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MOLECULAR ORBITAL THEORY

Molecular orbital theory proposed by Hund and Mulliken in 1932 explains the formation of a
covalent bond in a better way. According to molecular orbital theory all atomic orbitals of the
atoms participating in molecule formation get disturbed when the concerned nuclei approach
nearer. They all get mixed up to give rise to an equivalent number of new orbitals that belong to
the molecule now. These are called molecular orbitals. Thus, every molecule is supposed to have
molecular orbitals associated with it in much the same way as a single isolated atom has. The main
features of molecular orbital theory can be summed up as follows:
(i) The electrons in a molecule are present in the various molecular orbitals as the electrons of
atoms are present in the various atomic orbitals.
(ii) While an electron in an atomic orbital is influenced by one nucleus, in a molecular orbital it
is influenced by two or more nuclei depending upon the number of atoms in the molecule.
Thus, an atomic orbital is monocentric while a molecular orbital is polycentric.
(iii) The atomic orbitals of comparable energies and proper symmetry combine to form molecular
orbitals.
(iv) The number of molecular orbitals formed is equal to the number of combining atomic
orbitals. When two atomic orbitals combine, two molecular orbitals are formed. One is
known as bonding molecular orbital while the other is called antibonding molecular orbital.
(v) The bonding molecular orbital has lower energy and hence greater stability than the
corresponding antibonding molecular orbital.
(vi) Just as the electron probability distribution around a nucleus in an atom is given by an atomic
orbital, the electron probability distribution around a group of nuclei in a molecule is given
by a molecular orbital.
(vii) The molecular orbitals like atomic orbitals are filled in accordance with the Aufbau principle,
obeying the Pauli’s exclusion principle and the Hund’s rule.
Linear Combination of Atomic orbitals (LCAO method)
According to wave mechanics the atomic orbitals can be expressed as wave functions (ψs)
which represent the amplitude of electron waves. Their values can be calculated from the solutions
of Schrödinger’s wave equation. In a similar way, Schrödinger’s wave equation can be applied to
molecular orbitals but with slight difficulty. To cope with the difficulty an approximate method
known as Linear Combination of atomic orbitals is applied.
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According to this method, the molecular orbitals are formed by the linear combination
(addition or subtraction/ constructive interference or destructive interference) of atomic orbitals of
the constituent atoms of the molecule. Let us consider the simplest case of H2 molecule consisting
of two hydrogen atoms represented by HA and HB. The atomic orbitals of these atoms are
represented by the wave functions ψA and ψB. When these atoms approach each other there come
two possibilities.
(1) Molecular orbital is formed by the addition of wave functions of atomic orbitals. It can be
represented by ψ(MO) = ψA + ψB ………..(i)
The M.O. formed is called bonding molecular orbital. It lowers the energy and brings the
stability in the system.
(2) Molecular orbital is formed by the subtraction of wave functions of atomic orbitals. It can be
represented by ψ*(MO) = ψA – ψB ……….(ii)
The MO formed is called antibonding molecular orbital. This type of MO corresponds
to higher energy state. It has net disruptive effect. Hence, this MO is termed as antibonding
molecular orbital, distinguished by attaching an asterisk (*) mark with the symbolic name of the
molecular orbital. The molecular orbitals formed by the combination of 1s orbitals of two hydrogen
atoms is shown below: (Fig. 1)

Fig. 1. Formation of molecular orbitals from two s orbitals of hydrogen atoms.

The wave functions either have (+) or (–) sign. The positive sign shown on 1s orbitals of
hydrogen atoms shows that these orbitals are spherically symmetrical, and their wave functions
are associated with +ve sign in all directions. In case of p-orbitals one lobe has +ve sign while
other has –ve sign. The overlapping of atomic orbitals takes place if they have similar signs on
their lobes. The probability density in bonding and antibonding molecular orbitals is given by the
square of the wave functions shown in the equations (i) and (ii)
Ψ2(MO) = (ψA + ψB)2
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= ψA2 + ψB2 + 2ψAψB …………(iii)

Ψ2 (MO) = (ψA – ψB)2
= ψA2 + ψB2 – 2ψAψB………….(iv)
From equation (iii) probability density of bonding molecular orbital is greater than the sum
of the probability densities of isolated atoms by the factor 2ψAψB. Thus, the probability density of
electrons in bonding MO is greater than that in either of atomic orbitals (ψ2A or ψ2B).
From equation (iv) probability density of antibonding MO is lesser than the sum of
probability densities of isolated atoms by a factor 2ψAψB. Thus, the probability density of electrons
in antibonding MO is less than that in either of atomic orbitals (ψ2A or ψ2B). In a similar way, the
combination of two 2s orbitals produces a bonding σ2s and antibonding σ*2s molecular orbitals.
Molecular Orbitals from combination of p-Atomic Orbitals
Combination of p-orbitals is slightly complicated. There are three types of 2p orbitals
namely 2px, 2py and 2pz directed along the cartesian co-ordinates x, y and z respectively. By
convention we assume that z-axis is the intermolecular axis.
(1) Combination of 2pz atomic orbitals
When two 2pz orbitals on two atoms approach each other along the internuclear axis they
combine by the addition of wave function. This results in the formation of bonding σ 2pzorbital
while subtraction of wave functions give rise to antibonding molecular orbital σ*2pz. It is
represented as follows: (Fig. 2)

Fig. 2. Combination of 2 pz orbitals to form bonding and antibonding molecular orbitals.

(2) Combination of 2py and 2px atomic orbitals

When two 2py or 2px orbitals on two atoms are approaching in a manner that their axes are
mutually parallel. The side-wise overlap of these orbitals to give rise to the formation of molecular
orbitals that are not symmetrical about the internuclear axis and are called π molecular orbitals
represented by π2py or π2px bonding orbitals. These π2py and π2px bonding MOs have zero
electron density on the plane that contains the nuclear axis (nodal plane), while the electron density
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is concentrated in two regions above and below the nodal plane. The π*2py and π*2px antibonding
MOs have higher energy than their corresponding molecular and atomic orbitals. Since 2py and
2px atomic orbitals on an atom are degenerate (are of equal energy), the π molecular orbitals arising
out of them will also be degenerate i.e. π 2py and π 2px bonding molecular orbitals possess equal
energy and the same situation prevails in antibonding molecular orbitals π*2py and π*2px. (Fig. 3)

Fig. 3. Schematic representation of combination of 2py and 2px atomic orbitals

Formation of bonding and antibonding molecular orbitals by side-wise overlap of 2py
atomic orbitals. 2px Orbitals also combine in the similar way.
Combination of s and pz-orbitals:
s and pz-orbitals can also combine in a similar way along internuclear axis to form bonding
and antibonding molecular orbitals as shown in Fig. 4.

Fig. 4. Combination of s and p orbitals

p-d combinations of orbitals:
A p-orbital on one atom may overlap with a d-orbital on another atom, giving bonding and
antibonding combinations. Since the orbitals do not point along the line joining the two nuclei,
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overlap must be of the π type (Fig. 5). This type of bonding is responsible for the short bonds found
in the oxides and oxoacids of phosphorus and sulphur. It also occurs in transition metal complexes
such as the carbonyls and cyanides.

Fig. 5. Combination of p and d orbitals

Non-bonding combinations of orbitals:
All the cases of overlap of atomic orbitals considered so far have resulted in a bonding MO
of lower energy, and an antibonding MO of higher energy. To obtain a bonding MO with a
concentration of electron density in between the nuclei, the signs (symmetry) of the lobes which
overlap must be the same. Similarly, for antibonding MOs the signs of the overlapping lobes must
be different. In the combinations shown in Fig. 6 any stabilization which occurs from overlapping
(+) with (+) is destabilized by an equal amount of overlap of (+) with (-). There is no overall
change in energy, and this situation is termed non-bonding. It should be noted that in all of these
non-bonding cases the symmetry of the two atomic orbitals is different, i.e. rotation about the axis
changes the sign of one.

Fig. 6. Some non-bonding combinations of atomic orbitals.

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Differences between Atomic and Molecular orbitals

Atomic Orbitals Molecular Orbitals
Atomic orbitals monocentric. The electron Molecular orbitals are polycentric. The
cloud spreads around the nucleus of a single electron cloud spreads around all nuclei of the
atom. bonded atoms in the molecule.
The electrons present int atomic orbitals are The electrons present in the molecular orbitals
influenced by single nucleus. are influenced by more the one nucleus.
The shapes are simple except f-orbital Shapes are generally complex
The AOs are designated as s,p,d..etc. The MOs are designated as σ, σ*, π, π*

Conditions for the combination of Atomic Orbitals:

The atomic orbitals may combine when certain conditions are satisfied. For effective
combinations of atomic orbitals following are the conditions.
1) The energies of atomic orbitals should be comparable. For homonuclear diatomic
molecules of the type X2 similar atomic orbitals combine i.e. 1s orbital of one atom
combines with 1s orbital of another and similarly 2s orbital combines with 2s orbital of
another atom and so on. This means that 1s orbital cannot combine with 2s orbital because
of large energy difference between the two orbitals. In case heteronuclear molecules this
condition may not be valid.
2) The extent of overlap between the atomic orbitals should be to a considerable extent.
Greater the overlap between the atomic orbitals, greater is charge density between the
nuclei.
3) The symmetry of the combining atomic orbitals should be the same. The atomic orbitals
should have the same symmetry about the internuclear axis. For example, 2s orbital of one
atom can combine with 2s or 2pz orbital of another atom but not with the 2py or 2px orbital.
In other words, (+, +) or (–, –) interaction is allowed.
DIFFERENCE BETWEEN BONDING AND ANTIBONDING MOLECULAR ORBITALS
S.No. Bonding MO Anti-bonding MO
1 It is formed by addition of wave functions It is formed by subtraction wave
of atomic orbitals. functions of atomic orbitals.
2 The wave function of a bonding MO is The wave function of an antibonding
given by ψ(MO) = ψA + ψB MO is given by ψ∗(MO) = ψA – ψB
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3 Its formation takes place when the lobes of Its formation takes place when the
atomic orbitals have same signs. lobes of atomic orbitals have different
signs.
4 The energy of bonding MO is lower than The energy of antibonding MO is
that of atomic orbitals from which it is higher than that of atomic orbitals
formed. from which it is formed.
5 The electron density is high in the region The electron density is low in the
between the nuclei of bonded atoms. region between the nuclei of bonded
atoms.
6 Every electron in bonding MO contributes Every electron in antibonding
towards the attractive force. contributes towards repulsive force.

Difference between Sigma and Pi molecular orbitals

The main points of difference between sigma and Pi molecular orbitals.
S.NO. Sigma (σ) MO Pi (π) MO
1 It is formed by head-to-head It is formed by the sidewise overlapping
overlapping of atomic orbitals. of atomic orbitals.
2 The overlap is along internuclear axis. The overlap is perpendicular to
internuclear axis.
3 As a result of this strong bond is As a result of this weak bond is formed.
formed
4 This orbital is symmetrical to rotation This orbital is not symmetrical to rotation
about the line joining the two nuclei. about the line joining the two nuclei.
5 The region of overlap is greater. The region of overlap is lesser.
BOND ORDER: How many bonds present in a molecule or bond order is correctly predicted by
the Molecular Orbital theory. The bond order is one-half of the difference of the number of
electrons in the bonding molecular orbitals and the number of electrons in the antibonding
molecular orbitals. Mathematically,
(𝑁𝑜. 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝐵𝑜𝑛𝑑𝑖𝑛𝑔 𝑀𝑂) − (𝑁𝑜. 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝐴𝑛𝑡𝑖 − 𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑀𝑂)
𝐵. 𝑂. =
2
𝑁𝑏 − 𝑁𝑎
𝐵. 𝑂 =
2
Where Nb is no of electrons in BMO and Na is no of electrons in ABMO
In common practice, only MOs formed from valence orbitals are considered for determining bond
order.
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The predicted bond orders are found to be in conformity with other methods of determining
it. Thus, Molecular Orbital theory helps in establishing whether the existence of a bond is feasible
or not.
In general,
(a) A molecule is stable if Nb > Na
(b) A molecule is unstable if Nb < Na
Information given by Bond order:
The bond order as determined by the above formula is very helpful as it gives us the
following valuable information:
(1) Stability of the Molecule/Ion: A molecule/ion is stable if Nb > Na
(2) Bond Energy: It depends upon the bond order. Bond order is directly proportional to bone
energy. Greater the bond order greater is the bond energy.
(3) Bond Length: Bond order is inversely proportional to the bond length. Higher the bond order,
smaller the bond length.
(4) Magnetic Properties: The presence of unpaired electrons in Molecular orbitals of a species
makes it paramagnetic in nature. Greater the number of unpaired electrons, the more will be its
paramagnetic character. On the other hand, if there are no unpaired electrons in MOs the species
will be diamagnetic in nature.
Examples of molecular orbital treatment for homonuclear diatomic molecules:
In the molecular orbital method, we consider the whole molecule rather than the constituent
atoms, and use molecular orbitals rather than atomic orbitals. In the build-up of the molecule, the
total number of electrons from all the atoms in the molecule is fed into molecular orbitals. The
Aufbau principle and Hund's rule are used as before. For simplicity homonuclear diatomic
molecules will be examined first. Homonuclear means that there is only one type of nucleus, that
is one element present, and diatomic means that the molecule is composed of two atoms.
Hydrogen, H2:
Hydrogen molecule is formed from 1s1 atomic orbitals of two atoms. They give rise to two
molecular orbitals σ1s and σ*1s (Fig. 7).
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Fig. 7. MO diagram of Hydrogen

The molecule has two electrons to be accommodated in these two molecular orbitals and
are filled as desired by Aufbau order of filling. Both these electrons go to the lower energy bonding
molecular orbital and the antibonding orbital remains vacant. The electronic configuration of the
molecule is represented by the equation:
2H (1s1) H2 [σ1s2, σ*1s0)]
𝑁𝑏 − 𝑁𝑎 2 − 0
𝐵. 𝑂 = = =1
2 2
The number of bonds in the molecule is one. Thus, two hydrogen atoms are bonded through only
one bond in the molecule. The molecule is diamagnetic because unpaired electrons are not present.
H2+ molecule ion:
This may be considered as a combination of a H atom with a H+ ion. This gives one electron
in the molecular ion which occupies the lowest energy MO: σ1s1 (Fig. 8a)
The electron occupies the σ1s1 bonding MO (fig 8a).
𝑁𝑏 − 𝑁𝑎 1 − 0 1
𝐵. 𝑂 = = =
2 2 2
This species exists but it is not common, since H2 is much more stable. However, H2+ can
be detected spectroscopically when H2 gas under reduced pressure is subjected to an electric
discharge.
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Fig. 8. MO diagrams of H2+, He2 and He2+ molecules

Helium, He2
Helium atoms have the configuration 1s2. For the formation of He2, the molecular orbitals
required are σ1s and σ*1s (Fig. 8c) which have to accommodate four electrons (two each
contributed by the atoms). Each one of these molecular orbitals would accommodate two electrons
as shown below (8b).
The molecule of helium is represented by the equation,
2He (1s2) He2 [σ (1s2) σ* (1s2)]
There are two electrons in each of the bonding and antibonding orbitals.
𝑁𝑏 − 𝑁𝑎 2 − 2
𝐵. 𝑂 = = =0
2 2
Since the bond order is zero there is no bond between two He atoms and this molecule does not
exist.
He2+ molecule ion:
This may be considered as a combination of a He atom and a He+ ion. There are three
electrons in the molecular ion which are arranged in MOs: σls2, σ*ls1 (Fig. 8c)
𝑁𝑏 − 𝑁𝑎 2 − 1 1
𝐵. 𝑂 = = =
2 2 2
Since the bond order is 0.5, the helium molecule ion can exist. It is very un-stable, but it
has been observed spectroscopically. It contains one unpaired electron; hence, it is paramagnetic
in nature.
Nitrogen, N2:
Each of the two N-atoms contribute five valence electrons and four atomic orbitals towards
the molecule. The molecule would have eight molecular orbitals and ten electrons to be
accommodated in them. The typical MO diagram of N2 is depicted in the following figure (fig. 9).
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Fig. 9. Molecular orbital diagram of Nitrogen molecule.

The electronic configuration in the molecule is represented as:
K, K’, σ2s2, σ*2s2, π2px2 = π2py2, σ2pz2, π*2px0 = π*2py0, σ*2pz0
There are eight electrons in the bonding molecular orbitals and only two in antibonding
orbital.
𝑁𝑏 − 𝑁𝑎 8 − 2
𝐵. 𝑂 = = =3
2 2
The bond order is 3. The two N atoms are bonded with three covalent bonds i.e., a triple
bond. N2 molecule is diamagnetic as it has no unpaired electrons.
O2 molecule: Each oxygen atom has 2 + 6 = 8 electrons. Thus, the O2 molecule contains a total of
16 electrons. These are arranged in MOs and shown diagrammatically in Figure 10.
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Fig. 10. MO diagram of Oxygen

The electronic configuration of the molecule is represented as:
σ1s2, σ*1s2, σ2s2, σ*2s2, σ2pz2, π2px2 = π2py2, π*2px1 = π* 2py1, σ*2pz0
The antibonding π*2px1 and π*2py1 orbitals are singly occupied in accordance with Hund's
rule. Unpaired electrons give rise to paramagnetism. Since there are two unpaired electrons with
parallel spins, this explains why oxygen is paramagnetic. If this MO treatment is compared with
the Lewis electron pair theory or the valence bond theory, they do not predict unpaired electrons
or paramagnetism. This was the first success of the Molecular orbital theory in predicting the
paramagnetism of O2, a fact not even thought of with a valence bond representation of O=O.
The bond order may be calculated as half the difference between the number of bonding
and antibonding electrons:
The bond order of O2 calculated as
𝑁𝑏 − 𝑁𝑎 8 − 4
𝐵. 𝑂 = = =2
2 2
The bond order is 2 which corresponds to a double bond.
O2- ion: The compound potassium superoxide KO2 contains the superoxide ion O2-. The O2- ion
has 17 electrons, and has one more electron than the 02 molecule. This extra electron occupies
either the π*2px or π*2py orbital. It does not matter which it occupies since they are degenerate.
K, K’, σ2s2, σ*2s2, σ2pz2, π2px2 = π2py2, π*2px2 = π*2py1, σ*2pz0
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𝑁𝑏 − 𝑁𝑎 8 − 5 1
𝐵. 𝑂 = = =1
2 2 2
This corresponds to a bond that is intermediate in length between a single and a double
bond. The superoxide ion has an unpaired electron and is therefore paramagnetic.
Examples of molecular orbital treatment for heteronuclear diatomic molecules:
The same principles apply when combining atomic orbitals from two different atoms as
applied when the atoms were identical, that is:
1). Only atomic orbitals of about the same energy can combine effectively. 2). They should have
the maximum overlap. 3). They must have the same symmetry.
The two atoms are different, the energies of their atomic orbitals are slightly different. The
problem is that in many cases the order of MO energy levels is not known with certainty.
NO molecule: The nitrogen atom has 2 + 5 = 7 electrons and the oxygen atom has 2 + 6 = 8
electrons, making 15 electrons in the molecule. The order of energy levels of the various MOs is
the same as for homonuclear diatomic molecules heavier than C2.
The electronic configuration: σ1s2, σ*1s2, σ2s2, σ*2s2, σ2pz2, π2px2 = π2py2, π*2px1 = π*2py0, σ*2pz0.
This is shown in Figure 11.

