32
General rule: The –ve half cell has the lower conc of ions
The +ve half cell has the higher conc of ions
The CR proceeds in the direction that equalizes the concs in the half-cells
Change in conc. due to current flow- the higher conc. is reduced & the lower conc. is
increased -Eqm is achieved when the two concns. are equal.
e.g. Ag(s)/Ag+(C1)//Ag+(C2)/Ag(s)
Zn(s)/Zn2+(0.1M)//Zn2+(1.0 M)/Zn(s)

33
Working:
Anode: Ni (s)  Ni2+[C1] + 2e –
(Lower concentration reaction)
Cathode: Ni2+[C2] + 2e –  Ni (s)
(Higher concentration reaction)
Net reaction: Ni2+[C2]  Ni2+[C1]
There is a change in concentration due to current flow. The higher concentration is
reduced and the lower concentration is increased. The equilibrium is attained when
the two concentration are equal.
Emf of the concentration cell :
Ecell = Ecathode-Eanode

= {E0 + (2.303RT)logC2 }- {E0+(2.303RT)logC1}

At 298 K,
Ecell = 0.0592/ n log [C2/C1]
Conclusions:
i) When the two solns. are at the same concentrations
log [C2/C1] = 0, No electricity flows
ii) When [C2/C1] > 1, log [C2/C1] is positive and E is positive. Electrode in contact
with lower electrolyte concentration acts as anode and electrode in contact with higher
electrolyte concentration acts as cathode. When the cell is in operation, the

34
concentration of ions at the increases and that at cathode decreases.
iii) The magnitude of cell potential depends on the ratio of the electrolytic
concentration. Higher the ratio higher is the emf. If [C2/C1] increases from 0.001 to
0.01 voltage doubles.

34
Solution 1:
Ecell = 0.0591/n log C2/C1
0.09 =(0.0591/2) log ( x / 0.001)
x =1.097M
Solution 2: Ecell=(2.303 RT/nF) log C2/C1
0.029 = 2.303RT/n) log (0.01/0.001)
0.029 =0.057 x 1/ n
n = 0.057/0.029 =̃ 2
Valency of mercurous ions is 2, Hg2 2+

35
36
37
Battery Technology

1
 Battery Technology
• Introduction to batteries

• Basic concepts

• Battery characteristics

• Classification Lead-acid, NiCd- & lithium ion batteries

• Fuel cells, Construction & working of alkaline FC & proton

exchange membrane FC
Battery is a chemical reactor that convert chemical energy in to
electrical energy on demand.

Device that stores chemical energy that can be used as a source of

direct current when required
Dry Cell

Components of Battery
* Container
* Separator
* Electrolyte
* Active materials
* Terminals
4
 Battery characteristics
Voltage: measure of amount of electrons flow from a negative to positive electrode
Current: measure of the rate at which battery is discharging
Capacity: amount of electricity that may obtained from the battery
Electricity storage density or Energy density: electricity per unit weight of the
battery (Watt-hours/kilogram (W-hr/kg)
Power density: Power per unit weight of the battery
Cycle life: number of complete charging/discharging cycles a battery can perform
Shelf life: Life time of the battery, to what extent the current can be stored for many
years without self discharge or The duration of storage under specified condition
at the end of which a battery retains the ability to give specified performance
Design life: It is the elapsed time before a battery becomes unusable whether it is in
active use or inactive
 Classification & comparison of commercial cells –
Differences & similarities
Primary Batteries Secondary Batteries
1.Cell reaction is irreversible Cell reaction is reversible

2. Must be discarded after its May be recharged a number of

active elements have been times from an external d.c. source
consumed during its useful life
3. Have relatively short shelf life Have very long shelf life
4. Function only as galvanic cells
Function as galvanic cells during
discharge as & as electrolytic cells
5. Cannot be used as energy during charging process.
storage devices Can be used as energy storage
devices (e.g. solar/ thermal energy
6. Cannot be recharged converted to electrical energy)
e.g. Dry cell, Li-MnO2 battery Can be recharged.
e.g.Lead acid battery, Ni-cd battery
 Basic requirements of cells

Primary cell Secondary cell

• Compact, light weight & • Long shelf-life in both
fabricated easily charged & discharged
• High energy density & conditions
constant voltage • Longer cycle life & design
• Benign environmental life
properties • High power to weight ratio
• Longer shelf life & • Short time for recharge.
discharge period • High voltage & high
• Leak proof containers & energy density
variety of design options.
• Economically priced
 Secondary Cells
▪ Generation of electric energy, that can be restored to its
original charged condition after its discharge by passing
current flowing in the opposite direction.

▪ large number of cycles of discharging & charging.

▪ known as rechargeable cells, storage cells, or accumulators.

e.g. Lead storage cell.
Nickel- cadmium cell.
Lithium- ion batteries.
 Lead Storage Battery

• Anode: Spongy lead on lead grid.

• Cathode: Porous PbO2.
• Electrolyte: H2SO4(aq)( 20 %)
(density 1.21-1.30g/ml)

• Cell Scheme:
Pb/PbSO4;H2SO4(aq);PbSO4;PbO2/Pb
O.C.V. = 2V (Pair of plates)

https://rampages.us/chhabran01/wp-
content/uploads/sites/14076/2015/12/Lead-storage.png
 Reactions during discharging

 Anode: Pb (s) → Pb2+ (aq) + 2e-

Pb2+(aq) + SO42-(aq) → PbSO4(s)
Pb(s)+ SO42-(aq) → PbSO4(aq) + 2e-

 Cathode:PbO2(s)+ 4H+(aq)+2e- →Pb2+(aq)+ 2H2O(l)

Pb2+(aq)+SO42-(aq)→PbSO4(s)

PbO2(s)+4H+(aq)+SO42-(aq)+2e- → PbSO4(s)+
2H2O(l)

 Overall: Pb (s)+PbO2 (s)+4H+(aq)+ 2SO42-(aq) →

2PbSO4 (s)+2H2O(l)
 Reactions during Charging:
Cathodic reaction: PbSO4(s) + 2e- → Pb(s)+ SO42- (aq)

Anodic reaction: PbSO4(s)+2H2O(l) → PbO2(s) + SO42-(aq) + 4H

+(aq) +2e-

Net reaction:2PbSO4 (s) + 2H2O(e) → Pb(s) + PbO2(s) +2H2SO4

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13
 Limitations
• Self discharge: They are subject to self discharge with H2
evolution at negative plates and O2 evolution at positive plates.

Pb +H2SO4 PbSO4 + H2
PbO2 + H2SO4 PbSO4 +H2O +1/2 O2

Electrolysis of water: Due to overcharging electrolysis of water

takes place. Hence water content must be regularly checked
and distilled water must be added.
2H2O (l) + electrical energy → 2H2 (g) + O2(g)
Consequences of overcharging:
(i)Reduce the acid volume level and damage the exposed electrode grids
(ii)Dangerous high-pressure build-up that can lead to a serious risk of
explosion.
• Modern maintenance-free batteries:

• without a gas – release vent. Gassing is controlled by using

• 1. Pb-Ca (0.1 % ) as the anode which inhibits the electrolysis

of water.

• 2. a catalyst (e.g. a mixture of 98% ceria (cerium oxide) & 2%

platinum) that combines the hydrogen & oxygen produced

during discharge back into water

 Lead Storage Battery
Advantages Disadvantages
• highly efficient • Sulfation
• good service for • low energy storage to weight ratio
several years • Cell Potential decreases with decrease
in conc. of sulfuric acid
• low internal self –
• not efficient at LT
discharge
• Overcharging may damage the exposed
• provide a large electrodes & may also lead to
current explosion in extreme cases
• Sulfuric acid is highly corrosive liquid
• Lead is toxic & hence environmental &
health problems
• corrosion of the lead grid at the lead
dioxide electrode
 Applications

*Automotive: For starting, lighting and

ignition of IC engine driven vehicles.
*Consumer Applications: Emergency lighting,
security and alarm system.
*Heavy duty Application: Trains, lift trucks,
mining machines etc.
Nickel Cadmium Cell
• Anode: spongy cadmium metal
• Cathode: nickel (III) compound NiO(OH) or Ni(OH)3 mixed
with 20% graphite powder
• Electrolyte: concentrated solution of KOH (compatibility with the
various electrodes, good conductivity & low freezing point) 20-
28% Aq. KOH
• Separator: Thin plastic pins / Layers of cellulose felt
Cell Scheme:
• Container: Steel case
Cd/Cd(OH)2,KOH,Ni(OH)2, Ni(OH)3/Ni
O.C.V. = 1.25V
Working: Discharging
Anode: Cd(s)+2OH-(aq) → Cd(OH)2(s) + 2e-
Cathode: 2NiO (OH) (s) + 2 H2O + 2 e- → 2Ni (OH)2(s) + 2OH-(aq)
________________________________________________
Cd(s) + 2NiO (OH) (s) + 2H2O → 2 Ni(OH)2 (s) + Cd(OH)2(s)
____________________________________________________
Charging reactions:

➢Anode (cathode during discharging)

2 Ni(OH)2(s) + 2OH-(aq) → 2 NiO(OH) (s) + H2O+2e-

➢Cathode: (anode during discharging)

Cd(OH)2 (s) + 2e-→ Cd(s) + 2OH-(aq)

➢Overall reaction: 2 Ni(OH)2 (s) + Cd(OH)2(s) →

2 NiO(OH) (s) + Cd(s) +2H2O(l)
 Nickel Cadmium Cell

Advantages Disadvantages
• Long cycle life • Environmental pollution hazard
• Constant voltage • Increased weight
• Long shelf life • High overall capital cost
• No gassing • KOH is a corrosive hazardous
• Long design life chemical
• Good performance at LT
• Produce large instantaneous
currents as high as 1000-8000 A
for one second.
 Applications:
• In flash lights, photoflash units & portable electronic equipment

such as radios, micro tape recorders, calculators, cordless phones,

electronic shavers, drills & garden tools. Used in emergency lighting

systems, alarm systems, personal audio equipment (walkman type

cassette players), kitchen appliances and other battery powered

small tools, toys & games.

22
 Lithium ion cells

Different configurations of Li ion batteries

 Lithium ion cells
➢ Cathode: a transition metal oxide MO2 of variable oxidation state (MnO2,
CoO2, NiO2) which can intercalate lithium usually cobalt dioxide, CoO2 is
used

➢ Anode: made up of graphite, in to which lithium ion is intercalated (LixC6).

➢ Separators: polyolefin’s (PP/PE/PP or just PE) using 3- to 8- μm layers

with 50% porosity.

➢ Electrolyte: 1-molar solution of a lithium salt in an organic solvent.

Eg: 1)Lithium hexafluorophosphate (LiPF6) in the solvent

propylene carbonate
2)Lithium tetrafluoroborate(LiBF4 ) in the solvent ethylene carbonate
Lithium ion cells
27
 Discharge reaction:-

The main principle is based on the movement of lithium ions

between anode and cathode through the electrolyte occurs
during charge and discharge process.

Anode reaction: Li ( C ) Li+ + e-

Cathode: Li+ + e- +CoO2 LiCoO2

The overall cell reaction is as follows:

Overall: CoO2 + Li ( C ) LiCoO2

Charging reaction:-

The main principle is based on the movement of lithium

ions between anode and cathode through the electrolyte
occurs during charge and discharge process.

Anode: LiCoO2 Li+ + e- + CoO2

Cathode reaction: Li+ + e- Li ( C )

The overall cell reaction is as follows:

Overall: CoO2 + Li ( C ) LiCoO2

Working of Li- ion cell

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30
 Lithium - ion Cell
Advantages Disadvantages
• Designed to overcome safety problems • Poor charge retention
• Long cycle life • Self discharge rate is about
• Small, light & provide high energy 10% per month
• High cost
density
• Can be operated in a wide temperature
range (Good low temperature
performance)
• High average voltage
• Li-highest oxidation potential
• High energy density due to low atomic
mass
Manufacture of Battery

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 Fuel cells
A fuel cell is a galvanic cell in which chemical energy of a fuel –
oxidant system is converted directly into electrical energy in a
continuous electrochemical process

The reactants (i.e. fuel + oxidant) are

constantly supplied from outside and the
products are removed at the same rate as
they are formed.
Anode:
Fuel → Oxidation products+ ne-
Cathode:
Oxidant + ne- → Reduction products 33
 Fuel cells

Micro fuel cell Toshiba fuel cell with refueling cartridge

Advantages:

High fuel to electricity conversion efficiency of 70-75% is

observed in fuel cells compared to thermal power plants (35-
40% )

Fuel cells do not cause noise pollution, chemical pollution &

thermal pollution normally associated with conventional power
plants.

A fuel cell produce a steady electric current as long as fresh

reactants are available.
Disadvantages

• Degradation or malfunction of components limits the practical

operating life and working of fuel cells on a large scale.

• Sensitive to fuel contaminants such as CO, H2S, NH3 & halides,

depending on the type of fuel cell. These contaminants must be
minimized in the fuels to enhance the cells’ efficiency

• High initial cost because of the expensive noble metals and

catalysts are required in the construction of certain fuel cells.
 Alkaline fuel cell

Anode: Porous graphite / porous nickel

electrode coated with finely divided Pt/Pd.
Cathode: Porous graphite
electrode/porous nickel electrode coated
with finely divided Pt/Pd.
Fuel: Hydrogen
Oxidant: oxygen
Electrolyte: 35-50% KOH.
Operating Temperature: 20 to 90oC.
O.C.V. =1.20V
 Alkaline fuel cell

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 Alkaline fuel cell
Working:
At Anode:
• H2(g) + 2OH-(aq) 2H2O(l) + 2e-
At Cathode:
1
• O2(g) + H2O(l) + 2e- 2OH-(aq)
2
1
Overall: H2+ O2 H2O(l)
2

*Water should be removed from the cell.

*O2should be free from impurities.
Alkaline fuel cell

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 Alkaline fuel cell
Advantages Disadvantages

❑ Active O2 electrode kinetics ❑ Electrolyte sensitive to CO2

❑ Flexible to a wide range of ❑ Reformer with a highly
electro-catalysts effective CO & CO2
removal system
Applications

As energy source in space shuttles e.g. Apollo spacecraft.

In submarines and other military vehicles.
Suitable in places where, environmental pollution and noise are
objectionable.
 Polymer electrolyte membrane fuel
cell

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 Proton exchange membrane cell
Construction

• Electrolyte:- Ion exchange polymeric membranes.

• Electrodes:- Typical gas diffusion electrodes, made up of

porous C coated with Pt catalyst.

• Fuel:- Hydrogen

• Oxidant:- Air

• Catalyst:- Platinum

• Operating temperature:- 30 – 80oC.

• Charge-carrier:- H+
 Perflourinated membrane by DuPont.

F F F F F F F F F
Role of conducting membrane
C C C C C C C C C

F F F F O F F F F
1. It acts as electrolyte to provide ionic
F C F
conduction b/w anode and cathode
F C F
2. Its serve as a separator for two
O
reactant gases
F C F

F C F

O=S=O
-
O
+
H

PERFLUOROSULFONIC ACID MEMBRANE

• Working
Anode reaction:
H2 2H+ + 2e-

Cathode reaction:
½ O2 + 2H+ + 2e- H 2O

Overall reaction:-
H 2 + ½ O2 H2O

❖ Optimized proton and water transport properties of

membrane are crucial for efficient fuel cell operation
 PEMFC
Advantages Disadvantages
• solid electrolyte provides • Dehydration of membrane reduces
excellent resistance to gas proton conductivity and excess
crossover. water can lead to flooding of the
electrolyte. Both the conditions
leading to poor performance.
• low operating temperature
allows rapid start-up
• Perflourinated membranes have high
cost
• capable of high current
densities • sensitive to poisoning by trace levels
of contaminants including CO,
sulfur species and ammonia.
 Differences and Similarities
Fuel cell Galvanic Cell
• Do not store chemical energy • Store chemical energy
• Reactants fed from outside the • Reactants form an integral part of
cell continuously its construction.
• Need expensive noble metal • These special conditions are not
catalysts & optimum required
operative conditions • Get-discharged when stored – up
• Do not get discharged & no energy is exhausted.
need of charging • Limited life span in use
• Never becomes dead as long
as fresh reactants are available
• Useful for long-term • Useful as portable power services.
electricity generation.
• Reaction products must be • No such problem
continuously removed
• No pollutants generated • Pollutants are generated after their
• Significantly higher power useful life
densities • Lower power density
 Summary

• Battery - device consisting of several galvanic cells that convert stored

CE into EE.
• Batteries – primary or secondary types.
• The construction, working & applications of lead acid battery, nicad
cell, lithium copper sulfide cell have been discussed .
• Fuel cell - converts the CE from a fuel into EE by oxidation process.
• Fuel cells require a constant source of fuel & oxygen /air to sustain the
oxidation reaction.
 Quiz 4
The emf of a cell consisting of a hydrogen and the normal calomel is 0.664 V at 25 ºC. Calculate
the pH of the solution containing the hydrogen electrode.
Ecell= Ecal (normal) –( −0.0591pH)
0.664 = 0.2810+0.0591 pH
0.383=0.0591 pH
pH= 6.48

A glass electrode dipped in a soln. of pH = 4 offered an emf of 0.2066 V with decinormal calomel
electrode at 298 K. When dipped in a soln. of unknown pH at the same temperature, the recorded
emf was 0.1076 V. Calculate the pH of the soln. [CE = 0.2412 V].
pH= (Ego− Ecell − Ecal(decinormal) ) / 0.0591
4=( Ego− 0.2066− 0.3335) /0.0591
Ego= 0.7765 V
pH= ( 0.7765− 0.1076−0.3335) / 0.0591
pH= 5.67

Write the cell scheme and determine the electrode potential of zinc immersed in 0.1 M ZnSO4.
Given E.M.F. of cell =1.0022 V and Eo (Calomel electrode) =0.2422V.
Zn / ZnSO4( 0.1M) // KCl; Hg2Cl2;Hg
Ecell = E cathode – E anode
1.0022 = 0.2422 – E Zn2+ / Zn
E Zn2+ / Zn = 0.2422 – 1.0022 49
= - 0.76 V
 Metal Finishing
Contents
• Theory of electroplating
• Polarization, decomposition potential & overvoltage
• Characteristics of a good deposit
• Factors influencing the nature of deposit
• Methods of cleaning the metal surface
• Hard chromium & decorative chromium plating
• Electro-less plating – Copper plating
 Metal Finishing
Process of deposition of an adherent metallic film of a noble metal on
a base metal or polymer surface

OBJECTIVES
➢ In general a metal or alloy used for a purpose does not meet all
the requirements. Metal finishing is one of the methods
employed to improve their lacking properties.

• Improving resistance to corrosion, scratch or abrasion and wear.

• Enhancing decorative appearance.
• Improving solder ability and electrical properties

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 Metal Finishing

Electroplating Electrolessplating
Using electricity Using reducing agents
Electroplating of chromium Electroless plating of copper
ELECTROPLATING
• Process in which a thin layer of coating metal is deposited on a base
metal by passing d.c. through an electrolytic soln., containing the
soluble salt of the coating metal
• Theory of electroplating; Anode, cathode, Electrolyte, Direct current

Essential Components
A d.c. electrical power source.
Anode : Inert material / coating metal
Cathode : Article to be plated.
Electrolytic bath: Solution of conducting
salt, metal to be plated in a soluble form,
buffer and additives.
Container: Made up of rubber lined steel,
wood or concrete.
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Metal Finishing - Dept. of Chemistry 4
Electroplating of Copper
• Anode : Made of coating metal.

• Cathode: Article to be plated.

• Electrolyte: CuSO4 solution.