Fig. 11. MO diagram of NO

The bonding and antibonding 2s orbitals cancel, and a σ bond is formed by the filled σ2pz2
orbital. A π bond is formed by the filled π2px2 orbital. The anti-bonding molecular orbital π*2px1
is half-filled.
𝑁𝑏 − 𝑁𝑎 10 − 5
𝐵. 𝑂 = = = 2.5
2 2
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The bond order is 2.5, that is in between a double and a triple bond. The bond order is 2.5
and the molecule is paramagnetic since it contains an unpaired electron. In NO there is a significant
difference of about 250 kJ mo1-1 in the energy of the AOs involved, so that combination of AOs
to give MOs is less effective than in O2 or N2. The bonds are therefore weaker than might be
expected. Removal of one electron to make NO+ results in a shorter and stronger bond because the
electron is removed from an antibonding orbital, thus increasing the bond order to 3.
CO Molecule: The carbon atom has 2 + 4 = 6 electrons and the oxygen atom has 2 + 6 = 8
electrons, making 14 electrons in the molecule. The order of energy levels of the various MOs is
the same as for homonuclear diatomic molecules heavier than C2.
The electronic configuration: σ1s2, σ*1s2, σ2s2, σ*2s2, π2px2 = π2py2, σ2pz2, π*2px0 = π*2py0, σ*2pz0.
This is shown in Figure 12.

MO diagram of CO

The σ2pz molecular orbital is formed by the overlap of 2pz orbitals and π bonds by overlap
of 2px and 2py atomic orbitals.
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𝑁𝑏 − 𝑁𝑎 8 − 2
𝐵. 𝑂 = = = 3.0
2 2
The bond order is 3.0 and the molecule is diamagnetic since it doesn’t contain any unpaired
electron.
Benzene:
The difference between the amount of energy we expect to get out on hydrogenation (360
kJ mol–1) and what is observed (208 kJ mol–1) is about 150 kJ mol–1. This represents a crude
measure of just how extra stable benzene really is relative to what it would be like with three
localized double bonds. In order to understand the origin of this stabilization, we must look at the
molecular orbitals. We can think of the π molecular orbitals of benzene as resulting from the
combination of the six p orbitals.
In benzene all carbons are sp2 hybridized. The three sp2 hybridized orbitals form bonds
with two carbon atoms and a hydrogen atom. Every carbon atom has one p orbital and all these six
p orbitals will combine to produce six π molecular orbitals (Ψ1, Ψ2, Ψ3, Ψ4, Ψ5 and Ψ6). The six
electrons will occupy these molecular orbitals (fig 14).
The molecular orbital (Ψ1) lowest in energy is formed by the in-phase combination or
constructive interference of all the wave functions of six p-orbitals. The Ψ1 MO will not contain
any nodal plane and it is a continuous long orbital. This orbital shows the bonding interaction
between all the carbon atoms and explains the extra stability and aromaticity of benzene.
Each of the other two bonding MOs of benzene (Ψ2 and Ψ3) has a nodal plane. These two
orbitals are degenerate. Ψ2 has four bonding interactions and two antibonding interactions, for a
net of two bonding interactions, and Ψ3 also has two bonding interactions. Thus, Ψ2 and Ψ3 are
bonding MOs, but they are not as strongly bonding as Ψ1. The Ψ2 and Ψ3 are HOMOs of benzene.
The next molecular orbitals Ψ4 and Ψ5 will have two nodal planes and again there are two
ways of arranging these, which lead to two degenerate molecular orbitals. These two MOs are anti-
bonding molecular orbitals and are LUMOs of benzene.
The final molecular orbital (Ψ6) will have three nodal planes and all the p orbitals
combining out-of-phase combination or destructive interference. This is an anti-bonding molecular
orbital.
These are the six π molecular orbitals for benzene. We can draw an energy level diagram
to represent them (fig. 14).
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Frost Circle Three Nodes

ABMOs
Two Nodes

LUMO

One node

HOMO

BMOs

Schematic representation of MOs of Benzene

Fig. 14. The MO diagram of benzene

Whilst the HOMOs for benzene are the degenerate π molecular orbitals (Ψ2 and Ψ3), the
next molecular orbital down in energy is not actually the π molecular orbital (Ψ1). This all-bonding
π molecular orbital (Ψ1) is so stable that four σ bonding molecular orbitals come in between the π
molecular Ψ1 and Ψ2 orbitals but are not shown in this molecular orbital energy level diagram.
The greatest contribution to stability comes from this lowest-energy π bonding molecular orbital
(Ψ1). This allows bonding interactions between all adjacent atoms.
Aromaticity of Benzene:
Conditions for Aromaticity
• The molecule must obey the Huckel rule i.e., molecule must contain (4n+2) π electrons.
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• The molecule must be cyclic, planar with uninterrupted cloud of π electrons above and
below the plane.
• Benzene contains (4n+2) π electrons. The MO diagram of benzene shows that the Ψ 1 MO
is a continuous long orbital spread all over the 6 carbon atoms. The uninterrupted π electron
cloud is delocalized on all six carbon atoms, above and below the plane.
• All the boding molecular orbitals are occupied and anti-bonding molecular orbitals are
unoccupied. This electron configuration contributes to the aromaticity and stability of
benzene.
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Thermodynamics
The study of the flow of heat or any other form of energy into or out of a system as it undergoes a physical or
chemical transformation is called Thermodynamics.
Scope of Thermodynamics:
(1) Most of the important laws of Physical Chemistry, including the van’t Hoff law of lowering of vapour pressure,
Phase Rule and the Distribution Law, can be derived from the laws ofthermodynamics.
(2) It tells whether a particular physical or chemical change is feasible or not under a given set ofconditions of
temperature, pressure and concentration.
(3) It also helps in predicting how far a physical or chemical change can proceed, until theequilibrium conditions are
established.
Limitations of Thermodynamics
(1) Thermodynamics is applicable to macroscopic systems consisting of matter in bulk andnot to microscopic
systems of individual atoms or molecules. It ignores the internal structure of atoms and molecules.
(2) Thermodynamics does not bother about the time factor. That is, it does not tell anythingregarding the rate of a
physical change or a chemical reaction. It is concerned only withthe initial and the final states of the system.
Thermodynamic terms and basic concepts
An important part of the study of thermodynamics is a few terms and definitions which must be understood clearly.
System, Boundary, Surroundings:
A system is that part of the universe which is under thermodynamic study and the rest of the universe is
surroundings.
The real or imaginary surface separating the system from the surroundings is called the boundary.In
experimental work, a specific amount of one or more substances constitutes the system. Thus 200 g of water contained in
a beaker constitutes a thermodynamic system. The beaker and the air in contact are the surroundings.
Similarly, one mole of oxygen confined in a cylinder fitted with a piston, is a thermodynamic system.The cylinder
and the piston and all other objects outside the cylinder, form the surroundings. Herethe boundary between the system
(oxygen) and the surroundings (cylinder and piston) is clearlydefined.
Types of thermodynamic systems:
There are three types of thermodynamic systems depending on the nature of the boundary. Ifthe boundary is closed or
sealed, no matter can pass through it. If the boundary is insulated, noenergy (say heat) can pass through it.
(1) Isolated System: When the boundary is both sealed and insulated, no interaction is possible with the
surroundings. Therefore, an isolated system is one that can transfer neither matter nor energy to and from
itssurroundings.
A substance, say boiling water, contained in a thermos flask, is anexample of an isolatedsystem.
(2) Closed System: Here the boundary is sealed but not insulated. Therefore, a closed system is one which
cannottransfer matter but can transfer energy in the form of heat, work and radiation to and from
itssurroundings.A specific quantity of hot water contained in a sealed tube, is an example of a closed
 2

system.While no water vapour can escape from this system, it can transfer heat through the walls of the tubeto the
surroundings.
A gas contained in a cylinder fitted with a piston constitutes a closed system. As the piston israised, the
gas expands and transfers heat (energy) in the form of work to the surroundings.
(3) Open System: In such a system the boundary is open and un-insulated. Therefore, an open system is onewhich
can transfer both energy and matter to and from its surroundings.Hot water contained in a beaker placed on
laboratory table is an open system. The water vapour(matter) and also heat (energy) is transferred to the
surroundings through the imaginary boundary.
Intensive and extensive properties:
The macroscopic or bulk properties of a system (volume, pressure, mass, etc.) can be dividedinto two classes:
(a) Intensive properties(b) Extensive properties
Intensive Properties:
A property which does not depend on the quantity of matter (amount of mass) present in the system is known as
Intensive Property.
Some examples of intensive properties are pressure, temperature, density, and concentration. Ifthe overall temperature of
a glass of water (our system) is 20ºC, then any drop of water in that glasshas a temperature of 20ºC. Similarly, if the
concentration of salt, NaCl, in the glass of water is0.1 mole/litre, then any drop of water from the glass also has a salt
concentration of 0.1 mole/litre.
Extensive Properties:
A property that does depend on the quantity of matter (amount of mass) present in the system is called an Extensive
Property.
Some examples of extensive properties are volume, number of moles, enthalpy, and Gibbs’ free energy.
By definition, the extensive properties are additive while intensive properties are not. Let usconsider the system ‘a
glass of water’. If we double the mass of water, the volume is doubled and soare the number of moles and the internal
energy of the system.
Intensive properties Extensive properties
Temperature Surface tension Mass
Pressure Refractive index Volume
Density Viscosity Internal energy
Boiling point Freezing point, Enthalpy

Thermodynamic Equilibrium and non–equilibrium states:

A system in which the state variables have constant values throughout the system is said to bein a state of
thermodynamic equilibrium.
 3

Suppose we have a gas confined in a cylinder that has a frictionless piston. If the piston isstationary, the state of
the gas can be specified by giving the values of pressure and volume. Thesystem is then in a state of equilibrium.
A system in which the state variables have different values in different parts of the system issaid to be in a
non-equilibrium state.
If the gas contained in a cylinder, as stated above, is compressed very rapidly by moving downthe piston, it passes
through states in which pressure and temperature cannot be specified, sincethese properties vary throughout the gas. The
gas near the piston is compressed and heated andthat at the far end of the cylinder is not. The gas then would be said to be
in non-equilibrium state.
Thermodynamics is concerned only with equilibrium states.
Thermodynamic processes:
When a thermodynamic system changes from one state to another, the operation is called aProcess. These
processes involve the change of conditions (temperature, pressure and volume).The various types of thermodynamic
processes are:
(1) Isothermal Processes: Those processes, in which the temperature remains fixed, are termed isothermal
processes.This is often achieved by placing the system in a thermostat (a constant temperature bath).
For an isothermal process dT = 0
(2) Adiabatic Processes: Those processes in which no heat can flow into or out of the system are called
adiabaticprocesses. Adiabatic conditions can be approached by carrying the process in an insulated containersuch
as ‘thermos’ bottle. High vacuum and highly polished surfaces help to achieve thermalinsulation.
For an adiabatic process dq= 0
(3) Isobaric Processes: Those processes which take place at constant pressure are called isobaric
processes.Forexample, heating of water to its boiling point and its vaporization take place at the same
atmosphericpressure. These changes are, therefore, designated as isobaric processes and are said to take
placeisobarically.
For an isobaric process dp= 0
(4) Isochoric Processes: Those processes in which the volume remains constant are known as isochoric
processes.Theheating of a substance in a non-expanding chamber is an example of isochoric process.
For isochoric processes dV= 0.
(5) Cyclic Process: When a system in a given state goes through a number of different processes and finallyreturns to
its initial state, the overall process is called a cycle or cyclic process.
For a cyclic process dE= 0, dH= 0.
Reversible and irreversible processes:
A thermodynamic reverse process is one that takes place infinitesimally slowly and its directionat any point
can be reversed by an infinitesimal change in the state of the system.
 4

In fact, a reversible process is considered to proceed from the initial state to the final statethrough an infinite
series of infinitesimally small stages. At the initial, final and all intermediatestages, the system is in equilibrium state. This
is so because an infinitesimal change in the state ofthe system at each intermediate step is negligible.
When a process goes from the initial to the final state in a single step and cannot be carried inthe reverse
order, is known an irreversible process. Here the system is in equilibrium state inthe beginning and at the end, but not
at points in between.
Reversible Process Irreversible Process
1 It takes place in infinite number of infinitesimally small It takes finite timefor completion.
steps and it wouldtake infinite time to occur.
2 It is imaginary as it assumes the presenceof frictionless It is real and can be performed actually.
and weightless piston.
3 It is in equilibrium state at all stages of theoperation. It is in equilibrium state only at the initialand final
stages of the operation.
4 All changes are reversed when the processis carried out in After this type of process has occurredall changes do
reversible direction. not returnto the initialstate by them.
5 It is extremely slow. It proceeds at measureable speed.
6 Work done by a reversible process isgreater than the Work done by an irreversible process issmaller than
corresponding irreversible process. the corresponding reversible process.
Nature of heat and work:
When a change in the state of a system occurs, energy is transferred to or from the surroundings. This energy may
be transferred as heat or mechanical work.
Heat: Heat is the process of energy transfer as a result of a temperature difference between the system and its
surroundings.
Walls that permit heating as a mode of transfer of energy are called diathermic. A metal container is diathermic.
Walls that do not permit heating even though there is a difference in temperature are called adiabatic (from the
Greek words for ‘not passing through’). The double walls of a vacuum flask are adiabatic to a good approximation.
Units of Heat: The unit of heat, which was used for many years, is calorie (cal). A calorie is defined as the quantity of
heat required to raise the temperature of 1 gram of water by 1º C in the vicinity of 15ºC. Since heat and work are
interrelated, SI unit of heat is the joule (J).
1 joule = 0.2390 calories; 1 calorie = 4.184 J; or 1 kcal = 4.184 kJ
Pressure–Volume Work:
In physics, mechanical work is defined as force multiplied by the distance through which theforce acts. In
elementary thermodynamics the only type of work generally considered is the workdone in expansion (or compression) of
a gas. This is known as pressure-volume work or PV work or expansion work.
 5

Consider a gas contained in a cylinder fitted with a frictionless piston. The pressure (force perunit area) of the gas,
P, exerts a force on the piston. This can be balanced by applying an equal butopposite pressure from outside on the piston.
Let it be designated as Pext. It is important to rememberthat it is the external pressure, Pext., and not the internal pressure of
the gas itself which is used inevaluating work.This is true whether it be expansion or contraction.If the gas expands at
constant pressure, the piston would move, say through a distance l.
Weknow that work = force × distance (by definition)
W= f × l ……………………..(1)
Since pressure is force per unit area,
f = Pext× A ……………………(2)
where A is the cross-section area of the piston.
From (1) and (2), we haveW = Pext × A × l
= Pext × ΔV
(Area x distance = Volume)
During the process volume of the gas changes from initial
volume V1 and to final volume V2.
𝑽𝟐

∴𝑾= 𝑷𝒅𝑽
𝑽𝟏

𝑾 = 𝑷(𝑽𝟐 − 𝑽𝟏 )
𝑾 = 𝑷∆𝑽
When work is done by the system W is +ve., i.e., V2>V1. ΔV is
positive, expansion takes place.
When work in done on the system by surroundings W is –ve. i.e., Figure. 1. Pressure volume work of a
system (gas) confined by a
V2<V1, compression takes place. frictionless piston.

It may be noted that the work done by a system is not a state

function. This is true of themechanical work of expansion. We shall showpresently that the work is related to the
processcarried out rather than to the internal and finalstates. This will be evident from a considerationof the reversible
expansion and an irreversibleprocess.
Units of Work
In CGS system the unit of work is erg which is defined as the work done when a resistance of 1 dyne is moved through a
distance of 1 centimeter. Since the erg is so small, a bigger unit, the joule (J) is now used.
1 joule = 107ergs or 1 erg = 10–7 J. We often use kilojoule (kJ) for large quantities of work; 1 kJ = 1000 J
Internal Energy (E):
Internal energy is the heat content of the system measured at constant volume and temperature.
It is defined as sum of all energies possessed by the system.
E = K.E + P.E
 6

K. E= Translational energy + rotational energy + Vibrational energy + Electronic energy

P.E = Intermolecular attractions + Interatomic attractions + attraction between Electrons and the nucleus
Internal energy is an extensive property and a state function. Absolute values of it cannot be calculated. Since it is
difficult to calculate translational and rotational energies. However, change in internal energy (ΔE) can be calculated
First Law of Thermodynamics: Statements:
(1) The energy can be neither created nor destroyed, although it is converted from one form to another.
(2) The total energy of an isolated system or universe remains constant.
(3) Whenever a quantity of energy of a particular type disappears equivalent amount of another type must be
produced.
(4) Total energy of system and surroundings remains constant (or conserved)
(5) It is impossible to construct a perpetual motion machine that can produce work without spending energy on it.
When a system is changed from state A to state B, it undergoes a change in the internal energy from EA to EB. Thus, we
can write
ΔE = EB – EA
This energy change is brought about by the evolution or absorption of heat and/or by work being done by the system.
Because the total energy of the system must remain constant, we can write the mathematical statement of the First Law as:
ΔE = q – w
where q = the amount of heat supplied to the system, w = work done by the system
Some Special Forms of First Law of Thermodynamics: Mathematical statement of the First law of Thermodynamics is
ΔE = q – w
Case 1:For a cyclic process involving isothermal expansion of an ideal gas
ΔE = 0∴q = w
Case 2:For an isochoric process (no change in volume) there is no work of expansion i.e. w = 0. Hence
ΔE = qv
Case 3:For an adiabatic process there is no change in heat gained or lost i.e. q = 0. Hence
ΔE = – w
In other words, the decrease in internal energy is exactly equal to the work done on the system by surroundings.
Case 4:For an isobaric process there is no change in pressure, i.e. P remains constant. Hence
ΔE = q – w or ΔE = q – PΔV
Limitations of First law:
Although the first law of thermodynamics is exact, but has certain limitations.
1) According to 1st law of thermodynamics energy of one form can be converted to another form but total energy
always remains constant but 1st law does not indicate whether a given process is spontaneous or not and if so in
which direction.
 7

2) First law does not account whether heat can flow from colder body to hotter body, whether gas can diffuse from
low to high pressure. All that 1st law is heat energy gained by one end is exactly equal to heat energy lost by the
other end.
3) According to 1st law, energy of one form should be converted into exactly equivalent amount of other form of
energy. Although various forms of energy are converted into one another, it is observed that no heat engine can
convert all the heat absorbed into exactly equivalent amount of work without any loss.
These above limitations of 1st law were explained on the basis of 2nd law of thermodynamics.
Second law of thermodynamics: Some of statements of 2nd law is,
1) All spontaneous processesare thermodynamically irreversible.
2) Without the help of external work heat cannot flow on its own from a colder to a hotter body.
3) It is impossible for any heat engine to convert all the heat absorbed into equivalent work without producing
changes elsewhere.
One of the statements of 2nd law given by Kelvin, states that;
“It is impossible for a cyclic process to take heat from a hotter reservoir and convert it into an equivalent work
without transferring a part of heat to a colder reservoir.”
This statement recognizes the fact that no heat engine is 100% efficient.
Statement for 2nd law given by Clausius:
“It is impossible for any cyclic process to transfer heat from a system at lower to a system at a higher
temperature without applying some work.”
This statement recognizes the fact that heat flows spontaneously.
Entropy:
Definition of entropy:
Entropy is a thermodynamic state quantity that is a measure of the randomness or disorder of the system.
Entropy is a measure of disorderness or randomness of a system. More is the disorder of the system; greater will
be its entropy. An increase in disorderness during a physical or chemical process indicates increase of entropy.
Consider a molecular system existing in two states A and B. In the state A the molecules are regularly arranged in
an orderly fashion and its entropy is low.
While in state B the molecules are randomly arranged and its entropy is high.
 8

Figure 6(a) State A is highly ordered, low entropy and less probable;
(b) State B is highly disordered high entropy and more probable.
Change of state A (regular arrangement) to state B (disorder) leads to increase of entropy.
According to law of probability state A is less probable than state B. As a result of state A changing to state B is
spontaneous.
On this basis it can be stated that “any change which can be accompanied by increase of entropy tends to be
spontaneous”.
Units of Entropy:Since entropy is equal to heat energy divided by absolute temperature, therefore it is measured in
entropy units (eu) which are Cal.deg-1.mol-1. (Or) Cal.K-1.mol-1.
In the SI system, the units are J.mol-1.deg-1. (Or) J.mol-1.K-1., these are represented by eu.
Entropy change for a reversible process:
A reversible process is the one, when heat is absorbed by the system reversibly and at the same time heat is lost
by the surroundings also reversibly.
In a reversible process
𝑄
∆𝑆 =
𝑇
𝑄
∆𝑆 =−
𝑇
Net change of entropy
𝑄 𝑄
∆𝑆 + ∆𝑆 = − =0
𝑇 𝑇
∴ ∆𝑆 + ∆𝑆 =0
For a thermodynamically reversible process, the net entropy changes of the combined system and surroundings
taken together are zero.
Entropy change for an irreversible process:
If any small part of a reversible process is carried out rapidly then the entire process becomes irreversible.
Even in such irreversible process, ΔS of the system will not depend upon the actual heat absorbed but it depends
upon heat absorbed reversibly.
 9

𝑸𝒓𝒆𝒗
∆𝑺𝒔𝒚𝒔 =
𝑻
If –Qirr is the heat lost by the surroundings at temperature T, then ΔS of the surroundings in an irreversible process is
given as
𝑸𝒊𝒓𝒓
∆𝑺𝒔𝒖𝒓𝒓 = −
𝑻

Net change of entropy

𝑸𝒓𝒆𝒘 𝑸𝒊𝒓𝒓
∆𝑺𝒔𝒚𝒔 + ∆𝑺𝒔𝒖𝒓𝒓 = −
𝑻 𝑻
It is known that the work done a reversible process is greater than irreversible.
𝑾𝒓𝒆𝒗 > 𝑾𝒊𝒓𝒓𝒆𝒗
According to first law of thermodynamics
𝒘∝𝑸
𝑸𝒓𝒆𝒗 > 𝑸𝒊𝒓𝒓
𝑸𝒓𝒆𝒘 𝑸𝒊𝒓𝒓
− >0
𝑻 𝑻
∴ ∆𝑺𝒔𝒚𝒔 + ∆𝑺𝒔𝒖𝒓𝒓 > 0
For a thermodynamically irreversible process, the net entropy change for the combined system and
surroundings together always greater than zero.For an irreversible process, the total entropy always increases.
The combined equation for entropy change is,
∆𝑺𝒔𝒚𝒔 + ∆𝑺𝒔𝒖𝒓𝒓 ≥ 𝟎
∆𝑺𝒔𝒚𝒔 + ∆𝑺𝒔𝒖𝒓𝒓 = 𝟎 (𝒇𝒐𝒓 𝒓𝒆𝒗𝒆𝒓𝒔𝒊𝒃𝒍𝒆 𝒑𝒓𝒐𝒄𝒆𝒔𝒔)
∆𝑺𝒔𝒚𝒔 + ∆𝑺𝒔𝒖𝒓𝒓 > 0 (𝑓𝑜𝑟 𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠)
Based on this another statement for second law given as “All spontaneous processes are accomplished by increase of
entropy”.
Physical significance of Entropy:
Entropy is a measure of disorder or randomness of a system. The entropy of the system increases if it goes from
more orderly state to less orderly state and vice–versa. This concept of entropy has led to the conclusion that all
substances in their normal crystalline state at absolute zero would be the most ordered state with zero entropy. At this
state, all motion ceases. In case of a perfect crystal the entropy is zero. This is third law of Thermodynamics
Entropy change in Universe:
Most of the processes occurring in nature are spontaneous and irreversible due to which the entropy of the
universe is continuously increasing.
The essentials of first law and second law of thermodynamics were combined by Clasius and stated as “energy of
the universe remains constant but entropy of the universe is continuously increasing and it tends to maximum”.
Entropy change-Phase change:
 10

Change of phase occurs during the following processes:

1) When solid melts to liquid or when liquid freezes to solid
2) When liquid evaporates to vapour or when vapour condenses to liquid.
Temperature remains constant as long as phase changes completely. Phase change occurs at constant temperature.
The heat evolved or absorbed during phase change at constant temperature is called latent heat (ΔHL)
Entropy change (ΔS) for any process is
∆𝑯𝑳
∆𝑺 =
𝑻
Entropy changes for melting
∆𝑯𝑳𝒎
∆𝑺𝒎 =
𝑻
Entropy change for vapourisation
∆𝑯𝑳𝑽
∆𝑺𝑽 =
𝑻
The process of melting and vapourization involve absorption of heat. They show increase in entropy and hence
ΔS for these processes is +ve.
The process of freezing and condensation involve evolution of heat, therefore they show decrease of entropy and
hence ΔS is –ve.
Gibbs free energy function (G):
 The amount of energy available to do useful work is known as Gibbs free energy.
 All spontaneous reactions are unidirectional and proceed in the direction where ΔG is negative.
 During a physical or chemical process spontaneous nature is decided by useful form of work. [except mechanical
work i.e. expansion or compression]
 Greater the amount of useful work more will be the decrease in ΔG and the process will be more spontaneous.

Gibbs free energyfunction G is expressed as G = H – TS …………………..(1)

Enthalpy (H), Entropy (S) are state functions, therefore function G is also a state function.
On applying initial and final states to equation (1), we get
G1 = H1–TS1 and G2 = H2 – TS2
The change in the free energy (ΔG) on moving from initial state to final state under isothermal conditions
ΔG = G2 – G1
On substituting above equations
ΔG = (H2 –TS2) – (H1 – TS1)
ΔG = ΔH – TΔS……………………..(2)
From definition of entropy TΔS = Qrev …………………………….i
From definition of enthalpy ΔH = ΔE + PdV…………………….ii
Substituting equations i and ii in equation (2)
 11

ΔG = ΔE + PdV – Qrev…………….(3)
From the first law of thermodynamics ΔE =Q – W
Applying this equation to a reversible process, we get
ΔE = Qrev – Wmax
ΔE – Qrev = −Wmax……………iii
Substituting equation (iii) in equation (3) ΔG = -Wmax + PdV
−ΔG = Wmax – PdV
−ΔG = Net Work.
For a process carried out at constant pressure, the decrease of function (G) gives the maximum work obtained
from system other than pressure-volume work (PV work).
In other words, the decrease of function (G) gives the network obtained from the system which can be electrical
work (or) chemical work.
Variation of free energy (G) with temperature (T) and pressure (P)
By definition of free energy function (G)
G = H – TS………………(1)
By definition of enthalpy the equation (1) can be written as
G = E + PV – TS………….(2)
On complete differentiation
dG = dE + PdV + VdP – TdS – SdT……………(3)
For an infinitesimal change in a reversible process, entropy change is given as

𝑸𝒓𝒆𝒗
𝒅𝑺 =
𝑻
From first law of thermodynamics
𝜹𝑸𝒓𝒆𝒗 = 𝒅𝑬 + 𝑷𝒅𝑽 (∵ 𝒅𝑬 = 𝜹𝑸 − 𝑷𝒅𝑽)
𝒅𝑬 + 𝑷𝒅𝑽
∴ 𝒅𝑺 =
𝑻
𝑻𝒅𝑺 = 𝒅𝑬 + 𝑷𝒅𝑽
On substituting the above equation in equation (3)
𝒅𝑮 = 𝒅𝑬 + 𝑷𝒅𝑽 + 𝑽𝒅𝑷 − (𝒅𝑬 + 𝑷𝒅𝑽) − 𝑺𝒅𝑻
∴ 𝒅𝑮 = 𝑽𝒅𝑷 − 𝑺𝒅𝑻 ⋯ ⋯ ⋯ ⋯ (𝐢)
The above equation gives the change of free energy with pressure and with temperature.
𝒅𝑮 = 𝑽𝒅𝑷 − 𝑺𝒅𝑻
At constant temperature, dT = 0
(dG)T = VdP
𝒅𝑮
= 𝑽 ⋯ ⋯ ⋯ ⋯ (𝐢𝐢)
𝒅𝑷 𝑻
 12

Equation II represents the change of free energy change with pressure at constant temperature.
𝒅𝑮 = 𝑽𝒅𝑷 − 𝑺𝒅𝑻
At constant pressure dP = 0
(dG)P = − SdT
𝒅𝑮
= −𝑺 ⋯ ⋯ ⋯ ⋯ ⋯ (𝐢𝐢𝐢)
𝒅𝑻 𝑷

Equation gives variation of free energy with temperature at constant pressure.

For an isothermal process, the change in free energy with pressure can be determined as follows.
Let G1 and G2 are quantities of free energy in initial state and final state. Let quantities of pressure by P 1 and P2 in
initial and final states.
Under isothermal conditions
(dG)T = VdP
On integration of above equation within G1 to G2 and P1 to P2
𝑮𝟐 𝑷𝟐

𝒅𝑮 = 𝑽𝒅𝑷
𝑮𝟏 𝑷𝟏

From ideal gas equation PV = nRT

𝒏𝑹𝑻
𝑽=
𝑷
𝑷𝟐
𝒏𝑹𝑻
𝑮𝟐 − 𝑮𝟏 = 𝒅𝑷
𝑷
𝑷𝟏

n, R, T are constants 𝑷𝟐
(∆𝑮)𝑻 = 𝒏𝑹𝑻 𝐥𝐧 ⋯ ⋯ ⋯ ⋯ ⋯ (𝑰)
𝑷𝟏

P1V1 = P2V2
𝑷𝟐 𝑽𝟏
=
𝑷𝟏 𝑽𝟐
𝑽𝟏
(∆𝑮)𝑻 = 𝒏𝑹𝑻 𝐥𝐧 ⋯ ⋯ ⋯ ⋯ ⋯ (𝑰𝑰)
𝑽𝟐

Equation I and II give the change of free energy with pressure at constant temperature for a finite process.
Gibbs-Helmholtz equation:
𝑮 = 𝑯 − 𝑻𝑺 ⋯ ⋯ ⋯ ⋯ ⋯ ⋯ (𝐢)
𝑮 = 𝑬 + 𝑷𝑽 − 𝑻𝑺 ⋯ ⋯ ⋯ ⋯ ⋯ (𝐢𝐢)
On complete differentiation
𝒅𝑮 = 𝒅𝑬 + 𝑷𝒅𝑽 + 𝑽𝒅𝑷 − 𝑻𝒅𝑺 − 𝑺𝒅𝑻 ⋯ ⋯ ⋯ (𝐢𝐢𝐢)
 13

But we know from first law

𝒅𝑸 = 𝒅𝑬 + 𝑷𝒅𝑽 ⋯ ⋯ ⋯ (𝒊𝒗))
From equations (iii) and (iv)
𝒅𝑮 = 𝒅𝑸 + 𝑽𝒅𝑷 − 𝑻𝒅𝑺 − 𝑺𝒅𝑻 ⋯ ⋯ ⋯ (𝐯)
From the entropy definition we know that
𝒅𝑸
𝒅𝑺 =
𝑻
𝑻𝒅𝑺 = 𝒅𝑸
Substituting the TdS value in equation (v)
𝒅𝑮 = 𝒅𝑸 + 𝑽𝒅𝑷 − 𝒅𝑸 − 𝑺𝒅𝑻 ⋯ ⋯ ⋯ (𝐯𝐢)
𝒅𝑮 = 𝑽𝒅𝑷 − 𝑺𝒅𝑻 ⋯ ⋯ ⋯ (𝐯𝐢𝐢)
At constant pressure dp=0, then
(𝒅𝑮)𝑷 = −𝑺𝒅𝑻
𝒅𝑮
= −𝑺
𝒅𝑻 𝑷

Where dG and dT represent the infinitesimally small changes in free energy and temperature respectively. The above
equation for the initial and final states can be written as below
𝒅𝑮𝟏
= −𝑺𝟏 ⋯ ⋯ ⋯ ⋯ (𝐯𝐢𝐢𝐢) 𝒇𝒐𝒓 𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝒔𝒕𝒂𝒕𝒆
𝒅𝑻 𝑷
𝒅𝑮𝟐
= −𝑺𝟐 ⋯ ⋯ ⋯ ⋯ (𝐢𝐱) 𝒇𝒐𝒓 𝒇𝒊𝒏𝒂𝒍 𝒔𝒕𝒂𝒕𝒆
𝒅𝑻 𝑷

Subtracting the equation viii for ix

𝒅𝑮𝟐 𝒅𝑮𝟏
− = −(𝑺𝟐 − 𝑺𝟏 )
𝒅𝑻 𝒑 𝒅𝑻 𝒑

𝝏(∆𝑮)
= −∆𝑺 ⋯ ⋯ ⋯ (𝐱)
𝒅𝑻 𝑷

Let G1, H1, and S1 be the free energy, enthalpy and entropy of the system in the initial state and G2, H2 and S2 are
the corresponding values in the final state brought about isothermally at temperature T. Thus
∆𝑮 = ∆𝑯 − 𝑻∆𝑺 ⋯ ⋯ ⋯ (𝐱𝐢)
Substituting the ΔG value form equation (x) in equation in (xi)

𝝏(∆𝑮)
∆𝑮 = ∆𝑯 + 𝑻 ⋯ ⋯ ⋯ (𝐱𝐢𝐢)
𝒅𝑻 𝑷

The above equation is the common form of Gibbs-Helmholtz equation. It is applicable to all processes occurring
at constant pressure.
Applications of Gibbs-Helmholtz equation:
1) The most important application of the equation is in the study of galvanic cells (or electrochemical cells).
 14

When a redox reaction, e.g., Zn + H2SO4 ZnSO4 + H2, is allowed to take place in a single beaker,
heat is evolved. Earlier it was believed that when the same reaction is allowed to take in an electrochemical cell, the
electrical energy produced was equivalent to heat evolved. However, later on it was not found to be correct in all cases.
According to Gibbs-Helmholtz the electrical energy produced was equal to the decrease in the free energy
accompanying the cell reaction. If n is the number of electrons given out by one of the electrodes (e.g., Zn in the present
case) or taken up by the other electrode. Then,
Quantity of electricity produced = nF
Let, E.M.F. of the cell = E
Decrease in free energy, ΔG = –nFE
Substituting the value of ΔG in equation (xii), we get
𝝏(∆𝑮)
∆𝑮 = ∆𝑯 + 𝑻 ⋯ ⋯ ⋯ (𝐱𝐢𝐢)
𝝏𝑻 𝑷
𝝏(−𝒏𝑭𝑬)
−𝒏𝑭𝑬 = ∆𝑯 + 𝑻 ⋯ ⋯ ⋯ (𝐱𝐢𝐢)
𝝏𝑻 𝑷
𝝏𝑬
𝒏𝑭𝑬 = −∆𝑯 + 𝑻𝒏𝑭 ⋯ ⋯ ⋯ (𝐱𝐢𝐢)
𝝏𝑻 𝑷

Thus knowing the temperature coefficient of the EMF of the cell i.e., (∂E/∂T) P, change in enthalpy can be
calculated if EMF (i.e., E) of the cell is known or vice-versa.
Evidently, the electrical energy produced (nFE) is equal to heat evolved (–ΔH) only when temperature coefficient
of the EMF of the cell, i.e., (∂E/∂T)P is zero.
2) The Gibbs-Helmholtz equation is useful in predicting the feasibility of the process.
Criteria for feasibility (Spontaneous) of a Process:
We observed that the net entropy change for the combined system and the surroundings can be taken as criteria
for the feasibility of spontaneity of a process.
If there is a net increase in the entropy of the system and the surroundings taken together
dSsystem + dSsurroundings> 0
the process would proceed irreversibly. i.e., it would be thermodynamically feasible
If the there is no net change in the entropy of the system and the surroundings taken together
dSsystem + dSsurroundings = 0
the process will be reversible. i.e., it will remain in a state of equilibrium and hence not possible.
However, the criterion of entropy change is not convenient as it requires the knowledge of entropy change of the
system as well as that of surroundings. Hence, other thermodynamic quantities are preferred for knowing the criteria of
feasibility of a process because in these quantities, knowledge of change of that particular thermodynamic quantity of only
system is sufficient. These quantities are energy, enthalpy, work function and free energy.
The entropy change criteria for the feasibility of an infinitesimal process, can be written as below
dSsystem + dSsurroundings ≥ 0 ………..(1)
 15

If we assume the change in surroundings as reversible and surroundings evolve dq heat reversibly, at Temperature T
Then
𝒅𝑸
𝒅𝑺𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈 = − ⋯ ⋯ ⋯ (𝟐)
𝑻
From the first law of Thermodynamics
𝒅𝑸𝒓𝒆𝒗 = 𝒅𝑬 + 𝑷𝒅𝑽 ⋯ ⋯ ⋯ ⋯ (𝟑)
Substituting the value of dQrev in equation (ii)
𝒅𝑸 (𝒅𝑬 + 𝑷𝒅𝑽)
𝒅𝑺𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈 = − =− ⋯ ⋯ ⋯ (𝟒)
𝑻 𝑻
From equation (1) we get dSsystem + dSsurroundings ≥ 0 ………..(1)
(𝒅𝑬 + 𝑷𝒅𝑽)
𝒅𝑺𝒔𝒚𝒔𝒕 − ≥𝟎
𝑻
𝑻𝒅𝑺 ≥ 𝒅𝑬 + 𝑷𝒅𝑽 ⋯ ⋯ ⋯ ⋯ (𝟓)
Note: The subscript ‘system’ has been omitted from dS for the sake of convenience.
In equation (5) the sign ‘>’ (greater than) stands for the irreversible process, while the sign ‘=’ (equal to) stands
for reversible process.
The equation (5) is the basic equation which leads to a number of criteria for predicting the feasibility of a
process.
1) Criterion in terms of change of entropy of the system:
If when E and V are constant, the dE= 0 and dV= 0 the equation (iii) reduces to
(dS)E,V≥ 0…………………..(6)
or (dS)(E,V)> 0 for an irreversible change and the process is feasible
and (dS)(E,V)= 0 for a reversible change (equilibrium)
2) Criterion in terms of change of internal energy of the system:
When S and V are constant, Then dS= 0 and dV= 0
The equation (iii) reduces to
(dE)S,V≤ 0………………………….(7)
or (dE)S,V< 0for an irreversible change and the process is feasible
and (dE)S,V= 0for a reversible change (equilibrium)
3) Criterion in terms of free energy change of the system:
By definition, the free energy (G) of a system is given by the following expression
G = H -TS
Or G = E + PV -TS [∵H = E + PV]
on differentiating we get
dG= dE+ PdV+ VdP-TdS-SdT
dE+PdV= dG+ VdP- TdS– SdT
Substituting in equations (iii) we get
 16