CuSO4 Cu2+ + SO42-

*On passing current,

Cu2+ + 2e Cu (Cathode)

Cu + SO42- CuSO4 + 2e.(Anode)

Continuous replenishment of electrolytic salt during electrolysis. If
anode is some inert material like graphite, then electrolytic salt is added
continuously to maintain proper coating metal ion concentration
Metal Finishing - Dept. of Chemistry 5
6
Electroplating process

7
Factors Governing Electroplating
• Decomposition Potential (D.P.)

• Polarization

• Overvoltage
Decomposition Potential
• Minimum external potential at which the electrolysis current
begins to increase appreciably & continuous electrolysis sets in is
known as decomposition potential of the electrolyte.
• Measurement
Factors affecting DP

• Strength of the current flowing through the cell

• Chemical nature of the electrodes

• Physical nature of the electrodes

• Activity of the electrolyte

• Absolute temperature

• Uses of DP
Overvoltage

• The decomposition of an electrolyte is expected to start as soon

as applied potential reaches the value of reversible emf of the
cell.

• But when products discharged at the electrodes are gases, then

the actual decomposition potential is invariably much higher
than its theoretical reversible electrode potential.

• The excess voltage is referred to as over voltage of the gas.

Overvoltage
• Difference between the actual applied emf to bring about continuous
electrolysis & the theoretical emf needed for such electrolysis.

• For instance the reversible potential of oxygen gas with smooth Pt electrode
is 1.23 V. But actual gas evolution takes place at a potential of 1.68 V. The
excess 0.45 V is the over voltage of oxygen on smooth Pt surface.
• Factors affecting overvoltage:
• Nature & physical state of the electrodes
• Current density
• Temperature
• Nature of the electrolyte
• Nature of the material deposited
Polarization
• Development of over potential in an electrolytic cell is called
polarization.
• Electrolytic processes occur at the electrodes of the cell.
• Polarization sets in the cell when the electrode processes become slow
and irreversible.
• Magnitude of over potential is directly proportional to the extent of
polarization.

Types of Polarization
➢Concentration polarization
➢kinetic or activation polarization
 CONCENTRATION POLARIZATION
• An electrochemical reaction occurs only at the surface of the two electrodes.
• Adjacent to the electrode surface reactant concentration decreases.
• The reactant species are transported to the electrode surface by processes
like diffusion and migration from the bulk of the solution.
• Current flowing through the cell drops when the rate of transport is
insufficient to match the electrode reaction.
• A potential higher than the theoretical value is required to maintain the
current at the necessary level.
• can be minimized by:
* By raising the temperature.
* Mechanical agitation of the solution.
ACTIVATION POLARIZATION

This is caused when any of the following steps become slow and
need activation energy

➢Adsorption of the reactant on the electrode.

➢Charge transfer across the metal -solution interface

➢Desorption of the product from the electrode

➢A higher potential than the theoretical value is to be applied to

maintain current at the necessary level.
Characteristics of a good deposit

• The deposit should be bright and lustrous.

• The deposit should be continuous, uniform, non porous and

adhesive.

• It should be hard and ductile.

• It should be of fine grained nature.

 Factors Influencing The Nature Of Deposit

• Current Density:
An optimum current density should be applied.

If low - leads to slow process, take more time to

complete the process
results in coarse grained deposit.

If high - leads to rough and brittle deposit.

results in burnt and spongy deposit.
 Metal salt and electrolyte concentration:
• Moderate/low electrolyte concentration should be maintained in
bath to get a better deposit.
• If concentration of metal ion is low the crystal size will be
smaller and a fine adherent film may be coated
• Firm and adherent deposits.

Temperature
• It should be between 35 oc and 65 oc.
• Lower temperature:
reduces the solubility of the metal salt. reduces the
mobility of the ions.
• Higher temperature:
affects the lining of the equipment, electrode surface
and the substrate.
Decomposition of organic agents.
 Agitation
• Agitation of the solution brings up a fresh supply of metal
salts to the cathode.
• It also sweeps away gas bubbles which may otherwise cause
pits.
• Rapid agitation may
stir up the sludge.
results in rough and porous deposits.
pH of the electrolytic bath:
• Suitable pH is maintained using appropriate buffers.
• In Ni plating borate buffer is used to maintain pH 4.5.
• At low pH more H2 evolution takes place on the cathode.
• At higher pH precipitation of hydroxides of metal takes place.
 Addition agents
• The wide range of additives are added in low concentrations,
serve to electroplating bath to modify the structure and properties of
the electrodeposits.
• Function:
• Makes the deposit smooth, fine grained, hard and adherent.

• Types of additives:
• Complexing agent:
Eg: Cyanide, sulphamate ions.
• Brighteners:
Eg: Aromatic sulphonates, thiourea.
• Wetting Agents:
Eg: Sodium lauryl sulphate.
• Levelers:
Eg: Cellulose derivative
Throwing power:

• Throwing power is defined as the degree of uniformity of metal

distribution or evenness of deposit thickness obtained on a cathode of

irregular shape.

• If the distribution of the deposit is uniform throughout the surface of

the article to be coated, the throwing power is considered good.

• Tendency of plating bath solution to give uniform coating

irrespective of the shape of the object

Methods of cleaning the metal surface
• Physical/Solvent cleaning: To dissolve oils and greases. Eg:
CCl4,CH2Cl2,CHCl=CCl2.
• Chemical/Alkali cleaning: To remove minute organic residues, removal of
tarnish and oxide films .
Eg: NaOH,Na2CO3,Na3PO4.
• Mechanical Cleaning: removal of the oxide layer or rust and other inorganic
deposits. Eg: Impact tools like sandpaper, knife scrapers, wire brushes etc.
• Pickling: Removal of oxide films by means of an acid. Eg: 10 - 30%
sulphuric acid
• Electro-polishing: The metal to be cleaned is made as anode in a suitable
acid solution.
 Electroplating of Chromium
Decorative Chromium:- A thin deposit of Cr applied over either
copper-nickel or nickel undercoat. 0.25 -0.75 µm
Hard Chromium:- Involves deposition of a thick coating of
chromium directly over the substrate. 2.5 – 300 µm.
Decorative coating Hard coating
Bath composition Chromic acid (250 g) + Chromic acid (250 g) +
H2SO4 (2.5 g) + H2SO4(2.5g)+ Trivalent-
Trivalent chromium(1g) chromium(1g)
Operating temp. 313-328 K 313-328 K
Anode Insoluble Pb-Sn alloy Insoluble Pb-Sn alloy
Cathode Article to be coated Article to be coated
Current density 20-40 mA/cm2 30-60 mA/cm2
Cathode efficiency 10 - 15 17 – 21
Applications Decorative applns with Coating of industrial
corrosion resistance finish on components like gauges,
automobiles, furniture, dies, cutting tools, piston
surgical & dental instruments rings & hydraulic rams.
Electroplating of Chromium

inert anodes are used

• The metal going into the solution is five times of the metal
getting deposited, resulting in the building up of excessive
chromic acid (Cr-III) concentration.

• This leads to imbalance of bath composition.

• Chromium metal becomes passive in the strongly acidic bath

and a black deposit is formed on the cathode.
 Electroplating of Chromium
• Chromium plating produces an attractive, wear resistant and
abrasion resistant surface.

• Chromium plating is not continuous; it is micro porous. Hence an

undercoat of copper and/or nickel is essential.

• Ni gives protection and chromium gives a decorative finish.

Applications:
*Decorative chromium provides a durable finish (on
automobiles, furniture, surgical & dental instruments).
*Hard chromium is applied to many components in almost
every industry.
Electrolessplating
• Method of depositing a metal or alloy over a substrate (conductor or
nonconductor) by controlled chemical reduction of the metal ions by a
suitable reducing agent without using electrical energy.

Metal ions + Reducing agent → Metal + Oxidized product.

Process of electroless plating: The process of electroless plating

involves the following steps:

(i) Preparation of active surface:

treatment with SnCl2 and PdCl2 on the plastic surface

SnCl2 + PdCl2 → Pd + SnCl4
Pd is coated on plastic.
 Electrolessplating
(ii) Preparation of plating bath (composition of the bath)

(a) Metal to be coated in the form of respective salt solution

(b) Reducing agents like formaldehyde and sodium hypophosphate
(c) Complexing agents like EDTA, tartrates, citrates to form metal
complexes to prevent excess deposition
(d) Stabilizers like thiourea, calcium ions to prevent decomposition of
the bath
(e) Accelerators like succinates, glycinates to increase the plating rate
(f) Brighteners like thiosulphate to give a lustrous appearance
(g) Buffers like boric acid to maintain the pH

(iii) Reduction step: Active surface is dipped in the bath and

deposition is carried out.

The rate of deposition is controlled by the amount of reducing agent

present and the type of chelating agent used.
Electroless plating of Copper

Composition of bath:
• Coating solution : CuSO4 solution (12 g/l)
• Reducing agent : HCHO (8 g/l)
• Buffer : NaOH (15 g/l) and Rochelle salt(14 g/l)
• Complexing agent : EDTA di sodium salt (20 g/l)
• Optimum pH : 11
• Optimum temperature : 25 0C.

Cu2+ + 2e Cu (reduction)
2HCHO + 4OH- 2HCOO- +2H2O + H2+ 2e-
(oxidation)
--------------------------------------------------------------------------------------------------
Cu 2+ + 2HCHO + OH- 2HCOO- +2H2O + H2 + Cu
---------------------------------------------------------------------------------------------------
28
Electrolessplating
Advantages Disadvantages
• More uniform coating with • Cost of waste treatment high
better TP than electroplating • Frequency of dumping
• No electrical energy required electroless bath high
• Superior quality deposits • Costs per unit weight of the
• Additives, levelers or complex deposited metal are more
filtration method not required • Needs pure chemicals
• Simple equipment • Chemical reductants
• Plating on articles made of expensive
insulators and semiconductors. • Metal salts & reductants are
• Coating is harder & better wear thermodynamically not
resistance stable
• Coatings possesses unique
• Impurities, dust or colloidal
mechanical and chemical particles promote
properties. decomposition of bath
components
 Electrolessplating

Applications
• Used for metalizing printed circuit boards.
• For producing through-hole connection necessary when double
sided printed circuit boards are fabricated.
• For plating on non conductors.
Comparison of electroplating & electroless plating
Particulars Electroplating Electrolessplating
Driving force Electrical energy Decrease in free energy of the
redox reaction
Cathodic Reaction Mn+ + ne- → M Mn+ + ne- → M
Cathode Article to be plated Article to be plated with
catalytic surface
Anode Separate anode Reducing agent in the soln.
Nature of deposit Pure metal or alloy Metal with reducing agent &
oxidized products as
impurities
Thickness-limit (µm) 1 - 100 1 – 100
Applicability Applicable to Can be used for conductors &
conductors only non-conductors
Throwing power Less TP; cannot be More TP; can be used for
(TP) used for irregular irregular & uneven shaped
shapes & intricate objects
parts
 Contents

▪ Introduction
▪ Classification
▪ Galvanic series
▪ Factors affecting
▪ Protection methods
▪ summary
 Learning Objectives

1. Unfold the practical aspects of metal corrosion with real life examples.
2. Be able to describe the mechanism of corrosion by electrochemical theory
3. Describe different forms of corrosion: galvanic, pitting, inter-granular, stress and
microbial influenced corrosion
4. Demonstrate an understanding of the importance of the factors affecting corrosion
5. Know about the different established and modern techniques to control corrosion
such as anodic/cathodic protection methods, organic /inorganic coatings
6. Distinguish between dry/wet corrosion, galvanizing/ tinning, electrochemical series/
galvanic series and organic/inorganic coating
 Definition

• Corrosion can be defined as spontaneous destruction or deterioration of

a metal by chemical, electrochemical or biochemical reaction.
Examples:
Rusting of iron
4Fe(s)+3O2(g)→ 2Fe2O3.H2O(s)
Tarnishing of silver
4Ag(s) +2 H2S(g) + O2(g) → 2Ag2S(s) + 2H2O(l)
Scales on copper
2Cu(s) + H2O(l) + O2(g) + CO2(g) →Cu2(OH)2CO3(s)
 Corrosion
Corrosion can be viewed as the reverse process of extractive
metallurgy.

State of higher energy State of lower energy

 Corrosion
Importance of Corrosion study
• Human Life and Safety
• Cost of Corrosion
• Conservation of Materials
• Academic interest

Consequences of Corrosion
• Maintenance and operating costs
• Plant shutdowns, loss of production
• Contamination and loss of valuable products
• Effects on Safety
• Loss of Aesthetic value
• Loss of technically imp. Surface properties
• Loss of efficiency
 Corrosion Classification

Corrosion

Dry corrosion Wet corrosion

(Chemical) (Electrochemical)
 Dry Corrosion

• Occurs due to the direct chemical reactions between the environment and the
metals / alloys
• Presence of an electrolyte is not at all essential for the corrosion to occur

Types:
Oxidation (due to reaction with oxygen)
Other gases (CO2, H2S, SO2, X2, etc.)
Liquid metal
 Oxidation Corrosion

occurs when metals are attacked by dry oxygen

Non porous
Metal + Oxygen→ Metal oxide (corrosion product) Adherent
Stable
Nature of the oxide film decides subsequent corrosion Protective
continous
• If a stable film is formed
ex. Al, Sn, Pb, and Cu
• Unstable metal film decomposes back into the metal and oxygen.
ex. Ag, Au, Pt.
• Volatile film layer volatilizes as soon as it is formed, thereby accelerating the
corrosion.
ex. MoO3
 Dry Corrosion

(ii) Corrosion by other gases :

Due to some gases SO2, Cl2, CO2, and H2S,
depends mainly on the chemical affinity between the metal and the gas involved.
Eg. dry Cl2 attacks silver metal and forms AgCl as a thin protective and non-porous
layer on the metal. As a result of this protective layer on the metal surface, the
intensity of corrosion decreases.
(iii) Liquid metal corrosion :
Occurs when a molten liquid is continuously passed on a solid metal surface or on
alloy. This behaviour may be either due to the dissolution of the molten liquid or due
to penetration of the molten liquid into the metal phase.
 Wet Corrosion

Wet corrosion occurs due to the existence of separate anodic and cathodic areas, between
which current flows through the conducting solution

At Anode:
M(s) → Mn+ + ne−

At Cathode:
(i) Hydrogen evolution
(ii) Absorption of oxygen depending upon the nature of corrosive environment.
 Wet Corrosion

Anodic reaction:
M → Mn+ + ne-
Fe → Fe2+ + 2e-

Cathodic reactions:
i) Hydrogen evolution:
2H+ (aq) + 2e− → H2 (dearated & acidic medium)

H2 liberation along with OH- ions formation

2H2O + 2e- →H2(g) + 2OH- (aq) ( deaerated & neutral)

ii) Reduction of oxygen in neutral medium:

O2 (aq) + 2H2O + 4e− → 4OH−(aq) (aerated & neutral)
Mechanism of rusting
 Mechanism of rusting
Rusting take place when iron is exposed to oxygen in the
presence of humidity/moisture.

At anodic sites [Fe → Fe 2+ + 2e−] x 2

At cathodic sites O2 (g) + 2H2O (l) + 4e− → 4OH−(aq) + H2
Overall reaction 2Fe + O2 (g) +2H2O (l) → 2Fe2+ (aq)+ 2OH−(aq) + H2

Reactions to the formation of hydrated ferric oxide (rust)

Fe2+(aq) + 2OH− (aq) → Fe (OH)2

In presence of enough oxygen, ferrous hydroxide reacts with moisture and oxygen
to give yellow rust.
4 Fe (OH)2 + 2 H2O + O2 → 2 [ Fe2O3. 3H2O] ( Yellow rust)

If the supply of oxygen is limited, the corrosion product may be black anhydrous
magnetite.
6 Fe (OH)2 + O2 → 2 [ Fe3O4. 3H2O] ( Black Rust)
Mechanism of rusting
 Comparison between Dry & Wet Corrosion

Dry Corrosion Wet Corrosion

Involves direct attack of Occurs due to the existence of
atmospheric gases separate anodic and cathodic
areas between which current
flows through the medium
Do not need a corrosive medium Needs corrosive medium
Types include oxidation corrosion, Types include galvanic, pitting,
liquid metal corrosion and stress and intergranular
corrosion by gases
Less prevailing More common
 Galvanic Series

Need for galvanic series

The electrochemical series does not take passivity into
account.
The electrochemical series does not account for
corrosion behavior of alloys.

• The series prepared by studying the corrosion of

metals and alloys in a given environment like sea
water.
 Characteristics of galvanic series

• Galvanic series include both metals and alloys.

• Metals and alloys are arranged in the increasing order of their corrosion resistance
in seawater.
• Metals and alloys having almost same corrosion characteristics are grouped within
a square bracket.
• Same metal can occupy two positions in the galvanic series; For example,
aluminum occurs both active and noble region depending upon its active and
passive states.
 Comparison between ES & GS
Electrochemical series Galvanic series
• EPs are measured by dipping pure metals
in their salt solution of 1M conc. without • Series developed by studying corrosion of
any oxide film. metals & alloys in unpolluted sea water,
without their oxide films.
• Position of a given metal in is fixed. • The position of a given metal may shift as it
takes active & passive states.
• Gives no information regarding the • Alloys are included based on their corrosion
position of alloys. behavior
• Metals & non- metals are included. • Metals and alloys are included

Similarity: In both, base metals are placed higher & noble metals lower
in the series
 Types of Corrosion

• Galvanic corrosion

• Pitting corrosion

• Inter-granular corrosion

• Stress corrosion
 Galvanic Corrosion

• Occurs when two dissimilar metals are in contact with an

electrolyte.
• Anode:
Metal with lower standard electrode potential value.
• Cathode:
Metal with higher standard electrode potential.
• Examples:
• Copper piping connected to steel tanks
• Steel screws in a brass marine hardware.
• Lead antimony solder around the copper wire.
• A steel propeller shaft in bronze bearing
• Steel pipe connected to copper plumbing
Galvanic Corrosion
 Galvanic Corrosion

This rainwater guttering is made of aluminium and would

normally resist corrosion well. Someone tied a copper
aerial wire around it, and the localised bimetallic cell led to
a “knife-cut” effect.
 Pitting Corrosion

A pit may be described as a cavity or hole with the surface

diameter about the same length as or less than the depth.
The important reasons for the pitting corrosion are:
➢ Surface roughness or non uniform finish
➢ Scratches or cut edges
➢ Local straining of metal, due to non uniform stress
➢ Depositions of extraneous matter such as sand, scale,
water drop, dust etc.
 Pitting Corrosion

Pitting is usually due to the breakdown or cracking of the

protective film on a metal at specific points
Pitting corrosion is characterized by small anodic area and
large cathodic area, resulting in accelerated corrosion at the
anodic area.
It is an autocatalytic process, with the initially formed pit
produces conditions which are both stimulating and
necessary for the continuing activity of the pit.
Pitting Corrosion
 Pitting Corrosion

Pitting is dangerous because it is a localized and intense form of

corrosion and failure occurs with extreme suddenness.
 Stress Corrosion

Stress corrosion of stainless steel type 304, autoclave.

(Mallinckrodt Chemical Works)
 Stress Corrosion

• Also known as stress cracking

• Cracking of metal caused by the combined effect of a tensile stress
and a specific corrosive environment on the metal. Here, the
corrosive agents are highly specific and selective.
• The metal atoms under stress possesses higher energy levels than
the one with free from stress.
• The stressed part of the metal becomes more active than the stress
free part.
• Hence: Anode - stressed part & Cathode - stress free part.
Stressed part undergoes corrosion
• Examples:
Season cracking of brass
Caustic embrittlement of steel
Stress Corrosion
 Caustic Embrittlement
• This is a dangerous and occurring in mild steel, exposed to
alkaline solutions at high temp. and stresses.
• Water fed into boilers may contain free alkali (Lime soda process).
Na2CO3(aq) + H2O → 2NaOH + CO2(g)
• Local stresses exist in metal sheets of boiler under rivets.
• Minute cracks develop on the metal sheets when the stress is
relieved.
• This very dilute alkaline water flows into the minute hair-cracks
and crevices by capillary action
• Inside the crack, the water evaporates and caustic soda conc.
builds up
• This conc. alkali dissolves iron as sodium ferroate in
crevices/cracks, where the metal is stressed and the conc. of alkali
is much higher than that in the body of the liquid.
 Caustic Embrittlement
• The sodium ferroate decomposes, a short distance away from its
point of formation

3Na2FeO2 + 4H2O → 6NaOH + Fe3O4 + H2

6Na2FeO2 + 6H2O + O2 → 12NaOH + 2Fe3O4
• NaOH is regenerated and magnetite is precipitated thereby
enhancing further dissolution of iron
• When iron changes to these oxides, metallic properties like
malleability and ductility are lost.
• It becomes brittle. The brittleness is caused by caustic alkali.
• NaOH concentration cell forms between the stressed and
unstressed part of the metal

Iron│Conc. NaOH; Dilute NaOH │Iron

(stressed) (unstressed)
ANODIC CATHODIC
 Caustic Embrittlement

Prevention:

• Na2SO4, tannin or lignin is added to water.