𝑻𝒅𝑺 ≥ 𝒅𝑬 + 𝑷𝒅𝑽
𝑻𝒅𝑺 ≥ 𝒅𝑮 + 𝑽𝒅𝑷 − 𝑻𝒅𝑺– 𝑺𝒅𝑻
or dG– VdP+ SdT≤ 0
At constant pressure in an isothermal process (T is also constant) this equation reduces to
(dG)P,T≤ 0……………………….(8)
or (dG)P,T< 0 for an irreversible change and the process is feasible
and (dG)P,T= 0 for a reversible change (equilibrium)
The equation (8) leads to the following conclusion.
If a process under constant conditions of temperature and pressure is accompanied by decrease in free energy (i.e.,
ΔG has a negative value), the process is irreversible; While if it occurs without change in free energy (i.e., ΔG=0), it is
said to be reversible and if it occurs an increase in free energy (i.e., ΔG has a positive value), it is not feasible.
The criterion in terms of free energy change is the most useful criterion to decide between reversibility and
irreversibility of a process because most of the processes take place at constant temperature and pressure.
 1

ELECTRO CHEMISTRY
ELECTROCHEMICAL CELLS:
A device for producing an electrical current from a chemical reaction (spontaneous redox
reaction) is called an electrochemical cell and also known as a galvanic cell or Voltaic cell. A simple
voltaic cell is shown in Fig.1. Here the spontaneous reaction of zinc metal with an aqueous solution of
copper sulphate is used.
Zn(s) + Cu2+ Zn2+ + Cu
A bar of zinc metal (anode) is placed in zinc sulphate solution (where oxidation takes place) in
the left container. A bar of copper metal
(cathode) is immersed in copper sulphate
solution (where reduction takes place) in
the right container. In other words, each
electrode may be regarded as a half-cell.
The zinc and copper electrodes are joined
by a copper wire. A salt bridge containing
potassium sulphate solution interconnects
the solutions in the anode compartment
and the cathode compartment.
The oxidation half-reaction occurs in the
anode compartment. Fig. 1 A simple voltaic (galvanic) cell.
Zn(s) Zn2+(aq) + 2e–
The reduction half-reaction takes place in the cathode compartment.
Cu2+(aq) + 2e– Cu(s)
The cell reaction: Zn(s) + Cu+2(aq) Zn+2(aq) + Cu(s)
When the cell is set up, electrons flow from zinc electrode through the wire to the copper
cathode. As a result, zinc dissolves in the anode solution to form Zn 2+ ions. The Cu2+ ions in the cathode
half-cell pick up electrons and are converted to Cu atoms on the cathode. At the same time, SO 42– ions
from the cathode half-cell migrate to the anode half-cell through the salt bridge. Likewise, Zn 2+ ions
from the anode half-cell move into the cathode half-cell. This flow of ions from one half-cell to the other
completes the electrical circuit which ensures continuous supply of current. The cell will operate till either
the zinc metal or copper ion is completely used up.
CELL TERMINOLOGY:
Before taking up the study of the electrochemical cells, we should be familiar with a few common
terms.
Current is the flow of electrons through a wire or any conductor.
Electrode: a metallic rod/bar/strip which conducts electrons into and out of a solution.
Anode is the electrode at which oxidation occurs. It sends electrons into the outer circuit. It has negative
charge and is shown as (–) in cell diagrams.
 2

Cathode is the electrode at which electrons are received (reduction occurs) from the outer circuit. It
has a positive charge and is shown as (+) in cell diagrams.
Electrolyte is the salt solutions in a cell.
Anode compartment is the compartment of the cell in which oxidation half-reaction occurs. It contains
the anode.
Cathode compartment is the compartment of the cell in which reduction half-reaction occurs. It
contains the cathode.
Half-cell. Each half of an electrochemical cell, where oxidation occurs and the half where reduction
occurs, is called the half cell.
Salt bridge: A salt bridge is a U-shaped device containing concentrated solution of an inert electrolyte
like KCl, KNO3, etc. or a solidified solution of those electrolytes in agar-agar solution and gelatin to
prevent intermixing of the solutions. It connects the oxidation and reduction half-cells of a galvanic cell.
The inert electrolytes present do not take part in redox reaction of the cell and don’t react with the
electrolyte that has been used.
Cell diagram or Representation of a Cell
A cell diagram is an abbreviated symbolic depiction of an electrochemical cell. For this purpose,
we will consider that a cell consists of two half-cells. Each half-cell is again made of a metal electrode
contact with metal ions in solution.
IUPAC Conventions: In 1953 IUPAC recommended the following conventions for writing cell diagrams.
We will illustrate these with reference to Zinc-Copper cell.
(1) A single vertical line (|) represents a phase boundary between metal electrode and ion
solution (electrolyte). Thus, the two half-cells in a voltaic cell are indicated as

Phase boundary

Zn | Zn2+ Cu2+ | Cu
Anode Half-Cell Cathode Half-Cell
It may be noted that the metal electrode in anode half-cell is on the left, while in cathode half- cell it
is on the right of the metal ion.
(2) A double vertical line (||) represents the salt bridge, porous partition or any other means of
permitting ion flow while preventing the electrolyte from mixing.
(3) Anode half-cell is written on the left and cathode half-cell on the right.
(4) In the complete cell diagram, the two half-cells are separated by a double vertical line
(salt bridge) in between. The zinc-copper cell can now be written as
Salt Bridge
Zn | Zn2+ || Cu2+ | Cu
Anode Cathode
Half-cell Half-cell
 3

(5) The symbol for an inert electrode, like the platinum electrode is often enclosed in a bracket. For
example,

The value of emf of a cell is written on the right of the cell diagram. Thus, a zinc-copper cell has emf
1.1V and is represented as

Electromotive force (emf) or Cell potential: In a Zn-Cu voltaic cell, electrons are released at the
anode and it becomes negatively charged. The negative electrode pushes electrons through the external
circuit by electrical repulsions. The copper electrode gets positive charge due to the discharge of Cu 2+
ions on it. Thus, electrons from the outer circuit are attracted into this electrode. The flow of current
through the circuit is determined by the ‘push’, of electrons at the anode and ‘attraction’ of electrons at
the cathode. These two forces constitute the ‘driving force’ or ‘electrical pressure’ that sends electrons
through the circuit. This driving force is called the electromotive force (abbreviated emf) or cell
potential. The emf of cell potential is measured in units of volts (V) and is also referred to as cell
voltage.
The magnitude of the emf of a cell reflects the tendency of electrons to flow externally from one
electrode to another. The electrons are transported through the cell solution by ions present and pass
from the positive electrode (Cu in case of Daniel cell) to the negative electrode. This corresponds to a
clockwise flow of electrons through the external circuit. Thus, the emf of the cell is given the +ve sign.
If the emf acts in the opposite direction through the cell circuit, it is quoted as –ve value. For example,
Daniel cell has an emf of 1.1V and the copper electrode is positive. This can be expressed in two ways:
Zn | ZnSO4 || CuSO4 | Cu E = + 1.1 V
Cu | CuSO4 || ZnSO4 | Zn E = – 1.1 V
The negative sign indicates that the cell is not feasible in the given direction. The reaction will
take place in the reverse direction.
Calculating the emf of a cell:
The electromotive force may be defined as the potential difference between two
electrodes of a galvanic cell or voltaic cell. Or
The difference of potential, which causes the current to flow from an electrode at higher
potential to the one of lower potential, is called the Electro motive force (emf) of the cell.
Mathematically, emf of an electrochemical cell is the algebraic sum of the single electrode
potential; provided proper signs are being given according to the actual reaction taking place on the
electrodes.
The emf of a cell can be calculated from the half-cell potentials of the two cells (anode and
cathode) by using the following formula
Ecell = Ecathode – Eanode
 4

= ER – EL (IUPAC convention 3)
Where ER and EL are the reduction potentials of the right-hand and left-hand electrodes respectively.
Standard emf of a cell:
The emf generated by an electrochemical cell is given by the symbol E. It can be measured with
the help of a potentiometer. The value of emf varies with the concentration of the reactants and products
in the cell solutions and the temperature of the cell. When the emf of a cell is determined under standard
conditions, it is called the standard emf. The standard conditions are (a) 1 M solutions of reactants
and products; and (b) temperature of 25°C. Thus, standard emf may be defined as: the emf of a cell
with 1 M solutions of reactants and products in solution measured at 25°C. Standard emf of a
cell is represented by the symbol E°. With gases 1 atm pressure is a standard condition instead of
concentration. For a simple Zn-Cu voltaic cell, the standard emf, E°, is 1.10 V. This means that the emf
of the cell operated with [Cu2+] and [Zn2+] both at 1 M and at 25°C is 1.10 V. That is,
Zn | Zn2+(aq, 1M) || Cu2+(aq,1M ) | Cu E = + 1.1 V
Single electrode potential:
An electrochemical cell consists of two half-cells. With an open-circuit, the metal electrode in
each half-cell transfers its ions into solution. Thus, an individual electrode develops a potential with
respect to the solution. The potential of a single electrode in a half-cell is called the Single electrode
potential. Thus, in a Daniel cell in which the electrodes are not connected externally, the anode Zn/Zn2+
develops a negative charge and the cathode Cu/Cu 2+, a positive charge. The amount of the charge
produced on individual electrode determines its single electrode potential. The single electrode potential
of a half-cell depends on: (a) concentration of ions in solution; (b) tendency to form ions; and (c)
temperature.
The tendency of an electrode to lose or gain electrons, when it is in contact with the solution of
its own ions. The metal which has a greater tendency to lose electrons becomes the anode, while which
has a greater tendency to gain electrons will behave as cathode.
It may be noted that absolute values of these electrode potentials cannot be determined directly.
These are found by connecting the half-cell with a standard hydrogen electrode whose reduction
potential has been arbitrarily fixed as zero.
Determination of electrode potential or emf of a half-cell:
By a single electrode potential, we also mean the emf of an isolated half-cell or its half- reaction.
The emf of a cell that is made of two half-cells can be determined by connecting them to a voltmeter.
However, there is no way of measuring the emf of a single half-cell directly. A convenient procedure to
do so is to combine the given half-cell with another standard half-cell. The emf of the newly constructed
cell, E, is determined with a voltmeter. The emf of the unknown half-cell, E°, can then be calculated
from the expression
Emeasured = ER – EL
If the standard half-cell acts as anode, the equation becomes.
ER = Emeasured (∵ EL = 0)
On the other hand, if standard half-cell is cathode, the equation takes the form
 5

EL = – Emeasured (∵ ER = 0)
The standard hydrogen half-cell or Standard
Hydrogen Electrode (SHE) is selected for coupling
with the unknown half-cell. It consists of a platinum
electrode immersed in a 1 M solution of H+ ions
maintained at 25°C. Hydrogen gas at one atmosphere
enters the glass hood and bubbles over the platinum
electrode.
The hydrogen gas at the platinum electrode passes into
solution, forming H+ ions and electrons.
The standard hydrogen electrode:
The emf of the standard hydrogen electrode is
Fig. 3 Standard hydrogen electrode
arbitrarily assigned the value of zero volts. So, SHE
can be used as a standard for other
electrodes. The half-cell whose potential is
desired is combined with the hydrogen
electrode and the emf of the complete cell
determined with a voltmeter. The emf of the
cell is the emf of the half-cell.
For example, it is desired to
determine the electrode potential of the zinc
electrode, Zn | Zn2+. It is connected with the
SHE as shown in Fig. 4. The complete
electrochemical cell may be represented as:
Zn | Zn2+ || H+ | H2 (1 atm), Pt
Ecell = ER – EL
Fig. 4. The Zinc electrode coupled with SHE
= 0 – 0.76 = – 0.76 V
The emf of the cell has been found to
be –0.76V which is the emf of the zinc half-cell. Similarly, the electrode potential of the copper
electrode, Cu2+|Cu can be determined by pairing it with the SHE when the electrochemical cell can be
represented as:
Pt, H2 (1 atm) | H+ || Cu2+ | Cu
The emf of this cell has been determined to be 0.34 V which is the electrode potential of the copper
half-cell.
E0cell = E0Cu|Cu2+ - E0SHE
0.34 – 0 = 0.34 V
SHE can act both as cathode and anode when joined with another half-cell (Fig. 5).
When it is placed on the right-hand side of the Zinc electrode, the hydrogen electrode reaction is
2H+ + 2e– H2
 6

The electrons flow to the SHE

and it acts as the cathode. When
the SHE is placed on the left-
hand side, the electrode reaction
is
H2 2H+ + 2e–
The electrons flow to the copper
electrode and the hydrogen
electrode as the anode.
Evidently, the SHE can act
both as anode and cathode
and, therefore can be used to Fig. 5. The two situations are shown in
determine the emf of any other
half-cell electrode (or single electrode).
In the procedure for determining the emf of a given half-cell, the standard hydrogen electrode
can be placed on the left-hand or the right-hand. The electrons flow from left-to-right and the given
half-cell electrode gains electrons (reduction). The observed emf of the combined electrochemical cell
is then the emf of the half-cell on the right-hand. Such emf values of half-cells, or half reactions, are
known as the Standard reduction potentials or Standard potentials. However, if the SHE be placed
on the right-hand side of the given half-cell, the potential so obtained is called as the Standard
oxidation potential. The latter potentials are the standard potentials with the sign reversed, the only
difference being that cells have been turned around.
According to IUPAC convention, the standard reduction potentials alone are the
standard potentials.
Electrochemical series: The electrochemical series consists of a list of elements have been
arranged in the increasing order of their standard electrode potentials. Or
When elements are arranged in increasing order of their standard electrode potential,
a series called electrochemical series obtained.
Applications of electrochemical series:
1) Predicting the oxidizing or reducing ability 2) Predicting cell emf 3) Predicting feasibility of
reaction 4) Predicting whether a metal will displace another metal from its salt solution or not
5) Predicting whether a metal will displace hydrogen from a dilute acid solution. 5) The relative
corrosion tendencies of the metal.
 7

Table 1. Standard reduction potentials or Standard potentials

Element Electrode Standard Electrode
Reaction (Reduction) Reduction potential Eo, volt

Strong reductant Li Li+ + e- → Li -3.05

K K+ + e - → K -2.925

Ca Ca2+ + 2e- → Ca -2.87

Na Na+ + e- → Na -2.714
Increasing reducing strength

Mg Mg2+ + 2e- → Mg -2.37

Al Al3+ + 3e- → Al -1.66

Zn Zn2+ + 2e- → Zn -0.7628

Cr Cr3+ + 3e- → Cr -0.74

Fe Fe2+ + 2e- → Fe -0.44

Cd Cd2+ + 2e- → Cd -0.403

Ni Ni2+ + 2e- → Ni -0.25

Increasing oxidizing strength

Sn Sn2+ + 2e- → Sn -0.14

H2 2H+ + 2e- → H2 0.00

Cu Cu2+ + 2e- → Cu +0.337

I2 I2 + 2e- → 2I- +0.535

Ag Ag+ + e- → Ag +0.799

Hg Hg2+ + 2e- → Hg +0.885

Br2 Br2 + 2e- → 2Br- +1.08

Cl2 Cl2 + 2e- → 2Cl- +1.36

Au Au3+ + 3e- → Au +1.50

F2 F2 + 2e- → 2F- +2.87 (Strongest oxidant)

Predicting the Oxidizing or Reducing Ability:
Let us consider a series of elements Cu, H2, Ni, Zn and their ions. These four elements could act
as reducing agents. On the other hand, their ions Cu 2+, H+, Ni2+ and Zn2+ can act as electron acceptors
or oxidizing agents. If we list the respective half-reactions (or electrodes) in order of increasing E°
values, we will have placed the reducing agents in ascending order of their ability to attract electrons.
It is noteworthy that the value of E° becomes more positive down the series. This means that
Cu2+ is the best oxidizing agent (most electron-attracting ion) of those in the list. That is, Cu 2+ shows
the greatest tendency to be reduced. Conversely, Zn 2+ is the worst oxidizing agent, being the least
 8

electron-attracting ion. Of the elements Cu, H2, Ni and Zn, Zn is the best reducing agent (best electron
donor), since E° for the half-reaction has the most positive value. By the reasoning, Cu is the worst
reducing agent.
Zn Zn2+ + 2e– E° = - 0.76 V
The table of half reaction potentials above tells us that at standard conditions the following reactions
occur spontaneously.
Some important points concerning the Table of Standard Reduction Potentials (Table 1) are:
(1) The more positive the value of E°, the better the oxidizing ability (the greater the tendency to be
reduced) of the ion or compound, on moving down ward in the Table.
(2) The more negative the value of E° the better the reducing ability of the ions, elements or compounds
on moving upward in the Table.
(3) Under standard conditions, any substance in this Table will spontaneously oxidize any other
substance higher than it in the Table.
Predicting cell emf: The standard emf, E°, of a cell is the standard reduction potential of right- hand
electrode (cathode) minus the standard reduction potential of the left-hand electrode anode). That is,
E°cell = E°right – E°left
= Cathode potential – Anode potential
Let us predict the emf of the cell
Zn(s) | Zn+2 (aq) || Ag+(aq) | Ag
By using the E° values from the Table
E°cell = E°right – E°left
= 0.80 – (– 0.763) = 0.80 + 0.763 = 1.563 V
The answer is so clear from Fig. 6.

Figure 6. Diagrammatic representation of Cell emf.

Predicting Feasibility of Reaction: The feasibility of a redox reaction can be predicted with the help
of the electrochemical series. The net emf of the reaction, Ecell, can be calculated from the expression
E°cell = E°cathode – E°anode
In general, if E°cell = + ve, the reaction is feasible; E°cell = – ve, the reaction is not feasible
SOLVED PROBLEM 1. Predict whether the reaction
2 Ag(s) + Zn2+ (aq) ⎯⎯→ Ag+ (aq) + Zn(s) is feasible or not. Consult the table for the E° values.
SOLUTION: The cell half reactions are
Anode: 2Ag(s) 2Ag+(aq) + 2e– E° = 0.80 V ;
Cathode: Zn2+(aq) + 2e– Zn(s) E° = – 0.763 V
E°cell = E°cathode – E°anode
∴ E°cell = – 0.763 V – 0.80 = – 1.563
 9

Since E°cell is negative, the given reaction is not feasible.