• Boiler can be constructed by welding the sheets to avoid local
stresses.
• Caustic embrittlement is avoided by using demineralized water
Inter-granular Corrosion
 Factors affecting the Corrosion

Primary Factors (Factors related to the corroding metals):

• Nature of metal and relative electrode potentials of metals

• Relative cathodic and anodic area
• Hydrogen over voltage
• Nature of the corrosion product

Secondary Factors (Factors related to the environment)

• Concentration and nature of electrolyte
• pH of the medium
• Temperature
• Polarization
Corrosion Control Techniques
 Corrosion Control Techniques

Various methods we discuss in this course for corrosion

prevention are

• Selection of materials & design improvement

• Change of the metal
• Change of environment
• Use of coatings for separating metal from
environment
 Corrosion Control by selection materials

• Noble and pure metals show greater resistance to corrosion

Impurities in metal causes heterogeneity, which decreases
corrosion-resistance of the metal
• Suitable alloying of metals
Corrosion-resistance of most of the metals is best increased by
alloying them with suitable elements, but the alloy should be
completely homogeneous
e.g., Cr is the best alloying metal for iron or steel
 Corrosion Control by proper designing
The design of the material should be such that corrosion, even if
it occurs, is uniform and does not result in an intense and
localized corrosion
Some important design principles are:
• Avoid the contact of two dissimilar metals having large
difference in their electrode potentials
• Whenever the direct joining of dissimilar metals, is unavoidable,
an insulating fitting may be applied in between them to avoid
direct metal-metal electrical contact
 Corrosion Control by proper designing

If the contact between two

dissimilar metals is
unavoidable, two metals are
chosen in such a way that
the anodic metal should be
as large as possible and
cathodic metal should be as
small as possible
 Corrosion Control by proper designing

• Avoid residual moisture

 Corrosion Control by proper designing
• Metallic equipment should be supported on legs to permit air
circulation and to avoid the formation of damp areas under the
equipment
 Corrosion Control by proper designing
• Avoid sharp corners

• The anodic metal should not be painted or coated because

any break in coating would lead to rapid localized
corrosion
• Residual stress in fabricated articles should be avoided
• Avoid crevices
Corrosion Control by cathodic protection

The principle involved in this method is to force the metal

to be protected to behave like a cathode, there by
corrosion does not occur.
Two different methods:

• Sacrificial anodic method

• Impressed current method

Corrosion Control by sacrificial anodic method

• Zn and Mg are more reactive metals than Fe and hence

they become anodic part in contact with Fe
• Effective only when proper quantities of sacrificial
anodes are used
• Number and spacing of anodes depend upon the system
to be protected
• Examples:
Ship's steel hulls, offshore drilling platforms, oil and gas
pipelines under sea, containers used to store water and
other liquids are protected by this method
Corrosion Control by sacrificial anodic method

Anode: 2Mg(s) → Mg2+ (aq) + 4e−

Cathode: O2 (g) + 2H2O(l) + 4e− → 4OH−(aq)
Net reaction: 2Mg (s) + O2 (g) + 2H2O (l) → 2Mg(OH)2
Corrosion Control by sacrificial anodic method

• Anodic part: More reactive

metal
• Cathodic part: Structure to be
protected
The anode is sacrificed to
protect the structure.

Advantages:
• No external power supply is required
• Can be used in remote and difficult to reach areas
• Low installation cost
• Minimum maintenance cost.
Corrosion Control by impressed current method
• The metallic structure is made cathode with the use of impressed
current by connecting it to the negative terminal of the external
power source
• The anode may be made up of steel, graphite and platinum group
metals
• The inert anode is surrounded by back fill consisting of coke
breeze, gypsum to improve electrical contact

Advantages:
•Applicable to large objects
•Uncoated parts can be protected
Limitations:
•Larger installation cost
•Higher maintenance cost
Corrosion Control by anodic protection method

• Some of the metals like Ti and ferrous alloys (stainless steel)

can not afford cathodic protection
• The principle of anodic protection is
the growth of protective oxide surface film by the application of
anodic current on the metal / alloy appliance in a suitable
oxidising environment
Corrosion Control by anodic protection method
• When a passivating metal is immersed in an electrolyte with
increasing oxidizing power behaves as shown in the
following graph.

Ef D
C Passive state
Ep

Ecrit

Potential
B
Activate state
A

Ip Icrit
Current
 Corrosion Control by anodic protection method
The anodic protection to a structure is applied by using a device
called potentiostat.
In operation, the potentiostat maintains a constant potential
between the tank and the reference electrode, corresponding to the
passive range.
Potentiostat

Platinum
Calomel ref. electrode Auxiliary electrode
(cathode)

Passivated metal
Oxidising medium or alloy (anode)
to be protected
Corrosion Control by anodic protection method

• Advantages:
Its applicability even in extremely corrosive environment.
Low current demand

• Limitations:
It is restricted to the metals that show active-passive behavior.
Its initial installation cost is high.
Cannot reduce the corrosion rate to zero unlike cathodic
protection.
This needs continuous supply of electric current.
 Corrosion Control by Inhibitors

• An inhibitor is a substance when added in small quantity to

the electrolyte medium, inhibits the anodic or cathodic
reactions

Types of inhibitors:

• Anodic Inhibitors
• Cathodic Inhibitors
 Corrosion Control by Anodic Inhibitors

• Substances used to stop anodic reaction.

• They form insoluble compounds with the metal ions formed at
the anodic part .
• These insoluble compounds form a protective film on the anodic
surface.
• This film isolates the anode from the electrolyte medium and
stops its corrosion.
• The anions such as chromate, tungstate, molybdate, phosphate
etc., are used to arrest anodic process.
• Effective only when they are added above their critical
concentrations.
• If the added inhibitor is insufficient, it cannot plug all the anodic
sites and leads to severe pitting corrosion
 Corrosion Control by Cathodic Inhibitors

• Substances used to retard cathodic reaction.

• They form a protective film on cathodic surface and isolate it
from the electrolyte medium thereby preventing corrosion.
• Two major reactions taking place on cathodic surface
depending on the nature of corrosive environment and are
Hydrogen evolution type
Oxygen absorption type
 Corrosion Control by Cathodic Inhibitors

• Substances used to retard cathodic reaction.

• They form a protective film on cathodic surface and isolate it
from the electrolyte medium thereby preventing corrosion.
• Two major reactions taking place on cathodic surface
depending on the nature of corrosive environment and are
Hydrogen evolution type
Oxygen absorption type
 Corrosion Control by Cathodic Inhibitors
Hydrogen evolution:
2H+ + 2e- H2 (acid medium)
This reaction can be prevented either by
(i) Retarding the diffusion of H+ to the cathode.
(ii) Increasing hydrogen over voltage
• Addition of certain organic compounds, containing N or S, retards
the diffusion of H+.
• Such substances when added to corroding environment, are
adsorbed on the cathodic sites forming a protective film that
suppresses cathodic reaction.
e.g., Urea, thiourea, mercaptans and other heterocyclic
compounds.
• Substances added deposit as adherent metallic film on the cathode
areas and thereby prevents the evolution of H2.
• Oxides of Arsenic, antimony or salts like sodium meta arsenite are
used since hydrogen overvoltage for these metals is quite high
 Corrosion Control by Cathodic Inhibitors
Oxygen absorption type:
(in neutral or slightly alkaline medium)
O2 + 2H2O + 4e- 4OH-
• This reaction can be easily stifled either by removing the oxygen
from the corrosive media or by decreasing the diffusion rate of
oxygen to cathode.
• Reducing agents such as N2H4, Na2SO3 etc., remove oxygen from
the corroding environment by combining with it.
N2H4 + O2 N2 + 2H2O
• Decreasing the diffusion rate of oxygen is achieved by adding salts
such as ZnSO4, MgSO4, NiSO4 etc., to the aqueous environment.
• They undergo hydrolysis and form a deposit of their insoluble
hydroxide on the cathodic sites.
Zn2+ + 2OH- Zn(OH)2.
 Corrosion Control by Cathodic Inhibitors

• The protective film being impermeable to oxygen prevents its

further diffusion to cathodic sites.
• The action of an inhibitor depends on the nature of the metal to be
protected as well as corrosive environment
• It is therefore necessary to choose an appropriate inhibitor for a
particular system
 Corrosion Control by Surface coatings

• A protective coating on the surface of metals and alloys

isolates them from corrosive environment, thereby preventing
the corrosion

• Types:
Metallic coatings
Inorganic coatings
Organic coatings
 Corrosion Control by Metal coatings

Coating of a metal on a substrate metal requiring protection against

corrosion is metallic coating
• Types:
Anodic metal coating: Coating the substrate metal with a more
anodic metal
Eg: Galvanizing
Cathodic metal coating: Coating the substrate metal with a more
cathodic metal
Eg: Tinning
 Galvanizing process

• Giving a Zn metal coating on iron and mild steel is known as

galvanizing
• When the coating breaks or cracks zinc acts as anode and the substrate
iron and mild steel acts as cathode
• Zinc becomes sacrificial anode and provides protection to iron and mild
steel.
roofing sheets, fencing wire, buckets, pipes, wires are usually
galvanized
Process:
• Done by hot dipping process
• Objects are degreased, pickled and cleaned
• They are dipped in molten zinc bath (425 – 430 oC)
• NH4Cl flux is spread over the bath to prevent its oxidation
• Excess liquid Zn is squeezed out and the objects with Zn coating are
cooled
Galvanizing process
 Tinning process
• Giving a coating of tin on iron and mild steel is called tinning
• Tinning protects the article until the coating covers the surface
completely, by isolating it from the environment
• When the coating cracks or breaks intense or pitting corrosion of the
articles at the exposed region occurs
• This is because tin is cathodic with iron and small anodic regions
are in contact with large cathodic area.
Process:
• Tinning is done by hot dipping
• Steel sheet is degreased , pickled and cleaned. It is dipped in molten
tin (250 oC)
• It is covered with ZnCl2 and NH4Cl flux to protect liquid tin from
oxidation by air
• Excess tin in then squeezed out from it by passing through rollers
kept in palm oil
 Tinning process

• As tin salts are nontoxic, Therefore tinned iron and mild steel
sheets are used to prepare tins, cans and containers for storing
food materials
• Galvanized sheets cannot be used to prepare tins or cans for
storing food materials, because zinc salts are toxic
 Comparison of Galvanizing & Tinning processes
Galvanizing Tinning
A process of coating Zn over iron / A process of coating Sn over iron to
steel to prevent it from rusting prevent it from corrosion
(anode metal coating) (cathode metal coating)
Hot rollers used to wipe excess coat Hot rollers are immersed in oil
are not immersed in oil
Galvanized containers cannot be used Tin coated containers can be used to
to store acidic foodstuffs because store foodstuffs because tin is
zinc reacts with food acids forming nontoxic and does not react to cause
highly toxic zinc compounds. any food poisoning

Zinc protects the underlying iron by Tin protects the base metal iron due
sacrificial action to its noble nature.
Zinc continues to protect iron by Tin protects the iron until the coating
sacrificial action in the event of is perfect and any break causes rapid
puncture/break in coating corrosion of iron
 Corrosion Control by Organic coatings

• Organic coatings are inert barriers (like paints, varnishes,

lacquers, and enamels) applied on a metallic surface for both
corrosion protection and decoration.
• These involve a relatively thin barrier between the substrate
material and the environment.
• These coatings should not be used where the environment
would rapidly attack the substrate material.
• The protective value of such a coating depends on
(i) its chemical inertness to the corrosive environment,
(ii) its good surface adhesion,
(iii) its impermeability to water, salts and gases and its proper
application method
 Corrosion Control by Inorganic coatings
(Chemical conversion coatings)

PHOSPHATE COATINGS:
• These are produced by the chemical reaction of base metal
with an aqueous solution of phosphoric acid and phosphates of
Fe, Zn, Mn along with Cu salts as accelerators.
• Coatings are usually applied to Fe, steel, and Zn by either
immersion or spraying or brushing.
• This type of coating is usually grey, and they may not offer
complete resistance to atmospheric corrosion and are mainly
used as an adherent base/primer coat for paint, lacquers, etc.
• Such coatings may impair the welding strength. The chemical
reaction between the phosphating solution and the base metal
results in the formation of a surface film, consisting of
crystalline Zn-Fe or Mn-Fe phosphates.
THANK YOU
The decomposition potential in an electroplating process is
1. The maximum potential that is required to start the plating process
2. The minimum potential that is required for a continuous plating process
3. The potential required to decompose the metal at anode
4. The potential required to deposit the metal at the cathode
Which polarization can be eliminated by raising the temperature of electroplating bath?
1. Activation
2. Concentration
3. Kinetic
4. Gaseous
Which of the following factors will not affect the nature of electrodeposit in electroplating?
1. Current density and pH
2. Organic additives and throwing power
3. Metal salt and electrolyte concentration
4. Reducing reagent and its concentration
https://forms.office.com/Pages/ResponsePage.aspx?id=Qr2-
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 Chemical fuels
Contents
• Introduction & Classification

• Gross Calorific value and Net Calorific value.

• Solid fuel (coal) – proximate & ultimate analysis.

• Liquid fuels: Petroleum-Refining, Cracking and reforming. Synthetic

Petrol: Methods of production.

• Gaseous fuels: bio-gas production and uses.

Chemical Fuels, Dept. of Chemistry 1

 Learning objectives
• Define calorific value and describe the classification of fuels

• Understand the terms NCV and GCV

• To know about the petroleum refining, cracking and reforming

techniques

• Understand about Synthetic fuels, production process

• To know about the production of bio-gas and their uses

Chemical Fuels, Dept. of Chemistry 2

Introduction
Chemical fuel: A combustible carbonaceous material which on proper
burning in the presence of oxygen liberates large amount of heat that can
be used for domestic & industrial purposes.

Eg. coal, petrol, water gas

Fuel+ oxygen → Oxidation products + heat

Organic matter + Oxygen → CO2 + H2O + heat

Chemical Fuels, Dept. of Chemistry 3

 Combustion components

❖Temperature – high enough to ignite the fuel and the

gases released during the process
❖Time- must be sufficient to complete the combustion
process.
❖Turbulence -to allow complete mixing of
combustible elements, fuel, and oxygen.

Chemical Fuels, Dept. of Chemistry 4

Classification of fuels

Chemical Fuels, Dept. of Chemistry 5

6
GCV- the amount of heat liberated when unit mass/volume of the
fuel is burnt completely in oxygen, and the products of
combustion are cooled to room temperature

NCV-the amount of heat produced when unit mass/volume of

fuel is completely burnt in air, and the products of combustion are
allowed to escape into the atmosphere

= GCV – Mass of hydrogen × 9 × latent heat of steam

= GCV – 9 x % of hydrogen × latent heat of steam
100
NCV = GCV – 0.09 × % H ×587
7
Calculate net calorific value of a coal sample having 2.5
%percentage of hydrogen and gross calorific value of 25969.3 ×
103 J/kg.

NCV = GCV – 0.09 × % H ×587×4.184×103

= 25969.3×103 - 0.09×2.5×587×4.184×103

= 25416.7 J/Kg

Note: 1 calories = 4.18 J

1 kcal =J

8
 Solid fuels
Natural fuels- wood & coal
Manufactured fuels- charcoal & coke.
Advantages
(a) Easily transportable.

(b) Conveniently stored without risk of any spontaneous explosion.

(c) Low production cost.

(d) Possess moderate ignition temperature.

Disadvantages
(a) High ash content.

(b) Wastage of large proportion of heat.

(c) Clinker formation when they burn.

(d) Combustion process cannot be easily controlled.

9
(e) High handling cost.
 Solid fuels
Coal - a fuel source
Charcoal is prepared by the dry distillation of wood. It is the best
fuel since it has no sulfur content. But it is costly.
Coke has increased C content is obtained by destructive
distillation of soft coals in closed retorts.
Peat (< 60% C Content) and coal – Currently used in the
generation of electricity
Coal Charcoal

Peat
Coke

10
 Analysis of coal- Proximate Analysis
Significance

• determination of moisture, volatile matter, ash, and fixed carbon.

• Establish the rank of coals

• Show the ratio of combustible to incombustible constituents

• Provide the basis for buying/selling

• Identify appropriate coal for different purposes

11
Analysis of coal – Procedure for proximate analysis

1. Moisture: Weigh coal sample into dry silica crucible. Heat for
1h at 110 0C. Cool & weigh. Calculate the loss in wt. as
percentage.
% moisture = Loss in weight × 100
Wt. of coal taken

moisture evaporates by taking some liberated heat in the form of

latent heat of evaporation, lowering the effective calorific value
of coal.

• Less moisture content → better quality coal

Chemical Fuels, Dept. of Chemistry 12

2. Volatile matter: Cover coal left in step 1. Place in a muffle
furnace at 950 0C for 7 minutes. Cool & weigh. Calculate the loss
in wt. as %age.

% Volatile matter = Loss in weight × 100

Wt. of coal taken

• Higher % volatile matter: high proportion of fuel will distill

over as vapor and a large portion of which escapes unburnt.
burns with a long flame, high smoke

Less volatile matter → better the rank of coal

13
3. Ash: Heat coal left in step 2 without lid in a muffle furnace at 750 0C to complete the
combustion & constant weight of residue is obtained.
% Ash = Wt. of ash left × 100
Wt. of coal taken
• Intrinsic ash: Mineral matter originally present in the vegetable material from which the
coal was formed, consists of oxides of K, Mg and Ca. Low %
• Extrinsic ash: Non-essential mineral matters such as clay, gypsum or other inorganic
matters. More %
• Ash-forming constituents → undesirable
(i) The calorific value of the coal is decreased
(ii) Removal and disposal of ash poses problems
(iii) The ash deposited in the fire bars interferes with the circulation of air
(iv) If the ash fuses to form a clinker on the fire bars, it hinders air circulation and promotes
corrosion of the fire bars.
However, some ash is desirable since it serves to protect the grates from direct contact with
incandescent coal, which might lead to oxidation of the grate bars. 14
Fixed carbon: Sum total of the % ages of volatile matter,

moisture & ash subtracted from 100.

i.e. 100 – (% moisture + % volatile matter + % ash)

• High percentage of fixed carbon → greater CV & better the

quality

15
• A coal sample of 2.5 g was weighed into a silica crucible.
After heating for one hour at 110 °C the residue weighed 2.415
g. The crucible was covered with a vented lid, strongly heated
for seven minutes at 950 °C and the residue weighed is 1.528
g. Calculate the percentage of moisture and volatile matter.

• Mass of moisture = 2.5 – 2.415 = 0.085 g

• Mass of volatile matter = 2.415 – 1.528 = 0.887 g

% moisture = Loss in weight × 100

Wt. of coal taken
• %age of moisture = 0.085 × 100 / 2.5 = 3.4 %

% Volatile matter = Loss in weight × 100

Wt. of coal taken
• % age of volatile matter = 0.887 × 100 / 2.5 = 35.48 % 16
 Analysis of coal - Ultimate analysis

• Significance

• To find the chemical composition of coal with respect to the

elements like C, H, O, N, S and ash
• To predict the suitability of coal for purpose of heating
• For combustion calculations
• To determine the composition of flue gases

17
 Analysis of coal - Ultimate analysis
1. C & H: Weigh coal & burn in pure O2. C & H convert into CO2 &
H2O on combustion. Absorb in weighed KOH & CaCl2 tubes. Increase in
the weights of tubes → amount of CO2 & H2O formed
% Carbon = Increase in wt .of KOH tube × 12 × 100
Wt. of coal taken × 44

% Hydrogen = Increase in wt. of CaCl2 tube × 2 ×100

Wt. of coal taken ×18

•High percentage of C & H → better coal quality

18
2. Nitrogen: Digest known quantity of coal in a Kjeldhal flask with
conc. H2SO4 & HgSO4 with K2SO4 catalyst. Treat clear soln. with excess
NaOH. Distill liberated NH3 into known volume of std. acid solution.
Determine volume of residual acid by back titration with std. NaOH soln.
• % of nitrogen = Weight of nitrogen X 100
Wt. of coal taken
• 1000 ml, 1Normal acid = 14 g of N
V ml, N Normal = 14 × N × V/1000
% Nitrogen = Vol. of acid used × Nacid ×14 × 100
Wt. of coal taken ×1000
% Nitrogen = Vol. of acid used × Nacid ×1.4
Wt. of coal taken

* Less nitrogen content → Good coal quality

19
Chemical Fuels, Dept. of Chemistry
3. Sulfur: Weigh coal sample & burn in bomb calorimeter. Sulfur
converts to sulfates. Treat washings with BaCl2 soln. to obtain BaSO4 ppt
(at. wt. = 233). Filter, wash, ignite & weigh. Calculate S present in coal.

% Sulfur = Wt. of BaSO4 obtained × 32 × 100

Wt. of coal taken × 233
Corrosive combustion products
* Low sulfur-coal is useful

4. Ash: Determine as described under proximate analysis.

5. Oxygen: Determine by difference as follows:

% Oxygen = 100 – % (C + H + N + S + Ash)

Lower oxygen content → greater CV

Chemical Fuels, Dept. of Chemistry 20
1. About 0.6 g of a coal sample was allowed to undergo
combustion in a bomb calorimeter. The calorific value of the
sample was found to be 8600 cal/g. The ash formed was
extracted with acid, and this was heated with BaCl2 solution.
The weight of dried barium sulfate obtained was found to be
0.05 g. Calculate the % of S in the coal sample.

21
1. About 1.6 g of coal sample was kjeldahlised and NH3 gas thus
evolved was absorbed in 50 mL of 0.1 N sulphuric acid. After
absorption, the excess of acid required 6.5 mL of 0.1 N NaOH for
neutralization. Calculate the % of nitrogen in the sample.

22
About 0.5g of a coal sample was used for nitrogen estimation by
Kjelldahl method. The evolved ammonia was collected in 30 ml of
0.2 N HCl acid. To neutralize excess acid 20 ml 0.1 N sodium
hydroxide was required. Calculate the percentage of nitrogen in the
sample.

V acid = 30 – 10 = 20 mL 20 x 0.1 = ? X 0.2

Strength of acid = 0.2 %
Nitrogen = Vol. of acid used × Nacid ×1.4 × 100
Wt. of coal taken×1000
=1.12

23
 Numerical Problems
• 1. About 1.5 g of coal was used for nitrogen estimation by
Kjeldahl method. The evolved ammonia was collected in 25
mL of 0.1 N H2SO4. the excess acid was neutralized by 15
mL of 0.1 N NaOH. Calculate the % nitrogen in the sample.

• 2. The residue obtained when 2.5 g of coal was heated in a silica

crucible for 1 h at 110 oC weighed 2.42 g. This was heated strongly
for 7 minutes at 950 oC covered with a vented lid. The residue
weighed 1.55 g & it was further heated until a const. wt. of 0.25 g was
obtained. Calculate % moisture, volatile matter, ash & fixed carbon.

Chemical Fuels, Dept. of Chemistry 24

 Liquid fuels
❑ They are combustible molecules that can be harnessed to create
energy
❑ Formed by anaerobic decay of marine plant & animal life under the
influence of high T & P
❑ Complex mixture of hydrocarbons
❑ Refining- separation of crude oil into different useful fractions on the
basis of their boiling points
❑ Petroleum- An important primary liquid fuel

Chemical Fuels, Dept. of Chemistry 25

 Petroleum cracking

Decomposition of higher mw into lower mw hydrocarbons.

Cracking

Catalytic Cracking
Thermal Cracking
Low T & P, Presence of catalyst e.g.
[high T & P, Absence of catalyst]
gives mixtures of products containing high
(Al2O3 + SiO2)
proportions of hydrocarbons with double
bonds- alkenes.
free radicals are formed

Chemical Fuels, Dept. of Chemistry 26

 Catalytic cracking
• Zeolites as the catalyst.
• Alkane is brought into contact with the catalyst at a
temperature of about 500 oC and moderately low pressures.
• The zeolites as catalysts give high percentages of
hydrocarbons with between 5 and 10 carbon atoms-
particularly useful for petrol. It also produces high proportions
of branched alkanes and aromatic hydrocarbons like benzene.
• The zeolite catalyst has sites which can remove hydrogen from
an alkane together with the two electrons which bound it to the
carbon. That leaves the carbon atom with a positive charge.
Ions like this are called carbonium ions. The reorganization of
these leads to various products of the reaction.

27
 Petroleum reforming

• Upgrading gasoline by increasing its octane number in presence of a

catalyst.

• Isomerization
H3C (CH2)4 CH3 H3C CH CH2 CH2 CH3
CH3

n-hexane 2-methyl petane

• Dehydrogenation:

Chemical Fuels, Dept. of Chemistry 28

• Cyclisation & dehydrogenation:

CH3 (CH2)4 CH3 + H2

n-Hexane Cyclohexane

+ 3H2

Cyclohexane Benzene

• Hydro cracking:

Cat
CH3 (CH2)8 CH3 + H2 2 CH3 (CH2)3 CH3
n-Decane n-Pentane

Chemical Fuels, Dept. of Chemistry 29

 Synthetic Petrol
• Method of producing Synthetic Petrol:
• 1. Polymerisation
• 2. Fischer-Tropsch method
• 3. Bergius process

Chemical Fuels, Dept. of Chemistry 30

 nCO + 2nH2 = CnH2n+ nH2O

nCO +(2n+1)H2 = CnH2n+2 + nH2O

Chemical Fuels, Dept. of Chemistry 31

 Gaseous fuel

• Fixed composition gases - acetylene, methane,

ethylene, and ethane.

• Composite industrial gases - blast furnace gas, coke

oven gas, producer gas, illuminating gas, blue water
gas, carbureted water gas, etc.

Chemical Fuels, Dept. of Chemistry 32

 Biogas
• Biogas is a type of biofuel that is naturally produced by
the decomposition of organic waste

• Process of producing biogas is also known as anaerobic

digestion

• The digestion chamber is fully submerged in water,

making it an anaerobic (oxygen-free) environment

Chemical Fuels, Dept. of Chemistry 33

• Bio-gas composition:
• Compound Formula %
• Methane CH4 50–75
• Carbon dioxide CO2 25–50
• Nitrogen N2 0–10
• Hydrogen H2 0–1
• Hydrogen sulfide H2S 0.1 –0.5
• Oxygen O2 0–0.5

Chemical Fuels, Dept. of Chemistry 34

 ,
Applications
• Biogas can be used for electricity production,
cooking, space heating, water heating and
process heating. If compressed, it can replace
compressed natural gas for use in vehicles,
where it can fuel an internal combustion
engine or fuel cells.

Chemical Fuels, Dept. of Chemistry 35

 Summary

✓ Types of fuels based on their origin & physical state

✓ Methods to determine GCV & NCV of fuels using bomb & boys
calorimeters

✓ Procedure of proximate & ultimate analysis of solid fuels like coal

✓ Liquid fuels- Refining, Cracking, Reforming, Knocking

✓ Gaseous fuels – Biogas

Chemical Fuels, Dept. of Chemistry 36

 MODERN METHODS OF CHEMICAL
ANALYSIS
Instrumentation

▪Difference between instrumental and non-

instrumental methods.
▪ Advantages of instrumental methods.
 Chemistry

Analysis of ore or elements

Precipitation

Distillation

➢ The separated components can be identified by their

colors, boiling or melting points, solubility's in a
series of solvents, odors, optical activities or their
refractive index.
➢ Physical properties of the analyte such as
conductivity, electrode potential, light absorption or
emission, mass-to-charge ratio, fluorescence etc.,
used for quantitative analysis.
➢ The techniques like distillation, extraction, and
precipitation, etc. were replaced by high efficient
chromatography and electrophoretic techniques for
separation of components of complex mixtures.
Volumetric analysis:-
In volumetric analysis, the volume or mass of a standard
reagent required to react completely with the analyte
will be determined by carrying out the titrations.
➢ Titrant (Known Concentration)
➢ Analyte (Unknown Concentration)
➢ Equivalence point
➢ End point
Types of titration:-
(i) Acid-base (iii) Precipitation
(ii) Complexometric (iv) Redox
Volumetric analysis:-
In volumetric analysis method, an appropriate indicator is to be
used.
Sl. Type of volumetric Phenomena Suitable Examples
No. method Indicators
1 Acid – Base titrations:
strong acid vs strong Phenolphthalein HCl vs. NaOH
base
weak acid vs strong base Phenolphthalein CH3COOH vs
Neutralization
NaOH
strong acid vs weak base Methyl orange HCl vs. NH4OH
weak acid vs weak base No suitable CH3COOH vs
indicator NH4OH
2 Complexometric Complex formation Eriochrome Zn (or Ca) vs.
titrations Black-T (EBT) EDTA disodium
salt
3 Precipitation titrations Precipitation Potassium Cl- vs. AgNO3
chromate
4 Redox titrations Reduction and Diphenylamine Fe2+ vs. Cr6+
oxidation reactions
The essential conditions for any volumetric method of analysis
are:
• The reaction must proceed to completion rapidly
• The reaction should not be complicated by additional or side
reactions
• There should be a detectable change (such as a sharp change in
color or formation of a precipitate) in the solution undergoing
titration at the stoichiometric endpoint
• A suitable indicator must be available for detecting the
endpoint.
Gravimetry:-
➢ In gravimetric analyses, the mass of the analyte or some
compound produced from the analyte after treating it with
appropriate reagent was determined.
➢ Its broadly classified as volatilization methods and
precipitation methods.
➢ Volatilization methods involve the drying or heating of a
sample to determine by weight of the content of volatile and or
non-volatile components.
➢ Precipitation methods involve the formation of a precipitate
through an appropriate reaction and weighing the precipitate.
The precipitation methods generally proceed through four steps:
➢ Precipitation: conversion of analyte into a precipitate by an
appropriate chemical using a selective reagent
➢ Digestion: allow the precipitate to be in contact with its
mother liquor and heat it on a steam bath during which
recrystallization occurs, and pure crystals/product is formed.
➢ Filtration: the digested precipitate will be filtered using
appropriate Whatman filter papers or sintered glass crucibles,
which are to be selected based on the type of precipitate and
the residue forming.
➢ Washing, drying and weighing: the filtered precipitate is to
be washed with a very dilute solution of its mother liquor then
ignited followed by weighing and drying until it gives a
constant weight.
 Function of instruments

• Signal is produced which reflects the chemical or

physical property of a chemical system.
• The resulting signal may be used directly or
transformed to one of a different nature, amplified
and read on some device.
Flow diagram of Instruments

Generation of a signal

Transformation of a signal

Amplification of the transformed signal

Presentation of the signal

 Instrumental analysis

Non-destructive methods
Destructive methods
(Sample remains
(Sample is destroyed)
unchanged)
Physical property measured Instrumental methods based on
measurement of property
Absorption of radiation Spectrophotometry (X-ray, UV, Visible,
IR, colorimetry, atomic absorption, NMR
and ESR
Emission of radiation Emission spectroscopy (X-ray, UV,
Visible, flame photometry, fluorescence,
radio chemical methods)
Scattering of radiation Turbidimetry, nephelometry, Raman
Refraction of radiation Refractometry, interferometry
Diffraction of radiation X-ray, Electron diffraction methods
Rotation of radiation Polarimetry, Optical rotatory dispersion,
Circular dichrosim
Electrical potential Potentiometry, Chronopotentiometry
Electrical conductance Conductivity
Electrical current Polarography, Amperometric titrations
Thermal properties Thermal conductivity and enthalpy
methods
Kinetic methods Rate of Reaction
➢ There is a group of instrumental procedures that are
adopted for separation and resolution of closely
related compounds.
➢ Most of these procedures are based on
chromatography, solvent extraction or
electrophoresis.
Spectroscopy:- It’s the branch of science dealing with
the study of interaction of electro magnetic radiation
with matter.
➢ Energy is absorbed or emitted by the matter in
discrete amount called quanta.
 Electromagnetic radiation

• Electromagnetic radiation is a form of energy that is

transmitted through space at on enormous velocity.
➢ It doesn’t require supporting medium.
➢ It is said to have a dual nature, exhibiting both wave
and particle characteristics.
• Electromagnetic radiation is an alternating electrical
and magnetic force field in space.
• The two components oscillate in planes perpendicular
to each other and perpendicular to the direction of
propagation of the radiation.
Amplitude:- It is an vector quantity that provides a
measure of the electric or magnetic field strength at a
maximum point in the wave.

Period:- The time required for the passage of

successive maxima or minima through a fixed point
in space is called a period (p) of the radiation.
• Frequency (γ): Frequency of an electromagnetic
wave is the number of oscillations that occur in 1
second.
• Frequency has units of reciprocal time. Its generally
expressed in cycles per Seconds or in Hertz (Hz).
• 1 Hz = 1 cycle s-1
• γ = 1/p ( P = Period)
• Depends on source
Wavelength (λ):- It is the distance between two
equivalent points on successive electromagnetic wave.
1λm = 10-4 cm = 10-3 cm = 10-6 m.
Wavenumber (γ) :- Frequency as the wave number which
is defined as the number of waves percentimeter in
vacuum.
1
γ = 

Velocity(c):- The velocity is dependent upon the medium

through which radiation is passing. It has the unit cm s-1.
wavelength x frequency = velocity
λ x γ = v (c)
Relation between Frequency, velocity and wavenumber

γ= 1……..(a)

C
but γ = …….(1) [since c = γ x λ ]

1 =  …….(2)
 C

C
λ =  …….. (3)
Equation (a) and (2) are equal

γ = C (or) γ = Cγ [C = 3 x 108 ms-1]
 Particle properties of electromagnetic radiation

➢ Wave nature of electromagnetic radiation fails to explain

many phenomena like photoelectric effect.
➢ To explain that, its assumed that the electromagnetic
radiation consists of a stream of discrete packets
(particles) of pure energy, called photons or quanta.
E = hγ ……..(1)
γ = C ………(2)

E = hC ………(3)


E = hCγ………(4)
 Types of spectroscopy

(i) γ-ray region:-

υ = 3 EHz to 300 Ehz (1 exa Hz = 1018 Hz)
λ = 100 pm to 1 pm
➢ γ rays have sufficient energy to bring about nuclear transformation.
➢ The γ-ray resonance spectroscopy is known as Mossbauer
Spectroscopy.
(ii) X-ray region:-
υ = 30 PHz to 3 EHz
λ = 10 nm to 100 pm
➢ The energy of X-rays is sufficient to cause the transitions of core
electrons of atoms and molecules.
➢ X-ray spectroscopy and X-ray photoelectron spectroscopy
(XPS) is associated with the X-ray region.
• Visible and Ultraviolet region: These are further made up of the
following regions.
Vacuum ultraviolet: 1 – 800 nm
Ultraviolet: 180 – 400 nm
Visible: 400 – 750 nm
• Infrared region: This region has been further divided into the
following sub-regions.
Infrared (near) : 0.7 – 2.5 
Infrared: 2.5 – 15 
Far infrared: 15 – 200 

Microwave region: (0.1 mm to 1 cm wavelength) This region

corresponds to changes in the rotation of molecules. Separations
between the rotational levels of molecules are of the order of
hundreds of joules per mole.
Radiofrequency region:
(10 m – 1 cm wavelength) The energy change involved in this
region arises due to the reversal of a spin of nucleus or electron.
This is of the order 0.001 – 10 J/mole.
 INTERACTION OF EMR WITH MATTER
➢ When EMR passes through matter, a variety of phenomena may
occur.
➢ If the photons of radiation possess the appropriate energies, they
may be absorbed by the matter and result in electronic
transitions, vibrational changes or rotational changes or
combination of these.
➢ After absorption, atoms or molecules become excited. They
give out energy quickly either by losing energy in the form of
heat or by re-emitting EMR.
 INTERACTION OF EMR WITH MATTER
➢ The portion of EMR which passes into the matter, instead of
being absorbed, may undergo scattering or reflection or may be
re-emitted at the same wavelength or a different wavelength.
➢ When EMR is neither absorbed nor scattered, it may change
orientation or polarization.
➢ In some cases, the molecules after absorbing radiation become
excited, but they do not lose energy very quickly but with some
delay.
➢ In such cases, the energy is re-emitted as radiation usually of
longer wavelength than was initially absorbed. This
phenomenon is called as fluorescence.
➢ If in some cases, there is a detectable time delay in re-emission,
the phenomena are termed as phosphorescence.
Molecular Spectroscopy

A molecule may possess internal energy which can be

subdivided into three classes.
ETotal = ETrans + Evib + Erot + Eele
Translational energy:-
➢ Energy is associated with the uniform velocity of a
molecule.
➢ This is generally described with respect to the centre
of mass of molecule.
Et = ½ mv2
Due to translational motion, the molecule is free to
move in the three perpendicular directions x,y and z.
Rotational energy:- This type of energy is associated
with the overall rotation of the molecule with the
atoms considered as fixed point masses.
Erot = ½ Iω2
I = Moment of Inertia
ω = Angular velocity
Vibrational energy: This type of energy is associated
with the oscillation of atoms which are considered as
point masses about equilibrium positions.
(d) Electronic energy:-
➢ The energy required to move the electron from the
ground state to an excited state varies with the type of
molecular bond in which the electron exists.
➢ Further, the vibrational and rotational energies of the
molecules are added to the electronic energies.
Eelectronic >> Evibrational >> Erotational >> Etranslational
Since the translational energy is negligibly small, we can write
the Born-Oppenheimer approximation as
Etotal = Erotational + Evibrational + Eelectronic
Interaction of Electromagnetic radiation with matter