SOLVED PROBLEM 2. Determine the feasibility of the reaction
2Al(s) + 2Sn4+(aq) 2Al3+ + 3Sn2+(aq) Consult the table for the E° values.
SOLUTION: The given reaction consists of the following half reactions
Anode: 2Al(s) 2Al3+ + 6e– E° = – 1.66 V
Cathode: 3Sn4+ + 6e– 3Sn2+ E° = + 0.15
E°cell = 0.15 – (– 1.66) = 1.81 V Since E°cell is positive, the reaction is feasible.
Predicting whether a metal will displace another metal from its salt solution or not: As already
shown, the metals near the top of the electrochemical series are strong reducing agents and are
themselves oxidized to metal ions. On the contrary, the metals lying bottom in the series are strong
oxidizing agents and their ions are readily reduced to the metal itself. For example, zinc lying down
above the series is oxidized to Zn2+ ion, while copper which is lower in the series is produced by reduction
of Cu2+ ion.
Zn Zn2+ + 2e–
Cu2+ + 2e– Cu↓
Thus, when zinc is placed in CuSO4 solution, Cu metal gets precipitated. In general, we can say
that a metal higher up in the electrochemical series can precipitate the one lower down in the
series. Silver cannot precipitate Cu from CuSO4, solution, since both metals have positions lower in the
series and are strong oxidizing agents.
Predicting whether a metal will displace hydrogen from a dilute acid solution: Any metal below
hydrogen in the electrochemical series is a weaker reducing agent than hydrogen itself and cannot
reduce H+ to H2. Any metal above hydrogen is a stronger reducing agent than hydrogen and will convert
H+ to H2. This explains why Zn lying above hydrogen reacts with dil. H2SO4 to liberate H2, while Cu lying
below hydrogen does not react.
Zn + H+ (dil. H2SO4) Zn2+ + H2 ↑
Cu + H+ (dil. H2SO4) Cu2+ + H2
The relative corrosion tendencies of the metal. The metals above the hydrogen in the series can
easily oxidised hence they undergo corrosion.
THE NERNST EQUATION:
The electrical energy generated by the galvanic cell can be quantitatively converted into work.
So, the emf of the cell is a measure of the maximum useful work that can be obtained under standard
condition.
The electrical energy or electrical work is equal to the product of emf of the cell and the electrical
charge that flow through the external circuit.
Wmax = nFEcell
Where, n is the no of moles of electrons transferred through wire
F is faraday constant i.e., 96500 coloumbs
Ecell is the emf of the cell.
 10

According to the thermodynamics, the free energy change (∆G) for a process is equal to the
maximum work that can be derived from a cell.
Wmax = ∆G
∆G = -nFEcell and ∆G0 = -nFE0cell
∆G0 = Standard free energy change
E0cell = Standard cell potential
The change in free energy is given by
∆𝑮 = ∆𝑮𝟎 + 𝑹𝑻𝒍𝒏 𝑸 Where Q= reaction quotient

On substituting the above expression

−𝒏𝑭𝑬𝒄𝒆𝒍𝒍 = −𝒏𝑭𝑬𝟎𝒄𝒆𝒍𝒍 + 𝑹𝑻𝒍𝒏 𝑸

On dividing the equation with –nF
𝑹𝑻
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎𝒄𝒆𝒍𝒍 − 𝒍𝒏𝑸
𝒏𝑭
Where, R= gas constant= 8.314 J; T= Temp in Kelvin, 298K; F= Faraday 96500 C

𝟎. 𝟎𝟓𝟗𝟐
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎𝒄𝒆𝒍𝒍 − 𝒍𝒐𝒈𝑸
𝒏
[𝑷𝒓𝒐𝒅𝒖𝒄𝒕]
Where, 𝑸 = [𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕]

𝟎. 𝟎𝟓𝟗𝟐 [𝒑𝒓𝒐𝒅𝒖𝒄𝒕]
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎𝒄𝒆𝒍𝒍 − 𝒍𝒐𝒈
𝒏 [𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕]
For a given general reaction
aA + bB cC + dD

𝟎. 𝟎𝟓𝟗𝟐 [𝑪]𝒄 [𝑫]𝒅

𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎𝒄𝒆𝒍𝒍 − 𝒍𝒐𝒈
𝒏 [𝑨]𝒂 [𝑩]𝒃
SOLVED PROBLEM. Calculate the emf of the cell.
Zn | Zn+ (0.001M) || Ag+ (0.1M) | Ag
The standard potential of Ag+|Ag half-cell is + 0.80 V and Zn2+|Zn is – 0.76 V.
SOLUTION: Step 1. Write the half-cell reactions of the anode and the cathode. Then add the anode
and cathode half reactions to obtain the cell reaction and the value of E°cell.
Cathode : 2Ag+ + 2e– 2Ag E° = +0.80 V
Anode : Zn Zn2+ + 2e– E° = – 0.76 V

Cell reaction: Zn + 2Ag+ Zn2+ + 2Ag E° = 1.56 V

Step2.

[𝐙𝐧+𝟐 ]
𝐐 𝐟𝐨𝐫 𝐭𝐡𝐞 𝐜𝐞𝐥𝐥 𝐫𝐞𝐚𝐜𝐭𝐢𝐨𝐧 =
[𝐀𝐠 + ]𝟐
Substitute the given values in the Nernst equation and solving for Ecell, we have
 11

𝟎. 𝟎𝟓𝟗𝟐
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎𝒄𝒆𝒍𝒍 − 𝒍𝒐𝒈𝑸
𝒏
𝟎. 𝟎𝟓𝟗𝟐 [𝐙𝐧+𝟐 ]
𝑬𝒄𝒆𝒍𝒍 = 𝟏. 𝟓𝟔 − 𝒍𝒐𝒈
𝟐 [𝑨𝒈+ ]𝟐
𝟎. 𝟎𝟓𝟗𝟐 [𝟏𝟎−𝟑 ]
𝑬𝒄𝒆𝒍𝒍 = 𝟏. 𝟓𝟔 − 𝒍𝒐𝒈
𝟐 [𝟏𝟎−𝟏 ]𝟐
= 𝟏. 𝟓𝟔 + 𝟎. 𝟎𝟐𝟗𝟓𝟓 = 𝟏. 𝟓𝟖𝟗𝟓𝟓 𝑽
Nernst equation of electrode potential:
We know experimentally that the potential of a single electrode or half-cell varies with the
concentration of ions in the cell. In 1889 Walter Nernst derived a mathematical relationship which enable
us to calculate the half-cell potential, E, from the standard electrode potential, E°, and the temperature
of the cell.
This relation known as the Nernst equation can be stated as
𝟐. 𝟑𝟎𝟑𝑹𝑻
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈𝑸 (𝟏)
𝒏𝑭
Where E° = standard electrode potential; R = gas constant; T = Kelvin temperature
n = number of electrons transferred in the half-reaction F = Faraday of electricity
Q = reaction quotient
Calculation of Half-cell potential:
For a reduction half-cell reaction
Mn+ + ne– M
The Nernst equation takes the form
𝟐. 𝟑𝟎𝟑𝑹𝑻 𝑴
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈 [ 𝒏+ ] (𝟐)
𝒏𝑭 𝑴
The concentration of solid metal [M] is considered as unity. Therefore, the Nernst equation can be
written as
𝟐. 𝟑𝟎𝟑𝑹𝑻 𝟏
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈 𝒏+ (𝟑)
𝒏𝑭 [𝑴 ]
Substituting the values of R, F and T at 25°C, the quantity 2.303 RT/F comes to be 0.0592. Thus, the
Nernst equation (3) can be written in its simplified form as
𝟎. 𝟎𝟓𝟗𝟐 𝟏
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈 𝒏+
𝒏 [𝑴 ]
This is the equation for a half-cell in which reduction occurs. In case it is an oxidation reaction, the sign
of E will have to be reversed.
SOLVED PROBLEM. What is the potential of a half-cell consisting of copper electrode in 0.015M CuSO4
solution at 25°C, E° =0.34 V.
SOLUTION: The half-cell reaction is
Cu2+ + 2e– Cu (reduction)
The Nernst equation for the oxidation half-cell reaction is
 12

𝟎. 𝟎𝟓𝟗𝟐 [𝑪𝒖]
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈
𝒏 [𝑪𝒖𝒏+ ]
The number of electrons transferred n = 2 and E° = 0.34 V. and solid copper [Cu] concentration is unity.
Substituting these values in the Nernst equation we have
𝟎. 𝟎𝟓𝟗𝟐 𝟏
𝑬 = 𝟎. 𝟑𝟒 − 𝒍𝒐𝒈
𝟐 𝟎. 𝟎𝟏𝟓
𝑬 = 𝟎. 𝟐𝟗𝟔 𝑽
Calculation of Equilibrium constant for the cell reaction
The Nernst equation for a cell is
𝟎. 𝟎𝟓𝟗𝟐
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝟎𝒄𝒆𝒍𝒍 − 𝒍𝒐𝒈𝑸
𝒏
At equilibrium ∆G=0 and E=0 and Q=K., Then
𝟎. 𝟎𝟓𝟗𝟐
𝟎 = 𝑬𝟎𝒄𝒆𝒍𝒍 − 𝒍𝒐𝒈𝑲
𝒏
𝒏𝑬𝟎𝒄𝒆𝒍𝒍
𝐥𝐨𝐠 𝑲 =
𝟎. 𝟎𝟓𝟗𝟐
SOLVED PROBLEM. Calculate the equilibrium constant for the reaction between silver nitrate and
metallic zinc.
SOLUTION: Step 1. Write the equation for the reaction

Zn + 2Ag+ Zn2+ + 2Ag E° = 1.56 V

Step 2. Substitute values in the Nernst equation at equilibrium

𝒏𝑬𝟎𝒄𝒆𝒍𝒍
𝐥𝐨𝐠 𝑲 =
𝟎. 𝟎𝟓𝟗𝟐
𝟎 = 𝟏. 𝟓𝟔 − 𝟎. 𝟎𝟑 𝒍𝒐𝒈𝑲
−𝟏. 𝟓𝟔 = −𝟎. 𝟎𝟑 𝒍𝒐𝒈𝑲
−𝟏. 𝟓𝟔
𝐥𝐨𝐠𝐊 = = 𝟓𝟐
𝟎. 𝟎𝟓 − 𝟎. 𝟎𝟑
K = 1×1052
Quinhydrone Electrode: It involves the redox reaction between quinone (Q) and hydroquinone (QH2).

Q + 2H+ + 2e– QH2

Figure.7 The Quinhydrone
electrode.
 13

The hydroquinone half-cell consists of

a platinum strip immersed in a saturated
solution of quinhydrone at a definite H+ ion
concentration. Quinhydrone is a molecular
compound which gives equimolar amounts of
quinone and hydroquinone in solution. The
electrode system may be represented as
Pt | QH2, Q, H+
The potential developed is measured against
a hydrogen electrode or calomel electrode. Fig.7 Quinhydrone electrode coupled with
Q+ 2H+ + 2e– QH2 saturated calomel electrode (dipping calomel
electrode)
The electrode potential at 250c is given by
Nernst equation

𝟐. 𝟑𝟎𝟑𝑹𝑻 [𝑸𝑯𝟐 ]
𝑬𝑸 = 𝑬𝟎𝑸 − 𝒍𝒐𝒈
𝒏𝒇 [𝑸][𝑯+ ]𝟐

𝟎. 𝟎𝟓𝟗𝟐 𝑽 [𝑸𝑯𝟐]
𝑬𝑸 = 𝑬𝟎𝑸 − 𝒍𝒐𝒈
𝟐 [𝑸][𝑯+ ]𝟐

Since quinone and hydroquinone are taken in equimolar amounts

i.e., [Q] = [QH2] = 1

𝟎. 𝟎𝟓𝟗𝟐 𝑽 𝟏
𝑬𝑸 = 𝑬𝟎𝑸 − 𝒍𝒐𝒈 + 𝟐
𝟐 [𝑯 ]

𝟎. 𝟎𝟓𝟗𝟐 𝑽
𝑬𝑸 = 𝑬𝟎𝑸 + 𝟐 𝒍𝒐𝒈[𝑯+ ]
𝟐

𝑬𝑸 = 𝑬𝟎𝑸 + 𝟎. 𝟎𝟓𝟗𝟐 𝑽 𝒍𝒐𝒈[𝑯+ ]

𝑬𝑸 = 𝑬𝟎𝑸 − 𝟎. 𝟎𝟓𝟗𝟐 𝑽 𝑷𝑯

[−𝒍𝒐𝒈[𝑯+ ] = pH]

𝑬𝑸 = 𝟎. 𝟔𝟗𝟗𝟒𝑽 − 𝟎. 𝟎𝟓𝟗𝟐 𝑽 𝐩𝐇

Since the electrode potential of the quinhydrone electrode depends upon the concentration of
hydrogen ions, it can be used for the determination of pH value just like a hydrogen electrode.
Construction: Quinhydrone electrode can very easily be set up by adding a pinch quinhydrone powder
(a sparingly soluble solid) to the experimental solution with stirring, until the solution is saturated and
a slight excess of it remains undissolved. Then, indicator electrode, usually of bright platinum, is inserted
in it.
 14

For determining the pH value, this half-cell is combined with any other reference electrode,
usually saturated calomel electrode and the emf of the cell so-formed (Fig. 7) is determined
potentiometrically. The complete cell may be represented as

(-) Hg, Hg2Cl2 | KCl (satd) || H2Q, Q, H+(unknown) | Pt (+)

𝐸𝐶𝑒𝑙𝑙 = ER− EL

= Equinhydrone − Ecalomel

𝐸𝑐𝑒𝑙𝑙 = (0.6994v – 0.0592 V pH) ‒ 0.2422

𝟎. 𝟔𝟗𝟗𝟒 − 𝟎. 𝟐𝟒𝟐𝟐‒ 𝑬𝒄𝒆𝒍𝒍

𝐩𝐇 =
𝟎. 𝟎𝟓𝟗𝟐
Advantages:

1. The electrode is very easy to setup. 2) The pH value obtained is very accurate. 3) Very small
quantities of the solution are sufficient for the measurement.

Limitations: The electrode cannot be used in alkaline solutions (pH>8.5) 2) It cannot be used in
solutions containing redox system, which would react with either quinhydrone or quinone. (Ex: Fe+2,
Mno2, etc.,)

Potentiometric titrations
A titration in which the equivalent or the end point of the reaction is determined with the help
of measurement of potential of a reaction mixture is known as potentiometric titrations.
In a potentiometric titration, a suitable electrode immersed in the solution to be titrated acts as
the ‘indicator electrode’ (Fig. 7). The indicator electrode is paired with a reference electrode and the
two electrodes are connected to an electronic voltmeter. The emf of the indicator electrode changes
gradually with the change of concentration of ions caused by the addition of titrant from the burette.
The equivalence Point is indicated by a sharp change in cell potential.
Since the reference electrode potential has a constant value, any change in the indicator
electrode potential is reflected by a similar change in the cell potential. Therefore, the equivalence point
can be found by plotting a graph between the cell emf and the volume of titrant added from the burette.
A sharp rise of the curve shows the equivalence point and the corresponding volume on the graph is the
volume of the solution used for the titration.
The potentiometric titrations may be of three types:
1) Acid-base titrations 2) Oxidation-reduction titrations 3) Precipitation titrations
Acid-base titrations:
Potentiometric measurement of EMF of a cell constructed using the test solution, HCl is used for
locating the end point in acid-base titration. The cell consists of a Saturated Calomel Electrode (SCE) as
reference electrode and quinhydrone (Q, QH2) as an indicator electrode. The EMF of the cell depends on
the H+ concentration of test solution. The quinhydrone is a powdered organic substance having
equimolar mixture of quinone (Q) and hydroquinone (QH2). When a pinch of hydroquinone is added to
 15

the acid solution in contact with platinum electrode, quinone, hydroquinone and H + ions form a reversible
redox system.

Q + 2H+ + 2e- QH2

Initially, before titration, the EMF measured will be high due to high H + concentration and on
addition of NaOH solution, it decreases due to decrease in concentration of H+ as a consequence of
neutralization to form H2O.
HCl + NaOH NaCl + H2O
After neutralization, the EMF decreases even below zero as indicated by -ve value. The cell can
be represented as:
(-) Hg, Hg2Cl2(s) | KCl (saturated) || H+ ions ( c=?), quinhydrone | Pt (+)
An oxidation takes place on the Calomel electrode and reduction tales place at quinhydrone
electrode.
𝐸𝐶𝑒𝑙𝑙 = ER− EL

= Equinhydrone − Ecalomel

𝐸𝑐𝑒𝑙𝑙 = (0.6994v – 0.0592 V pH) ‒ 0.2422

𝟎. 𝟔𝟗𝟗𝟒 − 𝟎. 𝟐𝟒𝟐𝟐‒ 𝑬𝒄𝒆𝒍𝒍

𝐩𝐇 =
𝟎. 𝟎𝟓𝟗𝟐

After each addition, the EMF of the cell is recorded. The EMF is then plotted against the volume
of alkali added. The shape of the curve for the titration of a strong acid against strong alkali (HCl versus
NaOH) is shown in Fig.8a. The steepest portion of the curve indicates the equivalent point of the titration.
However, the steepness of the curve is less marked and it is difficult to judge the end-point. So
now, we plot the curve, ΔE/ΔV against the volume of alkali used (Fig. 8b). The maximum of the curve
indicates the end-point.

Fig. 8 Curves of Acid-base titrations

Oxidation-reduction titrations:
Potentiometric measurement of EMF can be used for locating endpoint in the redox titration.
The cell consists of a saturated calomel electrode (SCE) as reference electrode and the platinum
electrode dipped in Fe+2 (test) solution as an indicator electrode. The EMF of the electrode depends upon
the ratio, [Fe+3/Fe+2].
 16

The cell can be represented as: (-) Hg, Hg2Cl2(s) |KCl (sat) || Fe+3, Fe+2 |Pt (+)
𝟐.𝟑𝟎𝟑𝑹𝑻 𝑭𝒆+𝟑
The EMF of the cell is given by, 𝑬 = 𝑬𝟎(𝑭𝒆+𝟑 𝑭𝒆+𝟐 ) + 𝒍𝒐𝒈 [𝑭𝒆+𝟐 ] − 𝑬𝑺𝑪𝑬
𝑭
e.g.: Fe+2 titrated against KMNO4
Initially, the concentration of Fe+2 in the solution is very low and the EMF measured will be low
and on addition of KMnO4 solution to Fe+2 solution, the concentration of Fe+3 increases (due to oxidation
of Fe+2) and the EMF increases.
5Fe+2 + MnO4- + 8H+ 5Fe+3 + Mn+2 + 4H2O
Finally, at the end point the EMF increases sharply and an inflection in the titration curve (Fig.
9) can be observed due to sharp decrease in Fe+2 concentration.

Fig. 15 Potentiometric titration curve of redox titration.

Precipitation titrations:
In precipitation reactions or titrations also, an electrode reversible to one of the ions is involved.
e.g.: Titrations of AgNO3 with NaCl where AgCl precipitates out.
Here Silver electrode is used along with Calomel electrode. The NaCl is taken in the burette and
AgNO3 is taken in the beaker containing electrodes. The emf of the cell is measured and plotted against
volume of NaCl added. The steepest portion of the curve indicates the equivalent point of the titration.
Advantages of potentiometric titrations:
1) Coloured solutions can be titrated without the use of an indicator.
2) Even weak acids, weak base titrations can be carried out.
3) Results obtained are very accurate.
4) The apparatus required is inexpensive, reliable and readily available.
5) can be used in the titrations of mixture of acids, bases, halides
 17

Ion-selective electrode (ISE): Ion selective electrode possess the ability to respond only to certain
specific ions, there by developing a potential with respect to that species only in a mixture and ignoring
the other ions totally.

Example: glass electrode is only H+ ions selective.