➢ If the photons of radiation absorbed or emitted by

matter may result in electronic, vibrational, rotational
changes or combination of these.
Portion of electromagnetic radiation = being absorbed
Portion of electromagnetic radiation = being reemitted.
➢ When electromagnetic radiation is neither absorbed
not scattered, it may undergo changes .
Reemitted radiation = Fluorescence.
Delayed emission = Phosphorescence.
• Rotational (Microwave) spectra: These spectra
result from transitions between the rotational energy
levels of a gaseous molecule on the absorption of
radiations falling in the microwave region.
• These spectra are shown by the molecules which
possess a permanent dipole moment, e.g., HCl, CO,
H2O vapor, NO, etc.
• Homonuclear diatomic molecules like H2, Cl2, etc.,
and linear polyatomic molecules such as CO2 which
do not possess a dipole moment, do not show
microwave spectra.
• Microwave spectra occur in the spectral range of 1 –
100 cm-1
• Vibrational and vibration-rotation (Infrared)
spectra:
• These spectra originate from transitions induced
between the vibrational energy levels of a molecule
on the absorption of radiations belonging to the
infrared region.
• IR spectra are shown by molecules when vibrational
motion is accompanied by a change in the dipole
moment of the molecule.
• These spectra occur in the spectral range of 400 –
4000 cm-1.
Electronic spectra:
➢ Electronic spectra arise from an electronic transition
in a molecule by absorption of radiations falling in
the visible and ultraviolet regions.
➢ While electronic spectra in the visible region span
12,500 – 25000 cm-1, those in the ultraviolet region
span 25000 – 70000 cm-1.
➢ Since vibrational and rotational transitions invariably
accompany electronic transitions in a molecule, the
electronic spectra of molecules are highly complex.
Spectrophotometry:
➢ When a monochromatic light of initial intensity Io
passes through a solution in a transparent vessel,
some of the light is absorbed so that the intensity of
the transmitted light I is less than Io.
➢ There is some loss of light intensity from scattering
by particles in the solution and reflection at the
interfaces, but mainly from absorption by the
solution.
➢ The relationship between I and Io depends on the
path length of the absorbing medium, b and the
concentration of the absorbing solution, c.
Lambert’s law:-
When a ray of monochromatic light passes through an
absorbing medium, its intensity decreases exponentially
as the length of the medium absorbing increases.
Beer’s law:-
When a monochromatic light passes through an
absorbing medium, its intensity decreases exponentially
as the concentration of the medium absorbing increases.
Transmittance:-
The ratio of intensities is known as the transmittance
(T), and this is usually expressed as the percentage.
The probability that the photons of a beam of intensity I will be
absorbed by the sample is directly proportional to the
concentration and thickness of the absorbing solution, and it can
be expressed as
dI/I = -αcdx …………. (2)
Where dI= Change in intensity produced by absorption of
radiation
dx= Thickness of the medium
C = Concentration of solution
α = Proportionality constant
- = reduction in intensity
Integration of Eq 2. between limits I =I0 at = 0 and I = I & x =b
gives,
 ln (I/I0) = 2.303 log (I/I0) = - αbc ………….. (3)

According to equation 3, the intensity of a beam of

monochromatic radiation decreases exponentially with an
increase in the thickness x and the concentration c of the medium.
This is Beer-Lambert law.
➢ Putting α/2.303 = ε and defining log (I0/I) as absorbance, A of
the solution, we get
A= log (I0/I) = εbc ………….. (4)
Where ε = Extinction coefficient of the medium
It is the characteristic of the solute and depends on the nature of
the solvent, temperature, and wavelength of the radiation
employed.
When the concentration is expressed in mol dm-3 and the path
length in cm, then ε is expressed in dm3 mol-1 cm-1 is referred as
molar absorption coefficient or molar extinction coefficient.
Limitations of the Beer-Lambert law:
• Chemical and instrumental factors limit the linearity of the Beer-
Lambert law. The probable causes of nonlinearity are:
• Deviations in absorptivity coefficients at high concentrations
(>0.01M) due to electrostatic interactions between molecules nearby
• Scattering of light due to particulates in the sample
• Fluorescence or phosphorescence of the sample
• Changes in refractive index at a high analyte concentration
• Shifts in chemical equilibria as a function of concentration
• Non-monochromatic radiation, deviations can be minimized by
using a relatively flat part of the absorption spectrum such as the
maximum of an absorption band
• Stray light
Numerical:
• The molar extinction coefficient of phenanthroline complex of
iron (II) is 1200 dm3 mol-1 cm-1, and the minimum detectable
absorbance is 0.01. Calculate the minimum concentration of
the complex that can be detected in the experiment if the path
length is 1.00 cm.
A = εbc
c = A/εb = 0.01 / 1.00 * 1200
= 8.33 x 10-6 M
 PROBLEMS

(1) Calculate the energy in Joule per quantum calories

per mole, and electron volts on photons of
wavelength 3000 Ao.
E = hγ
E = hC

h = 6.62 x 10-34 Joule.Sec C = 3 x 108 ms-1
λ = 3000 Ao = 3000 x 10-8 cm
E = 6.62 x 10-19 Joule
E = Nh γ
N = Avogadros number
Energy per mole = x/4.184 Joulr cal-1

= x/23060 cal mol-1ev-1

(2) Calculate γ, γ and E for typical ultraviolet radiation
of wavelength 2000 Ao . Express the value of E in ergs

E = hγ = hC = hc γ


E = h γ = 6.62 x 10-27 erg.sec x 1.5 x 1015 γcycles sec-1

= erg.
 (3) Calculate the wave number of radiation whose
wavelength is 4 μm

1 μm = 10-4 cm 4 μm = 4 x 10-4 cm

Wavenumber γ = 1/λ = ¼ x 10-4 cm = 2500 cm-1

(4) Calculate the frequency of radiation whose wavelength is
400 nm. Express this wavelength in wavenumber

Wavelength λ = 400 nm = 400 x 10 Å = 400 x 10 x 10-8

cm = 4 x 10-5 cm
Frequency, γ = C/λ = 3 x 1010 cm s-1 / 4 x 10-5 cm
= 7.5 x 10-4 Hz
Wavenumber, γ = 1/λ = 1/ 4 x 10-5 cm = 25000 cm
(5) Calculate the frequency of the radiation in Hertz of
wavelength 350 nm.

γ = c/λ, c = 3 x1010 cm sec-1 , λ = 3500 x 10-8 cm

γ = 3 x 1010 / 3500 x 10-8
= 8.57 x 1014 Hertz
(6) What is the wavenumber of the lines of frequency 4
x 1014 Hertz?

γ = γ /λ, = 4 x 1014 / 3.0 x 1010 = 1.33 x 104 cm-1

 (7) Calculate the wavenumber of the radiation if the
frequency is 2.06 x 1014 Hertz.

γ = C/λ
But γ = 1/λ
Therefore γ = γ/C = 2.06 x 1014 / 3.0 x 1010
= 6866 cm-1
 (8) Calculate quantum of energy, E in joules, J mol-1

E = hc/λ
E = 6.626 x 10-34 Js x 3.0 x 108 ms-1 / λ x 10-9 m
E(J) = 1.9878 x 10-16 /λ (nm) J
E (J mol-1 ) = 1.9878 x 10-16 J / λ (nm) x 6.023 x1023 mol-1
= 1.2 x 108/ λ (nm) J mol-1
 Online address for you tube videos

➢ https://www.youtube.com/watch?v=cxhA2p0dB-I
➢ https://www.youtube.com/watch?v=dkARLSQWHH8
➢ https://www.youtube.com/watch?v=vt3WO2rf9Qs
 References
(1) SPECTROSCOPY (ATOMIC AND
MOLECULAR) :- GURDEEP R. CHATWAL,
SHAM K. ANAND
(2) INSTRUMENTAL METHODS OF CHEMICAL
ANALYSIS :- GURDEEP R. CHATWAL, SHAM K.
ANAND
(3) FUNDAMENTALS OF MOLECULAR SPECTROSCOPY :-
COLIN N. BANWELL AND ELAINE E. McCASH
(4) FUNDAMENTALS OF ANALYTICAL CHEMISTRY:-
SKOOG, WEST, HOLLER, CROUCH
(5) ELEMENTARY ORGANIC SPECTROSCOPY:-
Y.R. SHARMA
 Modern Materials- Contents
• Fundamental Principles
• Bonding in solids
• Polymers
• Liquid Crystals
• Ceramics
• Composites
• Biomaterials
• Thin Films
• Nano materials
1
 References:
• Engg.Chemistry by
Jain and Jain

• Engg.Chemistry by
Dr. R.V.Gadag and Dr. A.Nithyananda Shetty

• Principles of Physical Chemistry by

Puri and Sharma

 Essentials of Engineering Chemistry by

S.K. Bhasin and Vijay Sharma
 Learning Objectives
 Understand the fundamental principles of material science
 Explain how functional needs are related to structure & bonding
 Apply experimental design techniques to material production
 Define liquid crystal phases & give specific examples
 Understand the essential concepts used in nanomaterial synthesis
 Discuss the types and applications of nanomaterials in different
fields.

3
 Fundamental principles of materials
Materials - substances used in the primary production or manufacturing
of a goods.

Different substances  different properties

 Contain different elements & different combinations of elements.
 Contain different types of chemical bonds
 Have different sizes of units
 The solid state structure may contain different types of assemblies
e.g., molecular packing arrangement may be different or the geometry
of linkage in an extended 3D structure may vary.

4
5
Non-metals such as C, Si, B, N, O, and P, and metals
such as Al, Mg, Ti, Sn, Fe, Cu, Cr and Ni.

Other elements such as Cd, Ga, Ge, Pt, Ag and Au are

also used in smaller quantities and for specialized
applications.

Material science involves the study of the relationship

between structure and properties of materials. The basis
of materials science involves relating the desired
properties and relative performance of a material in a
certain application, to the structure of the atoms and
phases.

6
Properties of materials are grouped into six categories
mechanical, electrical and magnetic properties, thermal
(transmission of heat, heat capacity), optical (absorption,
transmission and scattering of light), and the chemical stability
in contact with the environment (like corrosion resistance).

7
 Classification of materials

Solid materials Advanced materials Nanomaterials

Modern Materials, Dept. of Chemistry, MIT 8

Metals and alloys:
Elements which can lose their outer electrons.

The valence electrons are detached from atoms, and spread in an

'electron sea' that "glues" the metal ions together.

Usually strong, malleable, ductile, good electrical and thermal

conductors and are opaque to light but-exhibit typical metallic
luster. Example: aluminum, steel, brass, gold.

Ceramics:
An inorganic, non-metallic solid prepared by the action of heat and
subsequent cooling.

Usually combinations of metals or semiconductors with oxygen,

nitrogen or carbon forming corresponding oxides, nitrides, and
carbides. Examples: glass, porcelain, fire brick. 9
Polymers:
Polymers are substances of high molecular mass formed by the
joining together of monomers with low molecular mass.

Bound by covalent forces and also by weak van der Waals forces,
and usually synthetic polymers have a backbone of C-C bonds

Composites

Composed of two (or more) constituent materials with significantly

different properties.

The design goal of a composite is to achieve a combination of

properties that are not displayed by any individual materials, and
also to incorporate the best characteristics of each of the
component materials.
10
Advanced materials
Advanced materials have superior properties such as toughness,
hardness, durability and elasticity when compared to conventional
materials.

Materials that are used in high-technology applications are

sometimes termed advanced materials. Advanced materials
include

Semiconductors: A semiconductor is a material which has

electrical conductivity between that of a conductor such as
copper and that of an insulator such as glass. They are the
building blocks of modern electronics including transistors, solar
cells, light emitting diodes and integrated circuits.
Examples: Si, Ge, Ga, As.

11
Biomaterials

Material that has a biomedical or biological application. They

might have a therapeutic use or a diagnostic use and the material
must have properties that meet the demands of that applications.

Nanomaterials:

Nanomaterials are defined as materials with at least one external

dimension in the size range from 1-100 nanometers.

12
 Bonding in Materials

Covalent Metallic Secondary

Ionic Bond
Bond Bond Bonds

13
 Ionic Bond
The electrostatic attraction between the cation &
anion produced by electron transfer
A+ + B- → A+ B- + Lattice energy

electrovalent bond

2 Na(S) + Cl2(g) → 2NaCl (S)

14
15
The characteristic properties of ionic compounds

They are solids at room temperature

Crystals of ionic solids are hard and brittle.
They possess high melting points and high boiling
points.
They do not conduct electricity in the solid state.
They are good conductors of electricity when they are in
the molten state or in aqueous solution.
They are soluble in polar solvents but insoluble in
nonpolar solvents.
They do not exhibit isomerism.
16
 Covalent Bond
Formed by overlap of atomic orbitals & mutual
sharing of electrons.

17
The characteristic properties of covalent compounds

 gases, liquids or solids at room temperature

 soft and much readily broken

 have low melting points and boiling points

 soluble in organic solvents

 rigid and directional; causes stereoisomerism

 do not conduct electricity in any state

18
 Metallic bond
The bonding which holds the metal atoms firmly
together by force of attraction between metal ions &
the mobile electrons

19
A block of metal can be thought of as an array of positive ions
immersed in a sea of delocalized electrons.

The great cohesive forces resulting from the delocalization is

responsible for the great strength noted in metals.

The outer orbitals of a very large number of atoms overlap to form a

very large number of molecular orbitals that are delocalized over the
metal.

A large number of closely spaced energy levels form ‘bands’

20
21
 Secondary Bonds

Hydrogen Dipole-dipole Dipole-Induced

London Forces
Bonds Bonds dipole Bonds

22
Secondary bonding exists between virtually all atoms or molecules
but its presence may be obscured if any of the three primary
bonding types is present.

Secondary bonding is evidenced for the inert gases, which have

stable electron structures, and in addition, between molecules in
molecular structures that are covalently bonded.

Secondary bonding forces arise from atomic or molecular dipoles

23
Hydrogen bonds: The electrostatic attraction between an H-atom
covalently bonded to a highly electronegative atom X such as
nitrogen, oxygen or fluorine and a lone pair of electrons on X in
another molecule is called hydrogen bonding.

The hydrogen-bond attraction can occur between molecules

(intermolecular) or within different parts of a single molecule
(intramolecular).

Ion-dipole forces: This type of force exists between an ion

and the partial charge on the end of a polar molecule, e.g.
KBr/NaCl in water

24
Dipole-dipole bonds: The strongest secondary bonding type exists
between adjacent polar molecules.

HCl is an example of polar molecule. The positive end of one dipole

attracts the negative end of the other. There is a net attraction
between the polar molecules. Generally such attractions are about
1 % as strong as a covalent bond.

Dipole-induced dipole bonds:

polar molecules will induce a dipole in adjacent nonpolar
molecules, and a bond will form as a result of attractive forces
between the dipole and induced dipole.

The magnitude of this interaction depends on the magnitude of

dipole moment of the polar molecule and the polarizability of
the non-polar molecule. Eg. solution of polar solutes in nonpolar
solvents. ( oxygen and nitrogen in water) 25
All atoms are experiencing constant vibrational motion that can
cause instantaneous and short-lived distortions of this electrical
symmetry for some of the atoms or molecules, and the creation of
small electric dipoles.

One of these dipoles can in turn produce a displacement of the

electron distribution of an adjacent molecule or atom, which
induces the second one also to become a dipole that is then
weakly attracted or bonded to the first.

The momentary attraction between the molecules of a liquid

caused by instant dipole and induced dipole are called London
Forces.

26
27
 High polymers
DEFINITION:

The word polymer is derived from the two greek words

poly and mers

many parts or units

e.g.
mer mer mer
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH 3 H CH 3 H CH 3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

Polymers are macro molecules formed by linking smaller

molecules repeatedly, called monomers.
Examples:
Polyethylene is formed by linking a large number of
ethylene molecules
H H
H H
n C C Polymerisation
C C
H H n
H H
Ethylene polyethylene

polystyrene is formed by linking styrene molecules

H H H
H
n C C Polymerisation
C C
H n
H
styrene polystyrene
 The number of repeating units (n) in the chain is
known as the degree of polymerization.

e.g.,

D.P.

Polymers with high degree of polymerization are called

high polymers and these have very high molecular weights
(104 to 106).

Polymers with low degree of polymerization are called

oligomers.
Classification of Polymers

Polymers can be classified in several ways, based on

origin

structure

methods of formation

response to heat

properties (or applications)

Based on the origin
polymers can be classified as
Natural polymers
synthetic polymers
Natural polymers are those which are obtained naturally
e.g., Cellulose, Silk, Starch, RNA, DNA, Proteins etc.,

Synthetic polymers are those which are made by man

e.g., polyethylene, polystyrene, PVC, polyester, etc.,

semi-synthetic polymers which are chemically modified

natural polymers
e.g., cellulose acetate, cellulose nitrate, halogenated
rubbers etc.,
Based on the molecular structure
polymers can be classified as

Linear
Branched
Cross-linked
In linear polymers,
the monomeric units combine linearly with each other

secondary bonding
Branch polymers

Cross linked polymers

 Based on the method of formation

Addition polymers
Condensation polymers

Addition polymers are formed by self-addition of monomers

The molecular mass of a polymer is an integral multiple of
the molecular mass of a monomer

Condensation polymers are formed by condensation reaction

i.e., reaction between two or more monomer molecules
with the elimination of simple molecules like water,
ammonia, HCl etc.,
 Based on the response to heat

Thermo softening
Thermosetting

thermo softening or thermoplastics

soften on heating and can be converted into any shape
and can retain its shape on cooling

thermosetting polymers
under go chemical change on heating and convert
themselves into an infusible mass
Based on the properties or applications
Plastics
Elastomers
Fibers
Resins

Plastics
The polymers, which are soft enough at some temperature
to be moulded into a desired shape and hardened on cooling
so that they can retain that shape.
e.g., polystyrene, polyvinylchloride, polymethylmethacrylate etc.,
Elastomers
The polymers in which the structural units are either zig zag or
in helical chains.
They undergo elastic changes when subjected to an external force
but readily regain their original shape when the force is withdrawn

e.g., natural rubber, synthetic rubbers, silicone rubbers etc.,

Fibers
In these polymers, the molecular chains are arranged parallel to
each other in a spiral or helical pattern and
the molecular length is at least 100 times its diameter
e.g., nylons, terylene, etc.,
Resins
These polymers have a glossy appearance

These constitutes the major essential part of the plastics

These undergo the polymerization reactions and impart
different properties to plastics

e.g., polysulphide sealants, epoxy adhesives, etc.,

Functionality

the number of reactive sites or bonding sites

Some mono functional hydrocarbons

Alcohols Methyl alcohol

Acids Acetic acid

Aldehydes Formaldehyde

Some bi functional hydrocarbons

adipic acid (hexanedioic acid)

Terephthalic acid

ethylene glycol

1,6-hexanediamine
Stereo regular polymers (or) Tacticity of Polymers

Isotactic
On one side

Syndiotactic
Alternating sides

Atactic
Randomly placed

- Conversion from one stereoisomerism to another is not

possible by simple rotation about single chain bond; bonds
must be severed first, then reformed!
 Types of Polymerization
Polymerization occurs basically in two different modes.
• addition (chain growth) polymerization
• condensation (step growth) polymerization
 Addition
◦ monomers react through stages of initiation,
propagation, and termination
◦ initiators such as free radicals, cations, anions opens
the double bond of the monomer
◦ monomer becomes active and bonds with other such
monomers
◦ rapid chain reaction propagates
◦ reaction is terminated by another free radical or
another polymer
Condensation polymerization

- two monomers react to establish a covalent bond

- a small molecule, such as water, HCl, methanol or CO2 is

released.

- the reaction continues until one type of reactant is used

up
 DISTINGUISHING FEATURES OF
ADDITION AND CONDENSATION POLYMERISATION
ADDITION CONDENSATION
Monomers undergo self addition to Monomers undergo intermolecular
each other without loss of by products condensation with continuous elimination
of by products such as H2O, NH3, HCl, etc.,
It follows chain mechanism It follows step mechanism
Unsaturated vinyl compounds undergo Monomers containing the functional
addition polymerization groups (-OH, -COOH, -NH2, ….) undergo
this polymerization
Monomers are linked together Covalent linkages are through
through C – C covalent linkages their functional groups

High polymers are formed fast The reaction is slow and the polymer
molecular weight increases steadily
throughout the reaction
Linear polymers are produced Linear or cross linked polymers
with or without branching are produced

e.g., polystryrene, plexiglass, e.g., nylons, terylene, PF resins, etc.,

PVC, etc.,
STRUCTURE – PROPERTY RELATIONSHIP OF POLYMERS
1. Tensile Strength

the forces of attraction and slipping power

Based on forces of attraction:

Strength of the polymer is mainly determined by

the magnitude and distribution of attraction forces

between the polymer chains

These attractive forces are of two different types

primary or covalent bond
secondary or intermolecular forces
In straight chain and branched chain polymers - weak
intermolecular force of attraction

strength increases with increase in chain length -

as the longer chains are entangled (anchored) better

In cross-linked polymers, - covalent forces

Increase in Strength
Examples:
Linear Polymers: Polyethylene, polyvinyl chloride (PVC),
polystyrene, polymethyl methacrylate (plexiglass), nylon,
fluorocarbons (Teflon)

Branched Polymers: Many elastomers or polymeric rubbers

Cross-linked Polymers: Many elastomers or polymeric

rubbers are cross-linked (vulcanization process); most
thermosetting polymers

Network Polymers: Epoxies, phenol-formaldehydes.

Based on slipping power:

It is defined as the movement of molecules one over the other

It depends on the shape of the molecule

the movement of molecules one over other is easy

i.e., slipping power is high
in case of poly vinyl chloride (PVC), the bulky chlorine atoms are
present along the chain length hence movement is restricted

i.e., slipping power is less

Hence PVC has higher strength than PE

Cl Cl Cl Cl

Cl Cl Cl Cl

Cl Cl Cl Cl

Cl Cl Cl Cl
Polystyrene (PS) possess greater strength when compared to
PE and PVC because of the presence of bulky phenyl group.

In cross linked polymers, connected by strong covalent

forces and so the movement of the intermolecular chains is
totally restricted.
 2. Plastic deformation

When a polymer is subjected to some stress in the form

of heat or pressure or both, permanent deformation in
shape takes place, which is known as plastic deformation

linear molecules - because of the presence of only the

weak intermolecular forces show greatest degree of
plastic deformation, under pressure .

Such type of materials are called thermoplastic materials

cross-linked molecules - covalent bonds - plasticity does
not increase with rise in temperature or pressure or both in
cross-linked molecules.

Such type of polymers are known as thermosetting

polymers.
 3. Chemical Resistance

Chemical resistance of the polymer depends upon

the

• chemical nature of monomers and

• their molecular arrangement

Thus a polymer is more soluble in structurally similar solvent

polymers containing polar groups like – OH, - COOH etc.,

usually dissolve in polar solvents like water, ketone, alcohol etc.,
but these are chemically resistant to non-polar solvents
Similarly non-polar groups such as methyl, phenyl dissolve
only in non-polar solvents like benzene, toluene, etc.,
polymers of more aliphatic character - soluble in
aliphatic solvents, chemical resistance more in aromatic
solvents

polymers with more aromatic groups dissolve more in

aromatic solvents, chemical resistance more in aliphatic
solvents

Polymers containing ester groups - Hydrolysis with strong

alkalis at high temperature.

Polyamides like nylon containing –NHCO– group can undergo

easily the hydrolysis by strong acid or alkali.
 Polymers containing residual unsaturation - degradative
oxidation in air in presence of light or ozone.

Because of the dissolution of polymers in suitable solvents,

there occurs softening, swelling and loss of strength of
polymer material

Permeability of the solvents in the polymers also depends

on crystallinity. Hence crystalline polymers exhibits higher
chemical resistance than less crystalline polymers
because of denser packing.
4. Crystallinity

Polymers are part crystalline and part amorphous

An amorphous state is characterized by complete

random arrangement of molecules
crystalline form by regular arrangement of molecules

Crystalline
region

Amorphous
region
Some Highly Crystalline Polymers: Some Highly Amorphous Polymers:

Polypropylene Poly(methyl methacrylate)

Syndiotactic polystyrene Atactic polystyrene

Nylon Polycarbonate

Kevlar and Nomex Polyisoprene

Polyketones Polybutadiene
A linear polymer will have a high degree of crystallinity,
and be stronger, denser and more rigid.

• The more branched the polymer, the less dense

and less crystalline.

• Polymers with a long repeating unit or with low degree

of symmetry do not crystallize easily .

• Isotactic and syndiotactic polymers are stronger and

stiffer due to their regular packing arrangement.

• Optical properties: crystalline -> scatter light (Bragg)

amorphous -> transparent.
 5. Elasticity
Elasticity of the polymer is mainly because of the uncoiling and
recoiling of the molecular chains on the application of force
When a polymer is stretched the snarls begin to disentangle
and straighten out
i.e., the orientation of the chains occurs which in turn
enhances the forces of attraction between the chains
and thereby causing the stiffness of the materials
However when the strain is released snarls return to their
original arrangement.
• introducing cross-linking at suitable molecular positions
• introducing bulky side groups such as aromatic and
cyclic groups on repeating units
• introducing non-polar groups on the chains

By introducing a plasticizer the elasticity of polymer

can be enhanced.
•In general for ordinary compounds of low molar mass:

crystalline solid

melting

V A
liquid B

C
increase in volume at Tm F

Tm T
 GLASS TRANSITION TEMPERATURE (Tg)

Amorphous polymers do not have sharp melting points

They possess softening point .

At low temperature, polymers exist as glassy substances.

Since the molecular chains can not move at all easily in
this state, the solid tends to shatter, if it is hit .

If the solid polymer is heated, eventually it softens and

becomes flexible . This softness and flexibility is obtained
at the glass transition temperature.
 The glass transition temperature can be defined as
the temperature below which an amorphous polymer is
brittle, hard and glassy and above the temperature
it becomes flexible, soft and rubbery

Glassy state rubber state

(Hard and brittle plastic) (soft and flexible)

In the glassy state of the polymer, there is

neither molecular motion nor segmental motion

When all chain motions are not possible, the rigid solid results

On heating beyond Tg segmental motion becomes possible

but molecular mobility is disallowed. Hence flexible.
Factors influencing the glass transition temperature

Glass transition temperature of a polymer depends on

parameters such as

• chain geometry
• chain flexibility
• molecular aggregates
• hydrogen bond between polymer chains
• presence of plasticizers and
• presence of substrates in the polymer chains

A polymer having regular chain geometry show high

glass transition temperature
crystalline polymers have higher Tg‘s than amorphous polymers
HIGH-DENSITY POLYMERS
Linear polymers with chains that can pack closely
together. These polymers are often quite rigid.

LOW-DENSITY POLYMERS
Branched-chain polymers that cannot pack together as
closely. There is often a degree of cross-linking.
These polymers are often more flexible than high-
density polymers.
the bulky groups on chain, increases the Tg of the polymer

Polyethylene
Tg = - 110 0C

Polypropylene
Tg = - 18 0C

Polystyrene
Tg = 100 0C
 The presence of H-bonds between the polymer molecules
increases the Tg
• e.g., the Tg of nylon 6,6 (Tg = 50 0C) is higher than PE (Tg = -110 0C)

O O
H  H  H H
nylon 6,6 | ||   ||
   | polyethylene
C
  C      C   
C C C
N   N  
|  |
| | H H
H   H 
H  6 H 4
+ +
+ + + bonds
+ Waals
Van der
+
Hydrogen bonds
+ + +
+

+
O O
H H
H  H 
| || | || C C
   
  C   
C
 C  
C
 H H
N   N  
| |
|   |
 H   H 
H 6 H 4


With H-bonds Vs vanderWaals bonds, nylon is
expected to have (and does) higher Tg.
The presence of a plasticizer reduces the Tg of a polymer

The plasticizers are usually dialkyl phthalate esters,

such as dibutyl phthalate, a high boiling liquid.

O
C
O CH2CH2CH2CH3
O CH2CH2CH2CH3
C
O
dibutyl phthalate
The plasticizer separates the individual polymer chains
from one another. It acts as a lubricant which reduces
the attractions between the polymer chains.
The Tg of a polymer is influenced by its molecular weight
With increase in molecular mass, the Tg increases
However, it is not significantly affected if molecular weight is
around 20000

e.g., PE (low Mw) - 110 0C

PE (high Mw) - 90 0C
The glass transition temperature helps in choosing the right
processing temperature

It also gives the idea of

thermal expansion
heat capacity
electrical and mechanical properties
 Molecular Weight of Polymers

When a monomer is polymerized to form a polymer, a number of polymer

chains start growing at any instant, but all of them do not get terminated

after growing to the same size. The chain termination is a random process.

Hence, each polymer molecule formed can have a different number of

monomer units and thus different molecular weights

So, a polymer sample can be thought of a mixture of molecules of the

same chemical type, but of different molecular weights.

the molecular weight of a polymer can be expressed by
two most and experimentally verifiable methods.

(i) Number – average molecular weight

(ii) Weight – average molecular weight

In computing the number average molecular mass of a polymer,

we consider the number fractions.

In computing the weight average molecular mass of a

polymer, we consider the weight fractions.
Number average molecular mass of the whole polymer
is given by

Mn 
 nM
i i

n i

Total mass (w) of all the molecules in polymer divided by

total number of molecules present.
 In computing the weight average molecular mass of a
polymer, we consider the weight fractions

Total weight of the polymer (W) is given by

Wi = Sni Mi

Weight of fraction ‘one’ = W1= n1M1

Molecular weight contribution by fraction ‘one’

Mw = w1M1 / wi

n 1M 1 2

 ni M i
Weight average molecular mass of the whole polymer
is given by

Mw 
 ni Mi
2

n M i i
 Ratio of Mw to Mn is known as the polydispersity index (PDI)

a measure of the breadth of the molecular weight

PDI = 1 indicates Mw = Mn, i.e. all molecules have equal

length (monodisperse)

PDI = 1 is possible for natural proteins whereas synthetic

polymers have 1.5 < PDI < 5 .
The number-average molecular mass (Mn) is determined
by the measurement of colligative properties such as

lowering of vapour pressure

osmotic pressure
depression in freezing point
elevation in boiling point

The weight-average molecular mass (Mw) is determined by

light scattering and ultra-centrifugal techniques.

Polymer molecules with different degree of polymerization such as
500, 750, 850 and 1100 are mixed in molecular ratio 1: 2: 3: 4 in a
sample of high polymer of styrene. Calculate the number average
and weight average molecular weights. ( C6H5 CH CH2 )
Mn =1 x (500 x 104) + 2 x (750 x 104) + 3 x (850 x 104) + 4 x(1100 x 104)
------------------------------------------------------------------------------------
10

= 93080

Mw = 1 x (500 x 104)2 + 2 x (750 x 104)2 + 3 x (850 x 104)2 + 4 x (1100 x 104)2

--------------------------------------------------------------------------------------------
1 x (500 x 104) + 2 x (750 x 104) + 3 x (850 x 104) + 4 x (1100 x 104)

= 97,405.33
(1)A polypropylene [-CH2–CH(CH3)-] sample contains the
following composition.
Degree of polymerization 400 800 600
% of composition 25 35 40
Calculate Mn & Mw of polypropylene sample by
neglecting the end groups. Given that atomic masses of
C = 12 and H = 1 amu.

2)Polymer molecules with different degree of polymerization

500,750,950 and 1500 are mixed in molecular ratio 1:2:3:4 in a
sample of high polymer of ethylene. Calculate the no. average and
Wt average molecular mass.
Liquid Crystals
LIQUID CRYSTAL

A “double melting” behavior of cholesteryl benzoate.

The crystals of this material melted at 145.5oC into a
cloudy fluid, which upon further heating to 178.5oC
became clear.

They undergo more than a single transition in passing from

solid to liquid through different intermediate states on
heating.

Intermediate state - mesophase

Liquid Crystal – a stable phase of matter characterized by
anisotropic properties without the existence of a 3-dimensional
crystal lattice – generally lying between the solid and isotropic
(“liquid”) phase.

Anisotropy: they exhibit different optical properties when the

light is incident in different directions

Isotropy: Same properties in all directions

Isotropic
Liquids and gases
(uniform properties in all
directions).

vs.
Anisotropic
Liquid Crystals
have orientational order
LC state (mesomorphic state) is characterised by having a long-range
orientational order and possible partial positional order

i.e., the tendency of the molecules (mesogens) to point along a

common axis, called the director.

where theta is the angle between the

director and the long axis of each
molecule.
In a liquid crystal, the molecules possess orientational order, i.e.,
the molecules tend to remain oriented in a particular direction.

Director (n )
The direction of preferred orientation in a liquid crystal

Since the molecules are in constant motion, in liquid crystal phase

they spend more time pointing along the director than along any
other direction.

An average of 0° indicates perfect orientation and can be expected

in solids.
An average of greater than 45° indicates no orientational order and
found in liquids.

liquid crystals a smaller average angle with the director is observed

which indicates orientational order.
A distinct state of matter in which the degrees of molecular ordering
lie intermediate between the ordered crystalline state and the
completely disordered isotropic liquid state
Characteristics of LC

a. Liquid crystalline nature should be at room

temperature and the entire temperature range of the
device operation

b. Chemically, electrochemically, photochemically and

thermally stable

c. Permanent electric dipole, hence either a positive or

negative dielectric anisotropy.

d. Should possess easily polarizable substituents

 Types of LCs
 Thermotropic LCs, LC substances undergo transition by
variation in temperature
Mesophase formation is temperature dependent
Ex: p-azoxy anisole
 Lyotropic LCs, LC substances undergo transition by
the influence of solvent
Mesophase formation is solvent dependent
Ex: sodium stearate

Amphotropic LCs- exhibit both thermotropic and lyotropic

mesophases
Thermotropic LCs

Classification
Based on the molecular phase structure
Nematic:
Smectic
Columnar
Cubic
Nematic phase:

The least ordered mesophase (the closest to the

isotropic liquid state) is the nematic (N) phase, where
the molecules have only an orientational order
Smectic phases
In smectic (S) phase, in addition to the orientational
order the molecules possess less or more positional
order, such that the molecules organize in layered
structures.
Schematic of alignment in the smectic phases. The smectic A phase
(left) has molecules organized into layers. In the smectic C phase
(right), the molecules are tilted inside the layers.
Smectic B

Smectic B phase has the molecules arranged

within the layers in a hexagonally close-paced
array with the molecular long axes perpendicular
to the layer planes
Columnar Phases

Columnar (Col) phases are more ordered. Here the disc-

shaped cores have a tendency to stack one on the top of
another, forming columns

Arrangement of these columns into different lattice

patterns gives rise to a number of columnar
mesophases, namely columnar rectangular (Colr) and
columnar hexagonal (Colh)
(a) the general structure of Col phases, where the molecules are aligned in the
same orientation and, in addition, form columns,
(b) representation of Colr, and (c) representation of Colh.

Cubic Phase of LCs

This phase exhibited by lyotropic LC
Structures with micellar lattice units
 Thermotropic LCs
The essential requirement for a molecule to be a thermotropic
LC is a structure consisting of a central rigid core (often
aromatic) and a flexible peripheral moiety (generally aliphatic
groups).

1 . Calamitic LCs
2. Discotic LCs
3. Banana shaped LCs
4. Polycatenar LCs
 Calamitic LCs
Calamitic or rod-like LCs are those mesomorphic compounds that
possess an elongated shape, molecular length (l) being significantly
greater than the molecular breadth (b).

Ex:
The general molecular formulae of Calamitic LC s
Discotic LCs
A second type of mesogenic structure, based on discotic (disc-
shaped) molecular structures.

The first series of discotic compounds to exhibit mesophase

belonged to the hexa-substituted benzene derivatives.

Structure comprising a planar (usually aromatic) central rigid core

surrounded by a flexible periphery, represented mostly by pendant
chains (usually four, six, or eight),
Molecular structure of first series of discotic LCs discovered
Benzene hexa n-alkanoate derivatives
 Bent shape or Banana shaped LCs
 Mesomorphic compounds characterised by bent
molecular structures
 It exhibit both nematic and/or smectic phase.
 It consist of two mesogenic groups linked through a
rigid core so as to form bent shaped molecule but not
linear.
Examples of bent LCs
Polycatenar Liquid crystals
 Hybrid class of thermotropic LCs
 Described with intermediate molecular features between
rod-like and disc-like mesogens.
 the central core of polycatenar LCs comprises a
calamitic region.
 It exhibit both calamitic (nematics/smectic) and discotic
(columnar) depending on the specific molecular
structure of the components
E.g., the tetracatenar mesogens
The numbers of the flexible end chains of the core can be
indicated by using the term, m,n– polycatenary mesogen.
 Lyotropic LCs

Lyotropic LCs are two-component systems where an

amphiphile is dissolved in a solvent. Thus, lyotropic
mesophases are concentration and solvent dependent.

The amphiphilic compounds are characterized by two

distinct moieties, a hydrophilic polar “head” and a non polar
hydrophobic “tail”.

Examples of these kinds of molecules are soaps and

various phospholipids like those present in cell
membranes
Soap + polar solvent like water- micelle formation

Soap + non polar solvent like hexane – inverted micelle

where the hydrophobic tails shield the hydrophilic head

groups from the non-polar environment. Under certain
conditions, these micelles further aggregate to form
more complicated assemblies, such as lamellar and
hexagonal phases, which generate lyotropic liquid
crystal phases.

Lamellar phases are particularly significant as they form

the structural basis for biological membranes
Micellar aggregates and phases formed by Lyotropic liquid crystals
Application of liquid crystal

Liquid crystal display

Liquid crystal thermometers
In medicine
Optical imaging and recording
Non destructive mechanical testing
Polarization of light

Polarization of light
• When unpolarized light passes through a polarizing filter, only
one plane of polarization is transmitted. Two polarizing
filters used together transmit light differently depending on
their relative orientation.

Online Offline 33
 Construction of
Liquid Crystal Display

 Two bounding plates (usually glass slides), each with a

transparent conductive coating (such as indium tin oxide)
that acts as an electrode;
 A polymer alignment layer- undergoes a rubbing process
as grooves.
 Spacers to control the cell gap precisely

 Two crossed polarizers (the polarizer and the analyzer);

 LCD Alignment

When coming into contact with a finely grooved surface (alignment

layer), LC molecules line up parallel along groove due to their
rod-like shape.

[Coating ITO glass with a layer of PVA and rubbing repeatedly

creates these grooves.]
 LCD Orientation

The molecules along the upper plate point in direction 'a'

and those along the lower plate in direction 'b,' thus forcing
the liquid crystals into a twisted structural arrangement./
(figure shows a 90-degree twist) (TN type liquid crystal)
 Unique Properties of Liquid Crystals

The orientation of Liquid Crystals can be affected by…

• Pressure
• Temperature
• Electrical Field
Light movement
Offline (no voltage is applied)

• Light travels through the

spacing of the molecular
arrangement.
• The light also "twists" as it
passes through the twisted
liquid crystals.
• Light bends 90 degrees as it
follows the twist of the
molecules.
• Polarized light pass through
the analyzer (lower polarizer).

38
Molecules movement
Online (voltage is applied)

• Liquid crystal molecules

straighten out of their helix
pattern
• Molecules rearrange
themselves vertically (Along
with the electric field)
• No twisting thoughout the
movement
• Forcing the liquid crystals into
a straight structural
arrangement. (Electric force)

39
 Screen appear dark

Screen appear bright

When voltage is switched on
( LCD TV)
1.Light travels from the back of the TV toward the front from a large bright
light.
2.A horizontal polarizing filter in front of the light blocks out all light waves
except those vibrating horizontally.
3.Only light waves vibrating horizontally can get through.
4.A transistor switches off this pixel by switching on the electricity flowing
through its liquid crystals. That makes the crystals straighten out (so they're
completely untwisted), and the light travels straight through them unchanged.
5.Light waves emerge from the liquid crystals still vibrating horizontally.
6.A vertical polarizing filter in front of the liquid crystals blocks out all light
waves except those vibrating vertically. The horizontally vibrating light that
travelled through the liquid crystals cannot get through the vertical filter.
7.No light reaches the screen at this point. In other words, this pixel is dark.
When voltage is switched off
1.The bright light at the back of the screen shines as before.
2.The horizontal polarizing filter in front of the light blocks out all light waves
except those vibrating horizontally.
3.Only light waves vibrating horizontally can get through.
4.A transistor switches on this pixel by switching off the electricity flowing
through its liquid crystals. That makes the crystals twist. The twisted crystals
rotate light waves by 90° as they travel through.
5.Light waves that entered the liquid crystals vibrating horizontally emerge from
them vibrating vertically.
6.The vertical polarizing filter in front of the liquid crystals blocks out all light
waves except those vibrating vertically. The vertically vibrating light that
emerged from the liquid crystals can now get through the vertical filter.
7.The pixel is lit up. A red, blue, or green filter gives the pixel its color.
Structure of liquid crystal display: 1 – vertical polarization
filter, 2,4 – glass with electrodes, 3 – liquid crystals, 5 –
horizontal polarization filter, 6 – reflector
 Ceramics
“ceramic” - desirable properties of these materials are normally
achieved through a high-temperature heat treatment process called
firing.