Glass electrode: When two solutions of different PH values are separated by

a thin glass membrane, there develops a difference of potential between the
two surfaces of the membrane. The potential difference developed is
proportional to the difference in PH values. The Glass membrane functions as
an Ion-exchange Resin. There is an equilibrium set up between the Na+ ions
of glass and H+ ions in the solution. The potential difference varies with the
H+ ions concentration of the solution. The electrode potential is given by

At 250c 𝐸𝐺 = 𝐸𝐺0 − 0.0592𝑙𝑜𝑔[𝐻 + ]

𝐸𝐺 = 𝐸𝐺0 + 0.0592 𝑃𝐻

Construction: Glass electrode

A glass electrode is a type of ion-selective electrode and consists of thin-walled glass bulb
containing AgCl coated Ag electrode or simply a Pt electrode in 0.1M HCl (Fig. 11). The glass electrode
may be shown schematically

Ag│AgCl(s), HCl (0.1M)│Glass or Pt,0.1M HCl│Glass

Determination of pH of solution by using glass electrode: Glass electrode is dipped in a solution

whose PH is to be determined and it is
coupled with saturated calomel electrode
(Fig. 12). The EMF of the cell is measured.
The EMF of complete cell is given by

Ecell = Eright - Eleft

Ecell = ESCE - EGLASS

= 0.2422𝑉 − [𝐸𝐺0 + 0.0592 𝑃 𝐻 ]

0.2422 V − Ecell − EG0

PH =
0.0592 V
The value of the potential of calomel
electrode is known while Ecell can be found
experimentally. Therefore, we can find PH
of a given solution if E°G is known. The
E°G value of a glass electrode can be
determined by using a solution of known Fig. 12 a) Glass electrode and saturated calomel electrode
PH in the cell and measuring Ecell. This immersed in a solution of unknown pH. b) Combined
value of E°G is constant for a particular probe or electrode of Glass electrode and reference
glass electrode and can be used for any electrode (saturated Calomel electrode)
subsequent determinations of pH of
unknown solutions
 18

Advantages of glass electrode: 1) It is simple and can easily be used. 2) Equilibrium is rapidly achieved
3) The results are accurate 4) It is not easily poisoned.

Limitations of glass electrode: 1) The glass electrode can be used in solutions with P H range of 0-10.
Electrodes composed of special glasses can be used for measurements up to a PH of 12. However, above
12 PH cations of solution affect the glass interface and render the electrode useless. 2) Although, glass
membranes of electrode is very thin, yet its resistance is very high, which cannot be measured by
ordinary potentiometers. It is therefore, necessary to use special electronic potentiometers.
 BATTERIES

Battery: battery is an electrochemical cell, or often several electrochemical cells connected in series
that can be used as a source of direct electric current at a constant voltage.
Classification: batteries are classified into three categories depending on their recharging
capabilities.
1) Primary battery (non rechargeable) 2) Secondary battery (rechargeable) 2) Flow battery
(Fuel cell)
Primary battery: Primary battery is a cell in which the cell reaction is not reversible. Thus, once
the chemical reaction takes place to release the electrical energy, the cell gets exhausted. They are
use and throw type.
Example: dry or leclanche cell, lithium cells

Secondary battery: Secondary battery is a cell in which the cell reaction is reversible. They are
rechargeable cells. Once the battery gets exhausted, it can be recharged.
Example: Lead-acid cell (storage cell), Nickel-Cadmium cell, lithium-ion cells etc.,

Differences between primary and secondary batteries

Primary batteries Secondary batteries

1.Cell reaction is irreversible 1.Cell reaction is reversible

2.Must be discarded after use 2.May be recharged

3.Have relatively short shelf life 3.Have long shelf life

4.Function only as galvanic cells 4. Functions both galvanic cell& as electrolytic cell.

5.They cannot be recharged 5.They can be recharged

6.EX:Dry cell, Li-MnO2 6.EX: Lead-acid cell (storage cell), Nickel-Cadmium

cell, lithium ion cells etc.,
Lithium cells: Lithium cells belong to primary cells. The cells having lithium anodes are called
lithium cells. Based on the cathode used, the lithium cells can be classified into two categories.

1) Lithium cells with solid cathodes, 2) Lithium cells with liquid cathodes

1) Lithium cells with solid cathodes: These batteries may have solid or liquid electrolyte.
The Most widely used cell is Li-MnO2 cell (3V).

Anode: Lithium metal

Cathode: MnO2

Electrolyte: Lithium perchlorate in propylene

carbonate or dimethoxyethane

voltage (EMF) 3V

MnO2 should be heated to over 300 0C to remove

water before keeping it in the cathode, thereby increasing
the efficiency of the cell.

Cell reactions:

At anode: Li Li+ + e-

At cathode: MnO2+ e- MnO2-

Net Cell reaction: Li+ MnO2 LiMnO2

Li-MnO2 primary battery

Applications:
1) The coin type cells are used in watches and
calculators.
2. Cylindrical cells are used in fully automatic cameras

Lithium-ion battery: A lithium-ion battery (sometimes Li-ion battery or LIB) is a member of

a family of rechargeable battery types in which lithium ions move from the negative electrode to the
positive electrode during discharge and back when charging.

Anode Graphite (Lithium intercalated graphite)

Cathode lithium cobalt oxide (LiCoO2)

Electrolyte lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium

perchlorate (LiClO4), etc., which are dissolved in organic solvents such as
ethylene carbonate and dimethyl carbonate.

Voltage 3.7 V

The three primary functional components of a lithium-ion battery are the positive and
negative electrodes and electrolyte. The most commercially popular negative electrode is graphite.
The positive electrode is generally one of
three materials: a layered oxide (such
as lithium cobalt oxide), a polyanion (such
as lithium iron phosphate) or a spinel (such
as lithiummanganese oxide).
The electrolyte is typically a mixture
of organic carbonates such as ethylene
carbonate or diethyl carbonate containing
complexes of lithium ions. These non-
aqueous electrolytes generally use non-
coordinating anion salts such as lithium
hexafluorophosphate (LiPF6), lithium Lithium ion battery
hexafluoroarsenate monohydrate (LiAsF6),
lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4) and lithium triflate (LiCF3SO3).

Both electrodes allow lithium ions to move in and out of their interiors.
During insertion (or intercalation) ions move into the electrode. During the reverse process,
extraction (or deintercalation), ions move back out. When a lithium-ion based cell is discharging,
the positive Lithium ion moves from the negative electrode (usually graphite = "C 6" below) and
enters the positive electrode (lithium cobalt oxide). When the cell is charging, the reverse occurs.

The cell reaction:

At anode: Lix C xLi+ + C + xe-

At cathode: Li1-xCoO2 + xLi+ + xe- LiCoO2

Lix C + Li1-x CoO2 C + LiCoO2

Applications:

1) Lithium-ion batteries are common in consumer electronics

2) They are one of the most popular types of rechargeable batteries for portable electronics, with a
High energy density, small memory effect, and only a slow loss of charge when not in use
3) LIBs are also growing in popularity for military, battery electric vehicle and aerospace applications
Advantages: Portable and rechargeable
Fuel cells: The device in which chemical energy of fuel-oxidant system converted into electrical
energy is known as fuel cell.
Principle: The basic principle of the fuel cell is same as that of an electrochemical cell. The fuel cell
operates like a galvanic cell. The only difference is that the fuel and oxidant stored outside of the
cell. Fuel and oxidant are supplied continuously and separately to the electrodes at which they
undergo redox reactions.
Fuel + oxidant Oxidation product + Electricity.
Examples: 1) Hydrogen – oxygen fuel cell 2) Methanol-oxygen fuel cell
1) Hydrogen – Oxygen fuel cell: A typical example of pollution free cell is H2 –O2 fuel cell in
which the Fuel is hydrogen and the oxidizer is oxygen.

Construction and working:

Hydrogen – oxygen fuel cell consists of two porous electrodes made up of compressed carbon coated
with small amount of catalysts (Pt, Pd, Ag) and KOH or NaOH solution as the electrolyte.

During working, Hydrogen (the fuel) is bubbled through the anode compartment, where
it is oxidized. The oxygen (oxidizer) is bubbled through the cathode compartment, where it is
reduced. The following cell reactions occur.

At Anode: 2H2 + 4OH- 4H2O + 4e-

At cathode: O2 + 4e- + 2H2O 4OH-

Net reaction: 2H2 + O2 2H2O

The product discharged is water and the standard EMF of the cell is 1.23V

Applications: Hydrogen – oxygen fuel cells are used as auxiliary energy source in space vehicles
(e.g., Apollo space craft), submarines other military vehicles.
Limitations: 1) High energy cost of generating Hydrogen fuel
2) Problems in handling, storage and distribution of highly flammable hydrogen fuel.

2) Methanol-oxygen fuel cell:

Methanol – oxygen fuel cell, methanol used as the fuel and oxygen or air as the oxidant.

Construction and working: It consists of two electrodes separated by a proton exchange

membrane (PEM) and connected via an external circuit that allows the conversion of free energy
from the chemical reaction of methanol with air or oxygen to be directly converted into electrical
energy. Aqueous methanol is fed at the anode side. It diffuses through the diffusion layer to the
catalytic layer where it is electrochemically oxidized into mainly carbon dioxide, protons and
electrons. Protons formed during this reaction diffuse through the membrane to the cathode catalytic
layer. They participate in the reduction of oxygen to form water at cathode side. Oxygen may be
pure but can also come from air.
Cell reactions:

At anode: CH3OH+H2O CO2+6H++6e-

At cathode: 3/2O2+6H++6e- 3H2O

Net reaction: CH3OH+3/2O2 CO2+2H2O

Discharging voltage (EMF) of methanol-oxygen fuel cell is 1.19V

Applications:
1. Space craft applications
2. Fuel cell vehicles.

Limitations: 1) During the methanol oxidation reaction, CO2 is formed which is strongly absorbed
on to platinum catalyst, reducing the surface area and lowering the performance.
2)

Methanol-oxygen fuel cell

Methanol is toxic and flammable.

3) Limited in the power supply.
Advantages of fuel cell:
1) It can’t give pollution
2) More efficiency
3) Maintenance cost is low
4) These are compact and transportable
5) They have quick start system
6) They save fossil fuels
7) The by products are environmentally acceptable
8) It has high reliability in electricity generation.
 1

Stereochemistry
Representations of three-dimensional structures:
Wedge-Dash formula:
Molecules exist in three dimensions. We can depict three-dimensional geometry in molecules using
bonds represented by dashed wedges, solid wedges, and lines.
 A dashed wedge ( ) represents a bond that projects behind the plane of the paper.
 A solid wedge ( ) represents a bond that projects out of the plane of the paper.
 An ordinary line ( ) represents a bond that lies in the plane of the paper.
A carbon atom with four single bonds has tetrahedral geometry and can be drawn with two bonds in
the plane of the paper separated by approximately 109.80, one bond behind the plane using a dashed
wedge, and one bond in front of the plane using a solid wedge.
The dashed wedge and solid wedge bonds in tetrahedral geometry nearly eclipse each other when drawn
in proper three-dimensional perspective.
Fisher projection formula: This formula is a standard way of depicting 3D structures in two dimensions
(2D). It is useful for simpler representation of the compounds contain one or more chiral C atoms. In this
formula, the molecule is drawn in the form of cross with chiral atom at the intersection of the horizontal
and vertical lines. The horizontal lines represent the bonds directed towards the viewer and the vertical
lines away from the viewer. As far as possible, the vertical part of the projection formula thus obtained
represents the longest chain of C atoms with most oxidized C atom (mainly the principal functional group)
at the top. For example, (-CHO) group in glyceraldehyde, (-COOH) group in lactic acid, etc.
Interconversion of Fisher formula to Wedge-Dash formula:
CHO CHO
When drawing the 3D formulae from the corresponding Fisher
formula, it is better to draw the group at the lower end of the HO H HO

vertical line towards R.H.S. CH2OH

CH2OH H

Several Fisher projections can be drawn depending on the Fisher Formula Dash-Wedge Formula
Glyceraldehyde
bonds drawn in the horizontal and vertical positions respectively.
It is therefore necessary to compare two different formulae to
check whether they represent the same or different compounds. The following rules must be observed.
1) A Fisher projection should not be taken out of paper and turned over. It would lead to the Fisher
projection of the enantiomer, since it changes the configuration at chiral center.
 2

2) Even number of interchanges clockwise or anti-clockwise a a

Forbidden
leads to the same stereoisomer, while odd number of d c
turnover
c d

interchanges results in an enantiomer. b b

CHO CHO CHO

HO H HO CH2OH H CH2OH
One Second
interchange interchange
CH2OH H OH

I II III
(I) and (III) are equivalent Fisher projections

3) Rotation of Fisher projection by 180o on the CHO CH2OH

Rotate by 180o
plane of paper results in the equivalent Fisher HO H H OH
On the plane
projections. of paper
I CH2OH II CHO
(I) and (II) are equivalent Fisher prijections
Interconversion of Wedge Dash formula to Fischer
formula:
For molecules containing several C atoms, it is customary to orient the molecule in such a way that the C-
chain is vertical. Substituents which are left and right of the viewer are written at left and right,
respectively, and other two substituents which appear above and below are written at top and bottom
positions.
CHO
Vertical CHO CHO
chain Visualise the structure
H H C OH H OH
L.H.S CH2OH such that main C-chain
OH is vertical CH2OH CH2OH
R.H.S Fisher projection
Formula

Although the Fischer projections are planer structures, these can be rotated end-for-end on the plane of
the paper only in the multiples of 180 but not 90 at a time. Also, a Fischer projection formula may not be
taken out of the plane of the paper and flipped over.
Sawhorse Projection
Sawhorse projection formula: This is a simple method of representing three-
dimensional formula on paper. The molecule is viewed slightly from above and
from the right and projected on the paper. The bond between the two carbon
atoms is drawn diagonally and is slightly elongated for clarity. The lower left-
hand carbon is considered to be towards the front and upper right-hand carbon
towards the back.
Newman projection formula: Newman devised a simple and highly useful method of representing the
3D formula on paper. These are called Newman projections after his name. These projection formulae are
 3

obtained by viewing the molecule along the bond joining two carbon atoms. The carbon atom near the eye
is represented by a point and the three atoms or groups attached to it by three equally spaced (1200) radii.
The carbon atom farther from the eye is designated by a circle and three atoms or groups attached to it by
three equally spaced radial extensions. It can be represented as shown in (1) or (2).

Front C atom Back C atom (1) (2)

Stereoisomerism:
Two or more than two compounds having same molecular formula, same structural formula but
different arrangements of atoms or groups in space or in 3D are called stereoisomers and the phenomenon
is called as Stereoisomerism. Each different spatial arrangement of atoms which characterize a particular
stereoisomer is called configuration. Therefore, stereoisomers have the same molecular structure but
different configurations. Stereoisomerism is further divided into two types. A) at room temperature
Configurational isomerism B) Conformational isomerism
Configurational isomerism: Configurational isomers are stereoisomers that do not readily interconvert
and can be separated. Interconversion of configurational isomers requires bond breaking and bond making.
Configurational isomer further classified into two groups. 1) Geometrical isomers and 2) Optical
isomers.
Geometrical Isomerism:
 Stereo isomer which cannot interconvert into each other at room temperature due to restricted
rotation about C-C bond, known as geometrical isomers.
 Geometrical isomerism (G. I): Alkenes (>C C<), oximes (>C N—) and azo compounds
[—N N—], show Geometrical Isomers due to restricted rotation about double bond while
cycloalkanes show Geometrical Isomers due to restricted rotation about single bond.
Geometrical Isomerism in Alkenes: In alkenes, (C=C) bond is made of σ-bond and π-bonds. A π-bond
is made by sideways overlap of un-hybridized p-orbitals of two carbon atoms above and below plane of
two carbon atoms.
If one of the carbon atoms is rotated through 90o, orbitals will no longer overlap and π-bond
would break, which requires 25 KJ/mol of energy. Hence, rotation around (C=C) bond is not free but
restricted. Due to this restricted rotation, the relative position of atoms or groups attached to the carbon
atoms of the double bond gets fixed, which results in the formation of two distinct isomers called
geometrical isomers.
 4

Geometrical isomers may be considered diastereomers since, they have different physical
properties and are not mirror images of each other.

H 3C CH3 H 3C H
E x a m p le :
H H H CH3
C is -2 -B u te n e T r a n s - 2 -B u te n e
Note: Cis Trans is possible only when π bond break
Condition for Geometrical isomerism:
Only those alkenes show G. I. in which "Each sp2 carbon have different atoms or groups"
a a a x a y p p

b b b y a y q q
Geometrical isomers Geometrical isomers Not Geometrical isomers Not Geometrical isomers

Nomenclature systems of geometrical isomers:

(a) Cis–Trans nomenclature: If same groups at same side of the double bond then cis and if same
groups at different side then trans.
a a a b

b b b a
Same groups same side Same groups different sides
Cis-isomer Trans-isomer

H H Cl Cl
H3C H
Example:
H 3C CH 2CH 3 H CH2CH3 Br Br
Cis-2-Pentene Trans-2-pentene Not Geometrical isomers
S.No. Physical properties Comparison Remarks
1 Dipole moment cis > trans cis-isomer has resultant of dipoles while in trans
isomer dipole moments cancel out
 5

2 Boiling point cis > trans Molecules having higher dipole moment have
higher boiling point due to larger intermolecular
force of attraction
3 Solubility (in H2O) cis > trans More polar molecules are more soluble in H2O
4 Melting point trans > cis More symmetric isomers have higher melting
points due to better packing in crystalline lattice
& trans isomers are more symmetric than cis.
5 Stability trans > cis The molecule having more van der Waal strain
are less stable. In cis isomer the bulky group are
closer they have larger van der Waal strain.

(b) The E and Z Nomenclature of geometrical isomers:

LP HP LP LP
E (Entgegen): When high priority groups (HP) are opposite side.
Z (Zussaman): When high priority groups (LP) are same side. HP LP HP HP
E Z
Priority Rules:
Rule I: Priority is proportional to atomic number of atoms which is directly attached to sp2 carbon.

HP HP HP
Br Cl HP Br F Cl CH 3 Cl NH 2

Cl Cl
HP I F HP I Cl HP C NH 2 C CH 3
E Z Cl HP Cl
Cl Cl
E Z

Rule II: If rule-I is failed then consider next atom

H3C CH3
C,C,C
CH3
HP F C HP
Decreasing order of atomic number
CH3
H3CH2C C C,C,H
LP CH3 LP
H
Z
Rule III: – If multiple bond is present then consider them as: -
 6

C C

C C C C HC CH C C

C C C C

O N
C O C HC N C N
O N
O
[O,O,H]
N C C H
C C
N C OH
H [O,O,O]
HP H O HP
Z
Priority order for some groups is:
Br > Cl > OH > NH > COOH > CHO > CHOH > CN > C6H5 > HC CH > C(CH)3 > C CH2 >
CH(CH3)2
Rule IV: If isotopes are present then consider atomic weight.
H CH3
C C
HP D CH2CH3 HP
Z
H3C H H3C CH3 HP

Example: C C C C
HP Cl CH3 HP HP Cl H
Z E

H3CH2C CH2Cl [Cl,H,H] HP N C CBr 3 [Br,Br,Br]

Example: C C C C
H3C
HC C COOH [O,O,H] LP C CH2I [I,H,H]
H3C
CH3
E E
Optical isomerism:
Certain substances possess the property to rotate the plane of polarized light. Such substances are
called optically active substances and this phenomenon is called optical activity.
Optical activity: Light is propagated by a vibratory motion of the 'ether' particles present in the
atmosphere. Thus, in ordinary light vibrations occur in all planes at right angles to the line of propagation.
 20

Conformational isomerism:
The different arrangements of atoms in space that result from the free rotation around C-C bond axis
are called conformations or conformers. The phenomenon is called conformational isomerism.
H
H

H H C
H
H H
H
H
C H
H
H

Here θ (60°) is dihedral angle, angle between two planes.

Conformations of Butane [CH3—CH2—CH2—CH3]: Butane is four-member carbon alkane with molecular
formula C4H10. In butane we will define dihedral angle θ as angle between the two methyl groups.
To analyze the different conformations that result from rotation about C-2 and C-3 bond rotation of
one carbon atom in 60o increments either clockwise or anti-clockwise, while keeping the other carbon fixed.
Continue until you return to the original conformation.
Although each 60o about rotation converts a staggered conformation into an eclipsed conformation or
vice-versa, neither all the staggered conformations nor all the eclipsed conformations are the same.
In butane, torsional strain results from steric hindrance between the terminal methylgroups and
hydrogen atoms at C-2 and C-3. These interactions result in six important conformers of butaneshown as I–
VI below.
CH3 CH3
CH3 CH3 H CH3
H CH3 H H

H H H H H CH3 H H
H H H
H CH3
I Eclipsed II Gauche III Partial ecliped IV Anti
0o 60o 120o 180o
CH3
CH3 H
H3C H

H H H CH3
H H
H
VI Gauche V Partial ecliped
300o 240o

 The anti-conformation (IV)

(I) does not have torsional strain from steric hindrance because the groups are
staggered and the methyl groups are far apart. The anti-conformation is the most stable.
 The methyl groups in the gauche conformations (II)
III and (VI)
V are close enough to each other that the
dispersion forces between them are repulsive; the electron clouds of the two groups are so close that they
 21

repel each other. This repulsion causes the gauche conformations to have approximately 3.8 kJ mol-1
more energy than the anti-conformation.
 I IV,
The eclipsed conformations (II, VI) represent energy maxima in the potential energy diagram
III and V

II and VI
(Fig. 2). Eclipsed conformations III V have repulsive dispersion forces arising from the eclipsed

methyl groups and hydrogen atoms. Eclipsed conformation IV

I has the greatest energy of all because of

II and VI.
the added large repulsive dispersion forces between the eclipsed methyl groups as compared to III V

 Mainly three conformational isomers of butane and their stability order is

Anti ˃ Gauche (Skew) ˃ Eclipsed
 Although the barriers to rotation in a butane molecule are larger than those of an ethane molecule
(Section 4.8), they are still far too small to permit isolation of the gauche and anti-conformations at
normal temperatures. Only at extremely low temperatures would the molecules have insufficient energies
to surmount these barriers.

Fig. 2. Potential energy diagram of conformers of n-butane

 1

ORGANIC REACTIONS
Types of Organic Reactions
There are six main types of organic reactions that can take place. They are as follows:
1) Substitution reactions 2) Addition reactions 3) Elimination reactions
4) Oxidation-Reduction reactions 5) Cyclization reactions 6) Rearrangement reactions
Nucleophilic Substitution Reactions:
Nucleophilic substitution reactions are among the most fundamental types of organicreactions. In a
nucleophilic substitution reaction, a nucleophile (Nu:) displaces a leavinggroup (LG) in the
molecule/substrate that undergoes the substitution.
 The nucleophile is always a Lewis base, and it may be negatively charged or neutral.
 The leaving group is always a species that takes a pair of electrons with it when it departs.
Often (not always) the substrate is an alkyl halide (R-X) and the leaving group is a halide anion(X-). The
following equations include a generic nucleophilic substitution reaction andsome specific examples.
_ _
Nu + R LG R Nu + LG
The nucleophile is a The bond between the The nucleophile uses The leaving group gains
Lewis base that carbon and the leaving its electron pair to form the pair of electrons that
donates an electron group breaks, giving a new covalent bond originally bonded it in
pair tothe substrate. both electrons from the with the substrate the substrate.
bond to the leaving carbon.
group.

OH + H3C I H3C OH + I

CH3O + CH3CH2 Br CH3CH2 OCH3 + Br

I + + Cl
Cl I
R R

R N + H3C I R N CH3 + I

R R
Mechanisms of nucleophilic substitution reactions:
Nucleophilic substitution reactions occur in two path (mechanism) ways; 1) SN1 and SN2.
SN1 Mechanism: SN1 stands for uni-molecular nucleophilic substitution. The mechanism involves two
steps.Consider the hydrolysis of tert.butyl bromide with aqueous NaOH.
Step 1: The tert.butyl bromide ionizes to give a planar carbonium ion. The carbonium ion is planar because
thecentral positively charged carbon is sp2 hybridized.
R
R R
Slow C Br
R C
Br +
R R
Step-2: The nucleophile can attack the planar carbonium ion from either side to give the product
 2

R R
R R Fast
C R C OH + HO C R
R R R

OH
 The first step requires heterolytic cleavage of the
carbon–bromine bond.. Because no other bonds are
formed in this step, it should be highly endothermic and it
should have a high free energy of activation, as we see in
the free-energy diagram (Fig. 1.0).. The departure of the
halide takes place because of the ionizing ability of the
solvent, water.. Experiments indicate that in the gas phase
(i.e., in the absence off a solvent), the free energy of
activation is about 630 kJ mol-11. In aqueous solution, Fig. 1.0 Free energy diagram for SN1 reaction
however, the free energy of activation is much lower
about 84 kJ mol-1. Water molecules surround and stabilize the cation and anion that are produced
produced.
 Ionization is thee rate determining step because it is the slow step. In other words, the rate at which
alcohol is formed should depend upon the concentration of tertiary alkyl halide alone.
he reaction follows first order kinetics; therefore, reaction is called SN1.
Rate = K[R3C—Br]. The
 In the second step the intermediate tert-butyl
butyl cation reacts rapidly with hydroxide ion to produce a tert-
butyl alcohol.
 The reactivity order for SN1 reaction is proportional to the stability of carbocations formed by
halides.Reactivity ( N1):Benzyl
tivity order of halides (S Benzyl halide > Allylhalide > 3°halide > 2° halide > 1° halide >
methyl halide.
Reactions Because the carbocation formed in the first step of an SN1 reaction
The Stereochemistry of SN1 Reactions:
has a trigonal planarstructure, then the nucleophile may attack from either thefront side or the back side (see
above step-2). Hence, racemization occursbecause
occurs the reaction causes chiral molecules are beingconverted to
ratio eseSN1 type of reactions
an achiral intermediate and both isomers are formed in equal or nearly equal ratio.TheseS
almost always result in extensive and sometimescomplete racemization. For example, heating optically
active (S)-3-bromo-3-methylhexanewith
methylhexanewith aqueous acetone results in the formation of of 3-methyl-3-hexanol
as a racemic mixture of 50%(R)) and 50% (S).
(
H3CH2CH2C H3CH2CH2C CH2CH2CH3
H2O C OH + HO C + HBr
C Br H3C CH
H3
H3C A
Acetone
H3CH2C CH2CH H3
H3CH2C
50% 50%
(S)-3-Bromo-3-methylhex xane (S)-3-Methyl-3-hexanol (R)-3-Methyl-33-hexanol
(optically active) (optically inactive, a racemic form))
 3

SN2 mechanism: SN2 stands for bimolecular nucleophilic substitution. In this type of nucleophilic
substitutionreaction, the bond making and bond breaking occurs simultaneously.
 The nucleophile approaches the carbon bearing the leaving group from the back side
side, that is, from the
side directly opposite the leaving group.
 As the nucleophile forms a bond and the leaving group departs, the substrate carbon atom undergoes
inversion*—its
its tetrahedral bonding configuration isturned inside out.
 The formation of the bond between the nucleophile
nucleophile and the carbon atom provides most of the energy
necessary to break the bond between the carbon atom and the leaving group.
 The SN2 reaction proceeds in a single step (without any intermediates) through anunstable arrangement of
atoms called the transition state.
H H H H
H
C Cl H O C Cl H O C H + Cl
H H H
H O Transition state Now the
t bond between the
The negative hydroxide ion brings In the transition state, a bond oxygeen and carbon has
a pair of electrons to the partially between oxygen and carbon is formeed and the chloride
positive carbon from the back side partially formed and the bond ion haas departed. The
with respect to the leaving group. between carbon and chlorine is configguration of the carbon
The chlorine begins to move away partially broken. The configuration has in
nverted.
with the pair of electrons that of the carbon atom begins to invert.
bonded it to the carbon.
 The transition state is a fleeting arrangement of the atoms in
which the nucleophile and the leaving group are both partially
bonded to the carbon atom undergoing substitution. Because
the transition state involves both the nucleophile (e.g., a
hydroxide ion)
on) and the substrate (e.g., a molecule of
chloromethane), this mechanism accounts for the second-
order reaction kinetics.
 The SN2 reaction is said to be a concerted reaction,
reaction because
Fig. 1.1 Free energy diagram for SN2
bond forming and bond breaking occur in concert
(simultaneously) through a single transition state.
 Reactivities of alkyl halides in SN2 substitution is governed by steric factors.. The bulkier the group, that
less reactive it will be.
 Reactivity order of alkyl halide varies as follows: CH3X > 1°halide > 2°halide > 3° halide
 The order of reactivity among 1° alkyl halides is: CH3X > C2H5X > C3H7X etc. Remember that in case
alkyl halide is optically active, SN2 reactions lead to Walden inversion.
 4

 Thus, in short 3° alkyl halides react by SN1, 1° by SN2 and 2° by either or both of them SN1 and SN2
depend upon the nature of the alkyl halide and the reagent.
 For a given alkyl group the order of reactivity is - (for SN1 and SN2 both): RI > RBr > RCl > RF
The Stereochemistry of SN2 Reactions:
 The nucleophile approaches the substrate carbon from the back side with respect to the leaving group. In
other words, the bond to the nucleophile that is forming is opposite (at 1800) to the bond to the leaving
group that is breaking.
 Nucleophilic displacement of the leaving group in an SN2 reaction causes inversion of configuration at
the substrate carbon.
When cis-1-chloro-3-methylcyclopentane reacts with hydroxide ion in an SN2 reaction,the product is
trans-3-methylcyclopentanol. The hydroxyl group ends up bonded on theopposite side of the ring from the
chlorine it replaces:

H3C Cl H3C Cl H3C H

+ OH H
H H H OH H OH
cis-1-Chloro-3- Transition state trans-3-Methylcyclopentanol
methylcyclopentane

We can also observe inversion of configuration when an SN2 reaction occurs at achirality center in an
acyclic molecule.The reaction of (R)-(-)-2-bromooctane withsodium hydroxide provides an example.When
the reaction is carried out, we find that enantiomerically pure (R)-(-)-2-bromooctane[ ] =-34.25) has been
converted to enantiomerically pure (S)-(+)-2-octanol ([ ] =+9.90).
The reaction of (R)-(-)-2-bromooctane with hydroxide is an SN2 reaction and takes place with inversion of
configuration:
H3C CH3 CH3

OH C Br HO C Br HO C + Br
H H
C6H13 H C6H13
C6H13
(R)-(-)-2-Bromooctane (S)-(+)-2-Octanol
An inversion of configuration
Optical rotation = - 34.25o Optical rotation = + 9.90o
Enantiomeric purity = 100% Enantiomeric purity = 100%

 SN2 reactions that involve breaking a bond to a chirality center can be used to relate configurations of
molecules because the stereochemistry of the reaction is known.
Differences between SN1 and SN2 mechanism (reactions)
Properties SN1 SN2
Definition Substitution nucleophilic unimolecular Substitution nucleophilic bimolecular

Reaction occurs in two steps through the The reaction is a concerted reaction,
formation of a carbocation intermediate because bond forming and bond
breaking occur simultaneously through
 5

a single transition state

Reactivity of halide RI > RBr > RCl > RF RI > RBr > RCl > RF
leaving groups
Effect of structure R3CX > R2CHX > RCH2X > CH3X CH3X > RCH2X > R2CHX > R3CX
Rate is governed by stability Rate is governed by stearic effect
ofcarbocation that is formed inionization (crowding in transition state).
step.
Effect of solvent Rate increases with increasing polarity of Polar aprotic solvents give fastest
solvent and polar protic solvents are rates of substitution
preferred
Effect of nucleophile Rate of substitution is independentof both Rate depends on both nature
concentration and natureof nucleophile andconcentration of nucleophile
Stereochemistry Not stereospecific; racemization takes Stereospecific; 100 percent
place inversionof configuration at reaction
site occurs. Nucleophile attacks
carbon from sideopposite bond to
leaving group
Free radical substitution reactions:
The reactions which have mechanisms that involve homolysis ofcovalent bonds with the production of
intermediates possessing unpaired electrons calledradicals (or free radicals).

Homoloysis
A B A + B

This simple example illustrates the way we use single-barbed curved arrows to showthe movement of a
single electron. Inthis instance, each group, A and B break away with one of the electrons of the
covalentbond that joined them.
Production of Radicals: Energy in the form of heat or light must be supplied to cause homolysis of covalent
bonds.
Examples: Compounds with an oxygen–oxygen single bond, called peroxides, undergo homolysis readily
when heated, because the oxygen–oxygen bond is weak. The products are two radicals, called alkoxyl
radicals:

Homoloysis
R O O R R O + O R Homolysis of a
Heat or dialkyl peroxide
Light
Dialkyl peroxide Alkoxyl radicals

Halogen molecules (X2) also contain a relatively weak bond. Halogensundergo homolysis readily when
heated or irradiated with light of a wavelengththat can be absorbed by the halogen molecule.
Homoloysis Homolysis of a
X X X + X
Heat or halogen molecule.
Light
 6

The products of this homolysis are halogen atoms, and because halogen atoms containan unpaired
electron, they are radicals.

Free Radical Substitution (Halogenation of Alkanes):

Alkanes)
Alkanes react with molecular halogens to produce alkyl halides by a substitutionreaction called
Free radical substitution reaction orr radical halogenation.
A general reaction showing formation of a monohaloalkane by radical halogenation isshown below.
It is called radical halogenation because,the mechanisminvolves species with unpaired electrons called
radicals.
R H + X2 R X + HX
The halogen atom replaces one or more of the hydrogen atoms of the alkane, andthe corresponding
hydrogen halide is formed as a by-product.
product.
One complicating factor of alkane halogenations is that multiple
Multiple Halogen Substitution:One
substitutions almostalways occur unless we use an excess of the alkane. The followingexample illustrates
this phenomenon.. If we mix an equimolar ratio of methane andchlorine (both substances are gases at room
temperature)) and then either heat the mixtureor irradiate it with light of the appropriate wavelength, a
reaction begins to occur vigorouslyand ultimately produces the following mixture of products
products.

To understand the formation of this mixture,

mixture, we need to consider how the concentrationof reactants
and products changes as the reaction proceeds. Initially,only the compounds chlorine and methane are
present in the mixture, and the onlyreaction that can take place is one that produces chlorom
chloromethane and
hydrogen chloride. As the reaction progresses, the concentration of chloromethane in the mixtureincreases,
and a second substitution reaction begins to occur. Chloromethane reactswith chlorine to produce
dichloromethane. The dichloromethane produced
produced can then react to form trichloromethane, and
trichloromethane,as it accumulates in the mixture, can react with chlorine to producetetrachloromethane.
Each time a substitution of -Cl for -H
H takes place, a molecule ofH-Cl
ofH is produced.
Chlorination of Methane: Reaction The reaction of methane with chlorine (in the gas
thane: Mechanism of Reaction:The
phase) provides a good example forstudying the mechanism of radicalhalogenation.
CH4 + Cl2 CH3Cl + HCl (+ CH2Cl2, CHCl3 and CCl4)
 7

Several experimental observations help in understanding the mechanism of this reaction. The mechanism
broadly consists three steps. 1) Chain Initiation 2) Chain propagation 3) Chain termination.
Reaction
Light or
CH4 + Cl2 H3C Cl + HCl
heat
Mechanism:
Chain initiation: Heat or 2 Cl
Cl Cl
Halogen dissociation Light
Under the influence of heat or This step produces two
light a molecule of chlorine highly reactive chlorine
dissociates; each atom takes radicals.
one of the bonding electrons.
H H
Chain Propagation: Cl + H C H C H + HCl
A chlorine atom abstracts This step produces a
H
a hydrogen atom from a H molecule of hydrogen
methane molecule. chloride and a methyl
radical.
H

Cl Cl + C Cl + Cl C H

A methyl radical abstracts H

a chlorine atom from a This step produces a molecule of
chloromethane and a chlorine atom.
chlorine
The chlorine atom can now cause a
molecule.
repetition of step 2.