Consist of a combination of non –metallic substances mostly

silicates and metal oxides.

Some of the common ceramic materials include aluminum oxide,

silicon dioxide, silicon carbide, silicon nitride

Traditional ceramics - composed of clay minerals as well as cement

and glass.

Withstand a temperature of 1500 to 2000 0 C.

Mechanical behaviour of ceramic materials

Relatively stiff and strong,

Very hard, brittle, highly susceptible to fracture,
Higher stability and higher melting points.

Most of these are insulators like other covalent materials.

Optical characteristics

Ceramics may be transparent, translucent, or opaque.

some of the oxide ceramics (e.g.,Fe3O4) exhibit magnetic

behaviour.
Classification of ceramic materials on the basis of
application

Glasses - products of fusion rapidly cooled to a rigid condition

without crystallization.

Non crystalline silicates that contain other oxides. Optical

transparency is the most desirable properties of these materials.

The most common uses for these materials are as ovenware,

tableware, oven windows because of their strength and excellent
resistance to thermal shock.

Serve as electrical insulators and as substrates for printed circuit

boards and for heat exchangers and regenerators.
Clay products

Principal component of the white wares and structural clay

products.

Stuctural clay products include building bricks, tiles-

applications in which structural integrity is important.

Feldspar and quartz may be added which influence the changes

that occur during firing.

Fire clays are hydrated aluminosilicates of composition

Al2O3.2SiO2.2H2O.
Refractories – fire clay, silica, basic special meterials :

The materials that are employed at elevated temperatures and often in

reactive environments .

Typical applications include furnace linings for metal refining, glass

manufacturing, metallurgical heat treatment and power generation.

Acid refractories:

Consist of mostly acidic materials like alumina (Al2O3) and silica

(SiO2). Not attacked or affected by acidic materials, but easily affected
by basic materials.

Fireclay bricks are used in furnace construction to confine hot

atmosphere and to thermally insulate structures from excessive
temperatures.
Neutral refractories:

Used in areas where slags and atmosphere are either acidic or basic
and are chemically stable to both acids and bases.

The main raw materials belong to, but are not confined to, the M2O3
group. The common examples of these materials are alumina
(Al2O3), chromia (Cr2O3) and carbon.

Basic refractories:

The refractories that are rich in periclase or magnesia (MgO) are

termed basic; they may also contain calcium, chromium, and iron
compounds.

Used on areas where slags and atmosphere are basic; they are
stable to alkaline materials but could react with acids.
Abrasive meterials –

Metal oxides and nitrides, being hard and tough are used to cut,
grind and polish other softer materials.

Diamond, SiC, Tungsten carbide are common examples.

Cements – portland cement:

When mixed with water, inorganic cements form a paste that is

capable of assuming just about any desired shape. Subsequent
setting is a result of chemical reactions involving the cement
particles and occurs at the ambient temperature.

Portland cement is the most common hydraulic cement, the

chemical reaction is one of hydration.
Advanced ceramics

Composite materials, engine rotors, many of our modern

technologies use advanced ceramics because of their unique
mechanical, chemical, electrical magnetic and optical properties and
property combinations.

Examples: ceramic ball bearings, piezoelectric materials.

Properties:

 Glass ceramic materials have relatively high mechanical

strength; low coefficient of thermal expansion (to avoid
thermal shock) and high temperature capabilities, good
dielectric properties and good biological compatibility, ease of
fabrication.

 In refractories porosity must be controlled .Strength, load

bearing capacity and resistance to attack by corrosive materials
all increase with porosity reduction.

 Any residual porosity will have deleterious influence on both

elastic properties and strength.
Mechanical properties of ceramics:

 Mechanical properties of ceramics are inferior to Metals.

 Energy absorption is low. Strength and melting temperature

vary linearly.

 At low temperature, ceramics are brittle while close to its

melting temperature, non-crystalline ceramics becomes
ductile.

 The processing method of ceramics decides the strength and

are usually strong in compression than in tension.

.
Brittle fracture

 Fracture toughness is the ability of the ceramics to resist the

fracture is directly proportional to applied stress and length of
the crack

 When the tensile load is applied on crystalline or non-

crystalline ceramics, fracture takes place, before any
deformation sets in.

 Compressive strength is higher than tensile strength.

 Flaws in the ceramics behaves like stress magnifiers and forms

the cracks.
Stress-strain behavior

 As ceramics are brittle, they tend to fracture before it

reaches plastic deformation state.

 Three-point bending apparatus is used to measure stress-

strain behavior.

 Flexural or fracture strength σ fs is the stress at fracture

is directly proportional to load at fracture and indirectly
proportional to the thickness of the material
Elastic behavior

 Elastic deformation is reversible deformation, while plastic

deformation is permanent deformation.

 Elastic deformation can be due to tension / compression / shear

force.

 Metals and ceramics usually have linear elastic behavior.

 The elastic modulus is directly proportional to load at fracture

and indirectly proportional to the thickness of the material.
Applications of ceramics

 Die blanks- Wear resistance properties

 Cutting tools – for cutting Silicon wafers, grinding glasses

 Sensors – ZrO2 as oxygen sensor ( rapid response of the sensor to

change in oxygen concentration)

 Matts for automobile engines.

COMPOSITES

 Composite material- material system composed of two or more

macro constituents that differ in shape & chemical composition,
mutually insoluble

 It contains two or more physically distinct and mechanically

separable materials( metal, ceramic and polymer)

 It is made by dispersing one material in the other in a controlled

way to achieve optimum properties

1
Many composite materials are composed of two phases
 matrix phase and dispersed phase.

Matrix
It is a continuous phase in composite which completely surrounds the
other phase (or dispersed phase)
Ex: metal (MMC), polymer (PMC), ceramic (CMC)

Function of matrix phase:

 Binds dispersed phase
 Acts as medium to transport and distribute the load to dispersed
phase
 Protect the dispersed phase from chemical action and keep in
proper position and orientation along the direction of applied load

2
Dispersed phase or reinforcing phase
It is a discontinuous phase that is surrounded by the matrix
phase.
It is the structural constituent which determines the internal
structure of the composite

Ex: fibers (glass or carbon), particulates (small pieces of solid

material)

Function of dispersed phase:

 To enhance matrix properties
 Increases the strength, used at elevated temperature

3
Ex: i) Wood consists of strong and flexible cellulose fibers surrounded and
held together by a stiffer material called lignin

Synthetic composite: ii) fiberglass, in which small glass fibers are

embedded within a polymeric material (epoxy or polyester).

Properties of composite materials are determined by three

factors.
i) The materials used as component phases (property of two
phases)
ii) Geometry of dispersed phase (particle size, distribution,
orientation)
iii) The amount of phase and the way in which the phases interact
with one another.

4
Classification of composites

i) Particle reinforced:
Large particle
Dispersion strengthened

ii) Fiber reinforced:

Continuous (aligned)
Discontinuous(short)-Aligned and Randomly oriented

iii) Structural: Based on build-up of sandwiches in layered form

Laminates
Sandwich panels

5
Particle reinforced

Based on reinforcement and strengthening

mechanism
i) Large particle:
Concrete
 The dispersion phase (particulate) should be harder and stiffer
than matrix phase
 The matrix transfer some stress to the particulate, which bears
the major portion of the applied load
 Particles can have quite a variety of geometries, but they should
be of approximately the same dimension in all direction.
 Particle size is large and present in large concentration.

Ex: concrete where the aggregates ( sand and gravel) are the
particles and cement is the matrix.

6
7
i) Dispersion strengthened

 strengthening materials which are very small and hard (usually

less than 0.1 µm) are uniformly dispersed within the matrix
phase
 The matrix bears the major portion of an applied load and the
small dispersed particles hinder the motion of dislocations.
 Thus plastic deformation is restricted and hardness and strength
increases
 Particle size is small and present in small concentration.
 The dispersed phase may be metallic or nonmetallic materials

 Example: thoria (ThO2) dispersed Ni-alloys.

8
Fiber-reinforced composites

Dispersed phase : fiber (long length to diameter ratio)

Matrix phase: metal, polymer or ceramic
 The primary functions of the matrix are to Transfer stresses
between the reinforcing fibers (hold fibers together)
 To protect the fibers from mechanical and/or environmental
damages.

Fibre phase:
On the basis of diameter and character, fibres are grouped into
three different classifications as
Whiskers
Fibres
Wires.

9
Whiskers
 Thin single crystals that have large length to diameter ratios (lower
than fiber)
 Posses high strength due to its small size that have extremely high
degree of Crystallinity
 they are very expensive and difficult to incorporate into matrix.

Ex: graphite, silicon carbide, silicon nitride.

Silicon carbide whiskers

10
Fibres : They are either polycrystalline or amorphous and have
small diameters (ex: like glass, ceramic)
High length to diameter ratio
The stiff reinforcing fibres are responsible for carrying load
and ductility, toughened

Glass fiber and glass fiber mat carbon fiber mat

11
Wires: Fine wires have relatively large diameters. Typical
material include steel, molybdenum, tungsten.
Ex: wire mesh

12
The strength of fiber-reinforced composite depends on fiber
orientation and its concentration
a) Parallel alignment of the longitudinal axis of the fibers in a
single direction
c)Totally random alignment

13
Elastic Behavior—Longitudinal Loading
When the load is applied on the composite in the direction of the
orientation of continuous fiber, then its modulus of elasticity is
equal to the summation of the products of the modulus of elasticity
(E) and volume fraction (V) of the respective phases.

i.e., Modulus of elasticity of composite, E = (EV)matrix + (EV)fiber

When the load is applied on the composite perpendicular to the

orientation of continuous fiber, the inverse of the modulus of
elasticity is equal to the summation of the ratio of volume fraction
(V) and modulus of elasticity (E) of the respective phases.

𝟏 𝑽 𝑽
i.e., = +
𝑬 𝑬 𝒎𝒂𝒕𝒓𝒊𝒙 𝑬 𝒇𝒊𝒃𝒆𝒓

14
Structural composites
It composed of composite and homogenous materials.
The properties depend on properties of constituent materials and on
the geometrical design of various structural elements.

Laminar composites:
 It is made of two dimensional sheets or panels that have a
preferred high strength direction
 Layers are stacked and subsequently cemented together such that
the orientation of high strength direction varies with each
successive layer. Ex: Ply wood

15
Sandwich panels
Consists of two strong outer sheets, or faces separated by a layer of less dense
material or core which has lower stiffness and lower strength
Faces or skin: Laminates of glass or carbon fiber-reinforced thermoplastics or
mainly thermoset polymers
Core:
Polymeric foams like PVC, Polyurethane, PE, PS and synthetic rubber

Foam 16
17
 POLYMER COMPOSITES

Combination of two material- reinforcing material usually in the

form of fiber, sheet or particles,
Matrix is made of polymeric material

Materials used :Fiber- glass, carbon

Matrix: thermoplastic(polyolefines, vinylic polymers) and
thermosetting resines (polyester and epoxides)

18
Polymer matrix materials:

The matrix materials used in composites are polyesters, vinyl esters, epoxies,
polyetheretherketone (PEEK), polyphenylene sulfide (PPS), and polyetherimide
(PEI). PEEK, PPS and PEI are the polymeric resins with potential aerospace
applications.

i) Glass Fiber-Reinforced Polymer (GFRP) Composites,

ii) Carbon Fiber-Reinforced Polymer (CFRP) Composites, and
iii) Aramid Fiber-Reinforced Polymer Composites.
Advantages of polymer composites:
-Light weight.
-High strength to weight ratio.
-More durable than conventional materials like steel and
aluminium.
-Good corrosion resistance.
-High fatigue strength.
-High temperature resistance.

Applications:
-Composites of phenolic resins and nylon are used in heat
shields for space crafts.
-Which are used in automotive and railway applications.
-As structural material in construction industries.
20
Fibre glass or glass-reinforced plastic (GRP)

Matrix: Made by reacting a polyester with carbon-carbon double bonds

in its backbone and styrene- a mix of the styrene and polyester
Fibre: glass fibre

O
CH2

O +
O
O n Cross linked resin

Ex: Used car engines components aeroplane parts and boat hulls
21
Aramid Fiber-Reinforced Polymer Composite:

Aramid fibers - high-strength, high-modulus materials

desirable for their outstanding strength-to-weight ratios, which are

superior to metals.

Materials is known as poly(paraphenylene terephthalamide).

Most common are Kevlar™ and Nomex™.

Kevlar composites

Kevlar is an aromatic polyimide. Chemically it is poly(para

phenyleneterephthalamide).
Matrix: Kevlar
Fibres: carbon fibre or glass fibre as reinforcing agent.

NH
NH

n
O

In Kevlar aramid ring provides thermal stability and para-

structure provides high strength and modulus
para-phenylenediamine and terephthaloyl chloride

Kevlar® 29 is used in the manufacture of body armour (panels) for

lightweight military vehicles. A good example is the US Army’s
‘Bradley Fighting Vehicle’. This has been used extensively in Iraq
and Afghanistan.
Advantages:
-Light weight, high strength, thermally stable
-Resistant to impact and abrasion damage. It can be used as
protective layer on graphite laminates.
-Can be mixed with graphite to provide damage resistance and to
prevent failure.

Disadvantages:

-Fibres themselves absorb moisture, so Kevlar composites are

more sensitive to the environment than glass or graphite
composites.
-Poor compression resistance.

27
ii) Carbon Fiber Reinforced Polymer (CFRP) Composite:
Carbon is a high-performance fiber material that is most commonly
used reinforcement in advanced polymer matrix composites. The
reasons for this are as follows:
1. Carbon fibers have the highest specific modulus and specific
strength of all reinforcing fiber materials.
2. They retain their high tensile modulus and high strength at elevated
temperatures; high-temperature oxidation, however, may be a
problem.
3. At room temperature, carbon fibers are not affected by moisture or
a wide variety of solvents, acids, and bases.
4. These fibers exhibit a diversity of physical and mechanical
characteristics, allowing composites incorporating these fibers to have
specific engineered properties.
5. Fiber and composite manufacturing processes have been developed
that are relatively inexpensive and cost-effective. 28
Carbon-reinforced polymer composites are currently being utilized
extensively in sports and recreational equipment (fishing rods, golf
clubs), filament-wound rocket motor cases, pressure vessels, and
aircraft structural components—both military and commercial,
fixed wing and helicopters (e.g., as a wing, body, stabilizer, and
rudder components).

29
Biomaterials

https://indiveni.re/biomaterials/
https://orthoinfo.aaos.org/en/treatment/total-hip-replacement/

https://medlineplus.gov/ency/article/002974.htm
 Dental Implants

https://www.ariadentalcare.com/metal-free-zirconia-implants
 Biomaterials

- Any material of natural or synthetic origin that comes

in contact with tissue, blood or biological fluids, and
intended for use in prosthetic, diagnostic, therapeutic
or storage application.
e.g. metals, ceramics, polymers, glasses, carbons,
composite materials
https://www.youtube.com/watch?v=T_uMkdKS6wQ
 Requirements of Biomaterials
A biomaterial should broadly satisfy the following
requirements
Biocompatibility
Biofunctionality
Inert or specifically interactive
Mechanically and chemically stable - tensile strength,
yield strength, elastic modulus, corrosion and fatigue
resistance, surface finish, creep, and hardness.
Processable (for manufacturability)
 Classification based on materials used
Metallic/Alloy Biomaterials
Ceramic Biomaterials
Polymeric Biomaterials
Composite Biomaterials
 Metals and alloys
Favorable mechanical properties like strength and toughness, especially fracture
toughness and fatigue strength.
Eg. - Hip and knee prostheses and fracture fixation wires, pins, screws, and plates.

Stainless steel: (most common 316L) - Used in

orthopedics and dental implants has 60-65%
Fe, 17-19% Cr, 12-14% Ni, > 0.030% C and
minor amounts of N, Mn, Mo, P, Si, and S.
Ti alloys: characteristics such as high strength,
low density, lightweight, good resistance to
Metals and corrosion, inertness to body environment,
alloys enhanced biocompatibility, good mechanical
properties - suitable choice for implantation.

Co-Cr-Mo alloy: These are highly resistant to

corrosion even in chloride environment due to
spontaneous formation of passive oxide layer
within the human body environment.
Note - The corrosion products of Co-Cr-Mo are
more toxic than those of stainless steel 8
 Ceramic Biomaterials
Inorganic polycrystalline compounds that
contain metallic and non-metallic elements.
The bio-ceramics are highly chemically inert
in the body, hard, possess excellent
corrosion resistance, high wear resistance,
high modulus (stiffness) & compressive
strength and fine aesthetic properties (for
dental applications), but they are difficult to
fabricate.
Ceramics are used in several areas like
dentistry, orthopedics, and as medical
sensors.
Eg: Alumina, Zirconium, Calcium phosphate,
Silica, hydroxyapatite
 Ceramic Biomaterials
Based on the interaction with biological system Ceramic
Biomaterials are classified in to
1. Bio inert materials: A material that retains its structure in the body after
implantation and does not induce any immunologic host reactions.
Eg. Alumina (Al2O3) is used in hip prostheses and dental implants, because of its
combination of corrosion resistance, good biocompatibility, high wear resistance
and high strength.
2. Bioactive materials: Materials that form direct chemical bonds with bone or
even with the soft tissue of a living organism.
Eg. Bioglass and glass-ceramics widely used for filling bone defects permit
modification of the surface that occurs upon implantation.
3. Bioresobable biomaterials: Materials that degrade by a hydrolytic breakdown
in the body, while they are being replaced by regenerating natural tissue; the
chemical byproducts of the degrading materials are absorbed and released via
metabolic processes of the body. Eg. Calcium phosphate ceramics
 Polymeric Biomaterials:
Most widely used materials in biomedical applications.
The main advantages –
The unique properties of these compared to metal or
ceramic materials are flexibility, ease of manufacture to
produce various shapes (latex, film, sheet and fibers), ease
of secondary processability, surface modification,
reasonable cost, resistance to biochemical attack, good
biocompatibility, light weight, availability in a wide variety of
compositions with tailorable physical and mechanical
properties.
But they are leachable, absorb water and proteins, allows
surface contamination, wear and tear and difficult to
sterilize.
 Polymeric Biomaterials
Surfaces of materials are high-energy regions and
thereby facilitate chemical reactions that influence the
performance of biomaterials. Eg. Some biopolymers are
susceptible to chemical reactions that lead to
degradation through hydrolysis.
Polymer hydrolysis involves the scission of susceptible
molecular groups by reaction with H2O, catalyzed by
acid, base or enzyme.
 Polymeric Biomaterials
Molecular and structural factors influencing hydrolysis
are
a) Bond Stability - Susceptible linkages at bonds where
resonance stabilized intermediates are possible.
b) Hydrophobicity: ↑ hydrophobicity ⇒ ↓ hydrolysis
c) MW & architecture: higher MW ⇒ ↓ hydrolysis
d) Morphology: crystallinity ↓ hydrolysis crystallinity ↓
solubility porosity ↑ hydrolysis
e) Tg: less mobility ⇒ ↓ hydrolysis Rates of Hydrolysis:
anhydride > ester > amide > ether
 Polymeric Biomaterials
Esters: R-COO-R’ + H2O → R-COOH + HO-R’
An amorphous poly(lactide-co-glycolide) with rapid
degradation property is used as bioresorbable sutures,
controlled release matrices, tissue engineering
scaffolds etc.
Semicrystalline polyethylene terephthalate (Dacron)
with very slow hydrolysis property find application in
vascular grafts, arterial patches, heart pumps etc.
Ethers: R-O-Rˡ + H2O → R-CH2-OH + HO-CH2-Rˡ
Semicrystalline polyethylene oxide (PEO) used for
protein resistant coatings and hydrogels is flexible,
hydrolyzable, water soluble and bioinert. These
properties are derived from both primary and strong
secondary H-bonding.
However, some olefins (e.g., Ultrahigh molecular weight
polyethylene-UHMWPE: joint cup liners), halogenated
hydrocarbons (e.g., PVC: catheters; PTFE: vascular grafts), siloxanes
(e.g., PDMS: soft tissue prostheses) and sulfones (e.g., PSF: renal
dialysis membranes) exhibit stable polymer chemistry.
 Composite Biomaterials
Natural biocomposites - bone, wood, dentin, cartilage, and
skin.
Bone achieves most of its mechanical properties as a natural
composite material composed of calcium phosphate ceramics
in a highly organized polymeric collagen matrix.
Biocomposites are composite materials composed of a
biodegradable matrix and biodegradable natural fibers as
reinforcement in order to obtain properties that improve
every one of the components.
Composite materials allow a flexible design since their
structure and properties can be optimized and tailored to
specific applications. Eg. fiberglass with a polymeric matrix is
used in the current synthetic casting materials.
 THIN FILMS
Films with thickness ranging from 0.1- 300 µm.
Thin film coating produces specific surface properties
such as
▪ Chemically stable in the environment where it is used
▪ Adhere well to the substrate
▪ Uniform thickness
▪ Chemically pure or of controlled chemical composition
▪ Optical or magnetic properties, insulator or
semiconductor as required for particular applications
Bonding between thin film and substrate
Bonding forces may be
1) Primary chemical in nature.
• Bond energies in the range of 250 to 400
kJ/mol.
• Example - The oxide lattices of the metal oxide
on to the substrate.
2) Van der Waals and electrostatic forces.
▪ Bond energies in the range of 50-100 kJ/mol.
▪ Example - Deposition of organic polymer film
on a metal surface.
Uses
• As conductors, resistors & capacitors
• As optical coatings on lenses to reduce
reflection & to protect the softer glass against
scratches.
• As protective coatings on metals. Eg. Silver
plating, chrome plating.
• Ceramic film coating on metal surfaces to
increase hardness Eg. Tungsten carbide film on
drills.
Formation of thin films
The process of applying a thin film to a surface is
known as thin-film deposition or fabrication.
Different techniques of thin film formation
i) Physical vapor deposition (PVD)
ii) Chemical vapor deposition (CVD)
When the vapor source is a liquid or solid, the process
is called physical vapor deposition (PVD). When the
vapor source is a chemical vapor precursor the
process is called chemical vapor deposition (CVD).
Physical Vapor Deposition (PVD)

PVD processes are atomistic

deposition processes in which
material is vaporized from a
solid or liquid source in the
form of atoms or molecules,
transported as vapor through a
vacuum or low pressure
gaseous (or plasma)
environment to the substrate
where it condenses.
Physical Vapour Deposition is done in two methods – i) Vacuum
evaporation/deposition, ii) Sputtering
The chemical purity of evaporated films depends on the
nature and level of impurities that
(1) are initially present in the source
(2) contaminate the source from the heater, crucible, or
support materials
(3) originate from the residual gases present in the vacuum
system

8
 Vacuum deposition
Vacuum evaporation is one of the important methods for
depositing thin films using PVD technique.

This method is used to form

thin films of substances that
can be vaporized without
destroying their chemical
identities.
Example: Optical lenses are
coated with inorganic
materials such as MgF2, Al2O3
and SiO2.
The vacuum environment may serve the purposes such
as -
i) Providing low pressure plasma environment, a means
for controlling gas and vapour composition.
ii) A means for controlled flow of mass (quantity) into
the processing chamber.

Let us watch a video clipping which demonstrates the

process.
https://www.youtube.com/watch?v=f7UxBawRPj4
Advantages of PVD

▪ Coatings harder & more corrosion resistant

▪ Have high temperature & good impact strength,
excellent abrasion resistance & durable.
▪ Able to use several types of inorganic & organic
coating materials on diverse group of substrates
using a wide variety of finishes.
▪ Eco-friendly than traditional processes.
▪ Possible to change the target material without
disturbing the system so that multilayer films can be
formed.
Disadvantages of PVD:

▪ Extremely difficult to coat undercuts and similar

surface features (∴ known as line of sight
technique).
▪ High capital cost.
▪ Some processes operate at high vacuums &
temperatures.
▪ Requires appropriate cooling systems.
▪ The rate of coating deposition quite slow.
 Chemical Vapor Deposition (CVD)
In this method the surface is coated with a stable chemical
compound at a temperature below the melting point of the
surface.
It involves the dissociation and /or chemical reactions of
gaseous reactants in an activated (heat, light, plasma)
environment, followed by the formation of a stable solid
product.
Main components of CVD equipment
✓ Chemical vapor precursor supply system
✓ CVD reactor component consisting of load lock,
substrate holder and heating system
✓ Effluent gas handling system
Process principles and deposition mechanism: CVD
process involves the following key steps:
1. Generation of active gaseous reactant species.
2. Transport of these gaseous species into the reaction
chamber.
3. In homogeneous gas phase reactions, the intermediate
species are formed subsequent decomposition forming
powder and volatile by-products.
4. Adsorption of gaseous reactants on to the heated
substrate, and the heterogeneous reaction occurs at the
gas-solid interface (i.e. heated surface) which produces
the deposit and by-product species.
5. The deposits will diffuse along the heated substrate
surface forming the crystallization center and growth of
the film takes place.
6. Gaseous by-products are removed from the boundary
layer through diffusion
7. The unreacted gaseous precursors and by-products will
be transported away from the deposition chamber.
Examples: Titanium tetrabromide is evaporated and the gaseous
TiBr4 is mixed with hydrogen. The mixture is then passed over a
substrate heated to about 1300 °C, such as silica or alumina. The
metal halide undergoes reaction with hydrogen to form a thin film
of titanium metal on the substrate.
TiBr4(g) + 2H2(g) Ti(s) + 4HBr(g)
Films of silicon are formed by decomposing SiCl4 in the presence of
H2 at 1200 °C.
SiCl4(g) + 2H2(g) Si(s) + 4HCl(g)
Advantages
• Produces highly dense & pure materials
• Uniform films with good reproducibility & adhesion
• Good throwing power
• Control over crystal structure, surface morphology &
orientation of the products
• Deposition rate can be adjusted
• Use a wide range of chemical precursors
Drawbacks
• Chemical & safety hazards caused by the use of toxic
[Ni(CO4)], corrosive [SiCl4], flammable &/or explosive
[B2H6] precursor gases.
• By-products are sometimes hazardous in nature (CO, HF
etc.)
• Difficult to deposit multicomponent materials with well
controlled stoichiometry using multisource precursors.
• It leads to stress in films deposited on materials with
different thermal expansion coefficients, which can
cause mechanical instabilities in the deposited films.
• High fabrication cost.
 Comparison between PVD & CVD
Features PVD - Vacuum CVD
evaporation
Mechanism of Thermal energy Chemical reaction
deposition
Deposition rate High Moderate
Deposited species Atoms & ions Precursor molecules
dissociate into
atoms
Energy of Low (0.1-0.5 eV) Low; can be high
deposited species with plasma-
assisted CVD
Throwing power Poor Good
 Nanomaterials
• dimensions - 1 to 100 nm
• Large surface area to volume
 Classification
Based on
Origin
✓ Natural - Carbon nanotubes
✓ Artificial – Ag/Au nano particles, Polymeric nano composites
Dimension
This classification is based on the number of dimensions which
are not confined to the nanoscale range (< 100 nm).
✓ Zero dimensional, Eg: quantum dots
✓ 1 dimensional, Eg: nanotubes, nanowires
✓ 2 dimensional, Eg: nano films
✓ 3 dimensional, Eg: nano spheres (Bulk nano materials)
Bulk nano material, contain dispersion of nanoparticles like
bundles of nanotubes or nanowires, mainly used in drug delivery
systems
Ref: Bansi Dhar Malhotra, Md. Azahar Ali, in Nanomaterials for Biosensors, 2018
Poh, T.Y., Ali, N.A.B.M., Mac Aogáin, M. et al. Inhaled nanomaterials and the respiratory
microbiome: clinical, immunological and toxicological perspectives. Part Fibre
Toxicol 15, 46 (2018). https://doi.org/10.1186/s12989-018-0282-0
 Preparation of nano-materials

• Top down: Top-down methods start with micro – or

macroscale materials, which are then broken down
chemicals or physically to nanoparticles.
• Bottom up: Bottom up methods involve the
assembly of very small units (atoms, molecules or
small nanoparticles) to create larger nanomaterials
and systems.
1) Bottom up:
i) Vapor deposition
❖ Physical VD
❖ Chemical VD
ii) Chemical synthesis
❖ Sol gel method
❖ Reduction method
iii) Electrodeposition
2) Top-down:
i) Ball milling
ii) Solution combustion method
 Chemical Synthesis

a) Sol-gel method
Steps involved
▪ Preparation of a precursor solution
▪ Deposition of the sol onto a substrate
▪ Formation of gel
▪ Drying process
▪ Heat Treatment
1. Preparation of a precursor solution: The desired
colloidal particles are dispersed in a liquid to form a
sol. Typical precursors are metal alkoxides, which
undergo various forms of hydrolysis and poly-
condensation reactions. The formation of a metal oxide
involves connecting the metal centers with oxo (M-O-
M) or hydroxo (M-OH-M) bridges, therefore generating
metal-oxo or metal-hydroxo polymers in solution.
2. Deposition of the sol onto a substrate: The sol
solution is coated on a substrate by spraying, dipping or
spinning.
3. Formation of gel: The particles in the solid state are
polymerised through the removal of the stabilizing
components. This can be done either by heating the sol at a
low temperature or allowing it to stand for certain duration.
4. Drying process: Removal of the remaining liquid phase
requires a drying process, which is typically accompanied
by a significant amount of shrinkage and densification. The
rate at which the solvent can be evaporated or extracted is
ultimately determined by the distribution of porosity in the
gel.
5. Heat Treatment/firing: After drying, a thermal treatment,
or firing process, is often necessary to favor further poly-
condensation and enhance mechanical properties and
structural stability via final sintering, densification and
grain growth.
Advantages of Sol-Gel Technique:
❖The sol-gel method is cost effective
❖The process is carried out at low temperature
and hence chemical composition of the final
compound can be controlled
❖The small quantities of dopants, such as organic
dyes and rare earth elements, can also be
introduced in the sol to modify the overall
properties of the final product.
❖Very thin films of metal oxides can be produced
using this method
 Ball milling
• In ball milling technique the solid ceramic material
which is to be grinded is placed at the bottom of inside
drum.
• Small balls are allowed to rotate around the inside of a
drum and drop with gravity force on to a solid enclosed
in the drum and hence crush the solid into nanoparticle
size
 Video Presentation of Ball Milling

https://www.youtube.com/watch?v=MikiTYpg2aQ
 Video Presentation of sophisticated Ball Mill

https://www.youtube.com/watch?v=5ShOAS3EGGU
Examples:
In the production of naocrystalline Zirconia (ZrO2),
zirconium chloride is treated with magnesium oxide during
milling to form zirconia and magnesium chloride:
ZrCl4 + 2MgO → ZrO2 + 2MgCl2
The by-product, magnesium chloride, acts to prevent the
individual nanocrystallites of zirconia agglomerating.
It is washed out at the end of the process.
Disadvantage:
➢ Polymers cannot be reduced to nanoparticles by
grinding because of their molecular structure and their
impact resistance.
➢ It is difficult to avoid contamination of the
nanoparticles by the materials used in the abrasion
process and the particle sizes are not uniform.
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Q) The emf of the cell Cd|CdCl2. 2.5 H2O (saturated) || AgCl(s)| Ag is
0.6776V and 0.7915 V at 298 K and 273 K respectively. Calculate ΔH
and ΔG of the cell reaction at 273 K.
Ans-
Here n = 2, E = 0.6753 V at 298 K and 0.7915 at 273 K.
(δE/δT)p = (0.6776-0.7915) V/ (298-273) K
= -0.0046V/K
Now at 273K,
∆H = nF [ T (δE /δT)P –E]
=2 x 96,500 { [273x (-0.0046)] –0.7915V }
= -392KJ
ΔG= nFE
= 2x 96,500 x (-0.7915) = -152JK -1

Q) Describe the determination of carbon and hydrogen in a given coal

sample and calculate the amount of nitrogen present if2.6 g of coal
sample was Kjeldahlised and NH3 gas thus evolved was absorbed in
50 mL of 0.1 N sulphuric acid. After absorption, the excess of acid
required 7.5 mL of 0.1 N NaOH for neutralization. Calculate the % of
nitrogen in the sample.
Ans-
4.Description of estimation of Carbon
Percentage of carbon= (Increase in weight of KOH
tube × 12 × 100)/ (Weight of coal taken ×44)
Percentage of hydrogen = (Increase in weight of
CaCl2tube × 2 ×100) /(Weight of coal taken ×18)
Estimation of Nitrogen: (N1V1) H2S04 = (N2V2) NaOH
% Nitrogen = Vol. of acid used × Nacid×1.4 /Wt. Of coal taken
% Nitrogen = (42.5 × 0.1 × 1.4) / 2.6
= 2.28%
Q)The EMF of the cell Pt, H2(1 atm) | H+|| KCl (saturated) |
Hg2Cl2(s),Hg is 0.4350V at 298 K. An emf of 0.3260V was observed
when a combined glass electrode with 015 corning glass was introduced
in the same solution at 298 K. Besides, an EMF of 0.3848 V was
recorded when the same glass electrode was introduced in another
buffer solution and the temperature maintained at 298 K. Determine the
concentration of H+ ions in the buffer solution if the electrode potential of
saturated calomel electrode is 0.2444 V. Do you think that the
concentration of H+ ions measured is accurate and why? Why is the
glass electrode always stored in aqueous solution?
Ans-
Ecell= Ecal (Saturated) –(-0.0591pH) 0.4350
= 0.2444 + 0.0591 pH
pH= 0.1906/ 0.0591 = 3.2250
pH= (Ego−Ecell− Ecal (sat) ) / 0.0591
3.2250= ( Ego−0.3260−0.2444) /0.0591
Ego –0.5704= 0.1906Ego= 0.760 V
pH= ( 0.760− 0.3848−0.2444) / 0.0591pH = 2.213 -½M-
log [H+] = pH-log [H+]
= 2.213[H+] = 6.1 x 10-3
It is accurate
the pH is between 2 and 12, there is neither acid nor alkaline error
The glass membrane takes several hours to rehydrate
The ion exchange equilibrium is then reached slowly
Q)The emf of the cell Cd|CdCl2. 2.5 H2O (saturated) || AgCl(s)| Ag is
0.7777V and 0.8442V at 298 K and 273 K respectively. Calculate ΔH
and ΔS of the cell reaction at 298 K and ΔG at 305K.
Ans-
Here n = 2, E = 0.7777V at 298 K and 0.8442at 273 K.
(δE/δT)p = (0.7777-0.8442) V/ (298-273) K
= -0.00266 V/K
At298 K,
∆H = nF [T(δE /δT)P–E]
=2 x 96,500 { [298×(-0.00266)] –0.7777V }
= -303.1 kJ
ΔS = nF(δE / δT) P
= 2x 96,500 x (-0.00266) = -513.4J/K
At 305 K
E@305= E@298+(305-298)×(δE/δT)P
= 0.7777+(7×-0.00266)= 0.7591V
∆G = -nFE
= -2×96,500×0.7591 V
= -146.51kJ

Q) What is EoNi2+/Ni at 298 K if the emf of

Zn(s)/Zn2+(1M)││Ni2+(1M)/Ni(s) is 0.51V and Zn(s)/Zn2+(1M)││SCE is
1.002V (ESCE = 0.2422V).
Ans-
E cell= E calomel - Ezn
0.51 =[E0Ni -(-0.7598)]- 0.0591/2 log(1)/(1)
E0Ni = 0.51- 0.7598 = - 0.2498 V
E0Zn = 0.51- 0.7598 = - 0.2498 V
Ezn= 0.7598
Q)The emf of a cell, Pt | H2 | H+ (x) || KC l |Hg2Cl2 | Hg is 0.83V at 298K. Then
the pH of the unknown solution is
Ans-
pH = (Ecell – 0.2422)/0.0592 = (0.83-0.2422)/0.0592 = 9.9

2.Using the electrochemical series, calculate the emf in volts for the cell
Fe(s) | Fe2+(0.1 M) || Cd2+(0.2 M) | Cd at 298 K. Write the cell
reactions.
Ans
: From the series we have; Eo Cd2+/Cd = − 0.40 V ;
Eo Fe2+/Fe = − 0.44 V
At anode Fe →Fe2+ + 2 e−
At Cathode Cd2+ + 2 e− → Cd
Net reaction: Fe + Cd2+→ Fe2+ + Cd
EMF of the cell at 298 K is given by
Eocell = Eocathode − Eo anode = − 0.40 − (− 0.44) = 0.04 V
Ecell = Eocell − (0.0591 / n) log [ Fe2+ ] / [Cd2+]
= 0.04 −( 0.0591/ 2 ) log [0.1] / [0.2] = 0.0488 V

3. Find the molar concentration of Cd2+ ions in the given

electrochemical cell.
Zn / Zn2+ (0.1 M) // Cd2+(M)/ Cd
Given Eo Zn2+/Zn = − 0.76 V; Eo Cd2+/Cd = − 0.40 V ; and Ecell =
0.3305 V at 298 K
Ans: Cell representation
Zn│Zn2+(1M)││Ag+
(10M)│Ag
Cell reaction:
Zn + 2Ag+ → Zn2+ + 2Ag
Eo cell = Eo cathode – Eo anode
= 0.80 − ( −0.76) = 1.56 V
Ecell = E°cell − (0.0592/ 2) log [1]/[10]2
= 1.56 – (0.0591 /2) log [1] / [10]2 = 1.6192 V

4.Write the cell reactions and calculate the EMF in volts for the following
cell at 298K.
Mg/ Mg2+ (0.001M) // Cu2+ ( 0.0001M) / Cu .
Given Eo Cu2+/Cu = 0.34 V and Eo Mg2+/Mg = − 2.37V
Ans: At anode Mg → Mg2+ + 2 e−
At cathode Cu2+ + 2 e− → Cu
Net reaction Mg + Cu2+ → Mg 2+ + Cu
Ecell = Eocell − (0.0591/n ) log [ Mg2+]/ [Cu2+]
Eocell = Eocathode − Eo anode
= 0.34 – [ −2.37]
= 2.71V
Ecell = 2.71 – (0.0591 /2) log [0.001]/ [0.0001]
= 2.6805 V

Example of problem on concentration cells:

Ecell = 0.0591/n log C2 /C1
0.09 =(0.0591/2) log ( x / 0.001)
x =1.097M //unknown concentration
Q-Polymer molecules with different degree of polymerization such as
500, 750, 850 and 1100 are mixed in molecular ratio 1: 2: 3: 4 in a
sample of high polymer of styrene. Calculate the number average and
weight average molecular weights. ( C6H5 CH CH2 )
Ans-
Mn =1 x (500 x 104) + 2 x (750 x 104) + 3 x (850 x 104) + 4 x(1100 x
104) ------------------------------------------------------------------------------------ 10
= 93080
Mw = 1 x (500 x 104)2 + 2 x (750 x 104)2 + 3 x (850 x 104)2 + 4 x
(1100 x 104)2 -----------------------------------------------------------------------------
--------------- 1 x (500 x 104) + 2 x (750 x 104) + 3 x (850 x 104) + 4 x
(1100 x 104)
= 97,405.33

Calculate net calorific value of a coal sample having 2.5 %percentage of

hydrogen and gross calorific value of 25969.3 × 10^3 J/kg.
NCV = GCV – 0.09 × % H ×587
NCV = GCV – 0.09 × % H ×587×4.184×103
= 25969.3×103 - 0.09×2.5×587×4.184×103
= 25416.7 J/Kg
Note: 1 calories = 4.18 J 1 kcal =J