Chain termination step: Cl + Cl Cl Cl Coupling of any two

radicals depletes the
H H supply of reactive
Cl + CH H Cl C H intermediates and
terminates the chain.
H H Several pairings are
possible for radical
H H coupling termination
H H
H C + C H H C C H steps

H H H H

The reaction is promoted by heat or light. At room temperature methane and chlorine do not react
at a perceptible rate as long as the mixture is kept away from light. Methane and chlorine do react at room
temperature if the gaseous reaction mixture is irradiated with UV light at a wavelength absorbed by Cl2, and
they react in the dark if the gaseous mixture is heated to temperatures greater than 100o C. The light-
promoted reaction is highly efficient. A relatively small number of light photons permits the formation of
relatively large amounts of chlorinated product.
Step 1: Chain-initiating step: In the chain-initiating step radicals are created. In this case, Cl2 will absorb
the energy and split in to two chlorine radicals.
 8

Step 2: Chain propagation step:In this step, the chlorine radicals generated in the first step, will react with
methane to produce methyl radical and HCl. The methyl radical will react with another chlorine molecule to
produce chloromethane and chorine radical. So produced chlorine radical again will react with one more
methane molecule and the cycle goes on. Hence, in chain-propagating stepone radical generates
another.The chain nature of the reaction accounts for the observation that the light-promotedreaction is
highly efficient. The presence of a relatively few atoms of chlorine at any givenmoment is all that is needed
to cause the formation of many thousands of molecules ofchloromethane.
Step 3: Chain termination step:This usually happensby a process opposite to the first step, namely, a
combination of two like or unlike radicalsto form a new bond.
 Chlorine is relatively unselective; it does not discriminate greatly among the different types of hydrogen
atoms (primary, secondary, and tertiary) in an alkane.
 Because alkane chlorination usually yields a complex mixture of products, they are not useful as
synthetic methods when the goal is preparation of a specific alkyl chloride.
 Bromine is generally less reactive toward alkanes than chlorine, and bromine is more selective in the site
of attack when it does react.
 Bromination is selective for substitution where the most stable radical intermediate can be formed.
Electrophilic Aromatic Substitution Reactions:Some of the most important H E
E A +H A
reactions of aromatic compounds are those in which an electrophile replaces
one of the hydrogen atoms of the ring.These reactions, X
called electrophilic aromatic substitutions (EAS),
X2/ FeX3

allow the directintroduction of groups onto aromatic R NO2

RC
rings such as benzene, and they provide l/ SO 4
AlC + H2
l3 O3
syntheticroutes to many important HN
SO
compounds.Figure1.2 outlines five different types of AlC
l3
3 /H
l/ 2 SO
OC SO3 H
electrophilicaromatic substitutions that, including RC
4
ROC
carbon–carbonbond-forming reactions and
halogenations. Fig.1.2 EAS reactions
Although benzene is susceptible to electrophilic attack, it undergoes substitutionreactions rather than
addition reactions.
General mechanism for electrophilic aromatic substitution.
Step 1: The electrophile takes two electrons of the six-electron π system to forma σ bond to one carbon atom
of the benzene ring.
 9

Formation of this bond interrupts the cyclic system of π electrons, because in the formationof the
arenium ion the carbon that forms a bond to the electrophile becomes sp3hybridized and, therefore, no longer
has an available p orbital. Now only five carbonatoms of the ring are sp2 hybridized and still have p orbitals.
fi p orbitals. In the arenium ion
The four π electrons of thearenium ion are delocalized through these five
formed by electrophilic addition of bromine to benzene,the
benzene positive charge is distributed in the arenium
ionring, just as was shown in the contributing resonancestructures.
Step 2: A proton is removed from the carbon atom of the arenium ion that bearsthe electrophile, restoring
aromaticity to the ring.
The two electrons that bonded the proton to the ring become a part of the π system.The carbon atom
that bears the electrophile becomes sp2 hybridized again, and a benzenederivative with six fully delocalized π
electrons is formed. The proton is removed by anyof the bases present, for example, by the anion derived
from the electrophile.
Step 1:
H H H
E A E +A S
Slow, rate
E E d
determining
sttep

Arenium ion
(a delocalized cyclohexadienyl cation)
Step 2: H
E
E A + H A Fast step

There is firm experimental evidence that the arenium

ion is a true intermediate in electrophilicsubstitution reactions.
It is not a transition state. This means that in a free-
free
energydiagram (Fig. 1.3) the arenium ion lies in an energy
valley between two transition states.The free energy of
activation for step 1, DG‡(1),
‡(1), has been shown to be much
greaterthan the free energy of activation for step 2, DG‡(2),
D as
depicted in Figure 1.3. This isconsistent
consistent with what we would
expect. The reaction
tion leading from benzene and an
Fig. 1.3 Free energy diagram of EAS
electrophileto the arenium ion is highly endothermic, because
the aromatic stability of thebenzene ring is lost. The reaction leading from the arenium ion to the substituted
benzene,by contrast, is highly exothermic because it restores aromaticity to the system.Of the following two
steps, step 1 (the formation of the arenium ion) is usually therate-determining
determining step in electrophilic aromatic
substitution because of its higher freeenergy of activation.
activation
 10

Nitration of Benzene:Benzene undergoes nitration on reaction

NO2
HNO3
with a mixture of concentrated nitric acid andconcentrated
H2SO4
sulfuric acid.Concentrated sulfuric acid increases the rate of the
reaction by increasing the concentrationof the electrophile, the nitronium ion (NO2+), as shown in the first
two steps of thefollowing mechanism.
Step 1: In this step nitric acid accepts a proton from the stronger acid, sulfuric acid.

O O H O O
H O S O H + H O N H O N + H O S O
O O O O
Step. 2: Now that it is protonated, nitric acid can dissociate to form a nitronium ion.
H O O
H O N H2O + N
O O
Step. 3: The nitronium ion is the electrophile in nitration; it reacts with benzene to form a resonance-stabilized
arenium ion. H H H
O
Slow
+ N NO2 NO2 NO2
O

Arenium ion
Step. 4: The arenium ion then loses a proton to a Lewis base and becomes nitrobenzene.
H
NO2
+ O H
NO2
H

Electrophilic Addition:
The reaction in which reagent adds to a multiple bond to give less unsaturated or completely
saturatedproduct, are known as addition reactions. If such reactions are initiated by electrophiles, then they
are called as Electrophilic Addition reactions.
 Electrons in the π bond of alkenes/alkynes etc., react with electrophiles.
 Electrophiles are electron-seeking reagents. They have the property of being electrophilic.
Electrophiles include proton donors such as Bronsted–Lowry acids, neutral reagents such as bromine
(because it can be polarized so that one end is positive), and Lewis acids such as BH3, BF3, and
AlCl3.
Electrophilic Addition of Hydrogen Halides to Alkenes:
Hydrogen halides (HI, HBr, HCl, and HF) react with alkenes by accepting a pair of electrons fromthe π
bond to form aσ bond between the hydrogen and one of the carbon atoms, with lossof the halide ion. This
 11

leaves a vacant porbital and a + charge on the other carbon. The overallresult is the formation of a
carbocation and a halide ion from the alkene and HX.

C C + H X C C + X

H
Being highly reactive, the carbocation may then combine with the halide ion by acceptingone of its electron
pairs.

C C + X C C

H H X
These additions are sometimes carried out by dissolving the hydrogen halide in asolvent, such as
acetic acid or CH2Cl2, or by bubbling the gaseous hydrogen halide directlyinto the alkene and using the
alkene itself as the solvent.
The order of reactivity of the hydrogen halides in alkene addition isHI ˃ HBr ˃ HCl ˃ HF
Mechanism and Markovnikov’s Rule:
The addition of HX to an unsymmetrical alkene could conceivably occur in two ways.In practice,
however, one product usually predominates. For example, the addition of HBr to propene could conceivably
lead to either 1-bromopropane or 2-bromopropane.The main product, however, is 2-bromopropane.

+ H Br + Br

2-Bromopropane 1-Bromopropane
Major Minor
When 2-methylpropene reacts with HBr, the main product is 2-bromo-2-methylpropane,not 1-bromo-2-
methylpropane.

+ H Br + Br
Br

2-Methylpropene 2-Bromo-2-methylpropane 1-Bromo-2-methylpropane

Minor Major
Consideration of many examples like this led the Russian chemist Vladimir Markovnikov in 1870 to
formulate what is now known as Markovnikov’s rule.
Markovnikov’s rule states that in the addition ofHXto anunsymmetrical alkene, the hydrogen atom adds
to the carbon atom of the double bond thatalready has the greater number of hydrogen atoms. *
(or)
“The negative part of the addendum or reagent (X-) adds to the doubly bonded carbon atom which bears
the least number of hydrogens”
The addition of HBr to propene is an illustration:
 12

Alkene carbon H2C C CH3 H2C CH C

CH3
atom with the
greater number of H Br
hydrogen atoms H Br+ - Markovnikov add
dition
product

A mechanism for addition of a hydrogen halide to an alkene involves the following two steps:
Br
H3C CH2 CH2 H3C CH2 CH
C 2
o
1 Cation B
Br
Less-stable than 2o Cation 1-Bromoprropane
HBr (Minor pro
oduct formed)
H3C CH CH2
Slow
Br
H3C CH CH3 H3C CH CH
H3
Fast
2o Cation Br
Stable than 1o Cation 2-Bromopropaane
(main product))

Step 1
S Step 2
Slow and R
Rate determining step Fast Step

 The main product of the reaction is 2-bromopropane

2
because the more stable secondary carbocation is
formed preferentially in the first step.
 The more stable carbocation predominates because it
is formed faster.
We can understand why this is true if we examine the
free-energy diagrams in Fig. 1.4.
 The reaction leading to the secondary carbocation
(and ultimately to 2-bromopropane)
bromopropane) has the lower free
energy of activation. This is reasonable because its
energy diagrams for the addition of
Fig.1.4Free-energy
transition state resembles the more stable carbocation. DG‡(1o).
HBr to propene. DG‡(2o) is less than D

 The reaction leading to the primary carbocation (and ultimately to 1-bromopropane)

1 bromopropane) has a higher free
energy of activation because its transition state resembles a less stable primary carbocation. This second
reaction
action is much slower and does not compete appreciably with the first reaction.
Free radical addition reactions: Anti
nti-Markovnikov addition:
 13

When unsymmetrical alkenes are treated with HBr in the presence of peroxides, the hydrogen atom
becomesattached to the carbon atom with the fewer hydrogen atoms. This exception is known as anti-
Markovnikov addition and also called peroxide effect or Kharasch effect.
 Thiseffect is due to the difference in the mechanism of the addition.
 In the presence of peroxide the addition of HBr takes place via free radical mechanism.
For example, with propene, the addition takes place as follows:
RO OR
CH3 CH CH2 + H Br CH3 CH2 CH2 Br
Light

This anti-Markovnikov addition occurs only when HBr is used in the presenceof peroxides and does
not occur significantly with HF, HCl, and HI even whenperoxides are present.
Mechanism:1) Chain initiation:
Light
RO OR RO RO + H Br R OH + Br
alkoxy
alkyl peroxide
Free radical

2) Chain propagation:
HBr
H3C CH2 CH2 H3C CH2 CH3 + Br
Br Br
1o radical; less stable 2-Bromopropane
Br (Minor product formed)
CH3 CH CH2

HBr
H3C CH CH2 Br H3C CH2 CH2 Br + Br
Fast
1-Bromopropane
2o radical; more stable
(main product)
3) Chain termination:
R + R R R
R + Br R R

Br + Br Br Br

 The main product of the reaction is 1-bromopropane because the more stable secondary radical is formed
preferentially.
 The more stable free radical predominates because it is formed faster.
 The product formed is anti-Markovnikov product where, hydrogen attached to the carbon with fewer
number of hydrogen atoms.
Elimination Reactions: (Dehydrohalogenation):Elimination reactions of alkyl halides are important
reactions that compete with substitutionreactions. In anelimination reaction the fragments of some molecule
(YZ) areremoved (eliminated) from adjacent atoms of the reactant. This elimination leads to thecreation of a
multiple bond.
 14

A widely used method for synthesizing alkenes is the elimination of HX from adjacentatoms of an
alkyl halide. Heating the alkyl halide with a strong base causes the reactionto take place.When theelements
of a hydrogen halide are eliminated from a haloalkane in this way, the reactionis often called
dehydrohalogenation.
H
C C + B C C + H B + X
X Base

Since the hydrogen atom that is eliminated in dehydrohalogenationis from the β carbon atom, these
reactions are often called β-eliminations. They are alsooften referred to as 1,2 eliminations.
Various strong bases have been used for dehydrohalogenations. Potassium hydroxide dissolvedin
ethanol (KOH/EtOH) is a reagent sometimes used, but the conjugate bases ofalcohols, such as sodium
ethoxide (EtONa), often offer distinct advantages.
Mechanisms of Dehydrohalogenations:Elimination reactions occur by a variety of mechanisms. With alkyl
halides, twomechanismsare especially important because they are closely related to the SN2 andSN1 reactions
that we have just studied. One mechanism, called the E2 reaction, isbimolecularin the rate-determining step
and the other mechanism is the E1 reaction, whichis unimolecular in the rate-determining step.
The E2 mechanism (elimination, bimolecular):Many elimination reactions are successful only when
carried out in the presence of a strong base. For example, when isopropyl bromide is heated with sodium
ethoxidein ethanol to form propene,
 The reaction rate depends on the concentration of isopropyl bromide and the concentration of ethoxide
ion. The rate equation is first order in each reactant and second order overall.
Rate = k[CH3CHBrCH3][C2H5O-].
 From the reaction order we infer that the transition state for the rate-determining step must involve both
the alkyl halide and the alkoxide ion (base). The reaction must be bimolecular. We call this type of
elimination an E2 reaction.
 The base abstracts a proton from the β-carbon and simultaneously the leaving group departs from the α-
carbon along with the pair of bonding electrons. Considerable experimental evidence indicates that an E2
reaction takes place in the following way.
Reaction:
C2H5O + H3C CH CH3 H2C CH CH3
Br
Mechanism:
 15

C2H5O H CH3
C2H5O H CH3 H CH3
C C H C C H C C + C2H5OH + Br
H H
H Br H Br H H
The basic ethoxide ion begins to Transition state At completion of the
remove a proton from the b carbon Partial bonds in the transition state reaction, the double bond
using its electron pair to form a extend from the oxygen atom that is is fully formed and the
bond to it. At the same time, the removing the b hydrogen, through the alkene has a trigonal
electron pair of the b C—H bond carbon skeleton of the developing planar geometry at each
begins to move in to become the p double bond, to the departing leaving carbon atom. The other
bond of a double bond, and the group. The flow of electron density is products are a molecule of
bromine begins to depart with the from the base toward the leaving ethanol and a bromide ion.
electrons that bonded it to the a group as an electron pair fills the p
carbon. bonding orbital of the alkene.
The E1 Reaction:Some elimination reactions follow a pathway that exhibits first-order kinetics. We callthese types of
eliminations E1 reactions. For example, Dehydrohalogenation of tert.butyl chloride
 The main feature of this mechanism is that under the influence of solvation forces, the electron attractinggroup
("leaving group") breaks away along with the bonding electrons. The resultant carbonium ion
subsequentlyloses a proton to the solvent or to some other proton acceptor.
 The reaction thus has two stages of which the first is the rate-determining step and as a result the reactionrate
depends only on the concentration of the first reactant.
Rate = k[(CH3)3CCl]
Reaction:

(CH3)3CCl + H2O H2C C(CH3)2 + H3O + Cl

Mechanism:
Step 1
CH3 CH3
Slow
H3C C Cl C + Cl
H2O H3C CH3
CH3
Aided by the polar solvent, a This slow step produces the relatively
chlorine departs with the stable 3° carbocation and a chloride ion.
electron pair that bonded it to The ions are solvated (and stabilized) by
the carbon. surrounding water molecules.
Step 2

H CH3
H O H CH3
H C C C C + H O H
H
H CH3 H CH3 H
A molecule of water removes one of the This step produces
hydrogens from the b carbon of the the alkene
carbocation. These hydrogens are acidic due
to the adjacent positive charge. At the same
time an electron pair moves in to form a
double bond between the a and b carbon
atoms.
 16

Orientation in elimination reactions:

The elimination reactions of unsymmetrical substrates usually yield mixtures of all possible products. There
are two empirical rules governing the orientation in these reactions.
(a) The Saytzeff Rule: It states that neutral substrates (alkyl halides or sulphonates) capable of forminga double bond
in either direction of the chain preferably yield that alkene in which there is greaternumber of alkyl groups attached to
the double bond. This rule applies to E1 reaction and to mostof E2 reactions. The following examples are typical.
CH3

H2C C CH2 CH3 (20%)

CH3 CH3
H2O
H3C C CH2 CH3 H3C C CH2 CH3
E-1
Elimination CH3
Br
H3C C CH2 CH3 (80%)
The preferential formation of more substituted alkenes in the above reactions can be correlated with therelative
stability of various alkenes. Calculations from heats of combustion and hydrogenation establish thatthe stability of a
double bond is increases by alkyl substitution on the double-bonded carbon atoms. Thus,the stabilities of alkenes
follow the order:
R2C = CR2> RCH = CR2> RCH = CHR > RCH = CH2> CH2 = CH2
The greater stability of the more substituted alkene is sometimes explained on the basis of hyper conjugation.
(b) Hofmann Rule: Suggests usually less substituted products if leaving group are positively charged(+NR3,+SR2 etc.)
and fluorine, actually more acidic β-hydrogen is abstracted to produce alkene.

H H

H3C C CH2 N CH2 C H + OH H2C CH2 + H3C CH2 CH2 N R

R - H2O
H R H R
H
KOH Hoffman product
H3C CH2 CH CH2 H3C CH2 CH CH2
C2H5OH
F
Oxidation Reactions with KMNO4:Potassium permanganate is a strong oxidizing agent. It is often used in organic
chemistry to oxidize many compounds. The applications of KMnO4 are:
1) Oxidation of an alkyl group (with a benzylic hydrogen) on an aromatic ring.
CH3 COOH
KMnO4

2) Cold dilute alkaline solutions of KMnO4 convert alkenes into diols (glycols). This behavior is also used as
a qualitative test for the presence of double or triple bonds in a molecule, since the reaction decolorizes the
initially purple permanganate solution and generates a brown precipitate (MnO2).
Cold dilute alkaline solutions of KMnO4 converts a C=C to a cis-diol via a cyclic manganate ester formation.
 17

R R R R
C C dil. alkaline. KMnO4
H C C H
H H
OH OH
R R cis-diol
OH H2O
Syn-addition C C
O O
Mn
O O
Oxidation Reactions with K2Cr2O7:K2Cr2O7, is a common inorganic chemical reagent, most commonly used as
an oxidizing agentin various laboratory and industrial applications. As with all hexavalent chromium compounds, it is
harmful to health. It is a crystalline ionic solid with a very bright, red-orange color.
Potassium dichromate is usually prepared by the reaction of potassium chloride on sodium dichromate.
Alternatively, it can be also obtained from potassium chromate by roasting chromite ore with potassium hydroxide. It
is soluble in water and in the dissolution process it ionizes:
K2Cr2O7 2K+ + Cr2O7-2
Cr2O7-2 + H2O 2CrO4-2 + 2H+
Potassium dichromate is an oxidizing agent in organic chemistry, and is milder than potassium permanganate.
It is used to oxidize alcohols. It converts primary alcohols into aldehydes and, under more forcing conditions, into
carboxylic acids.Secondary alcohols are converted into ketones. For example, menthone may be prepared by oxidation
of menthol with acidified dichromate. Tertiary alcohols cannot be oxidized.

R R R
H3C K2Cr2O7 H3C K2Cr2O7
H3C R No-Reaction
OH O
OH
R = H or CH3 R = CH3
In an aqueous solution the color change exhibited can be used to test for distinguishing aldehydes from
ketones. Aldehydes reduce dichromate from the +6 to the +3 oxidation state, changing color from orange to green.
This color change arises because the aldehyde can be oxidized to the corresponding carboxylic acid. A ketone will
show no such change because it cannot be oxidized further, and so the solution will remain orange.
Reduction reactions with Lithium Aluminum Hydride (LiAlH4): Lithium aluminum hydride (LAH) is a strong
reducing agent. It can reduce a variety of functional groups such as aldehydes, esters, acids, ketones, nitriles, epoxides
and azides. It vigorously reacts with water and all the reactions are performed in polar aprotic solvents.
In industrial scale, it is prepared from sodium aluminum hydride which is prepared by reaction of sodium,
aluminum and hydrogen at high temperature and pressure.
Na + Al + 2H2 NaAlH4
NaAlH4+LiCl LiAlH4 + NaCl
Reduction of Aldehydes and Ketones:
The aldehydes and ketones are reduced to give the corresponding alcohols when treated with LAH. For the
reduction of aldehydes and ketones, the reaction is generally performed in ether solvents at low temperature.
 18

O O OH OH
LiAlH4
Or Or
R H R R Ether R H R R
R= alkyl R= alkyl

Mechanism:
The hydride from LAH is transferred to the carbonyl group to form alkoxy anion which then forms complex with
aluminum. Similarly, four hydride atoms are replaced by four alkoxy groups and the aluminum complex thus formed is
then hydrolyzed by dilute acid to give the desired alcohol.
H R
H
O O
H H O
O
R H R H
H Al H O Al H O Al H
R H R R
H H H
H H H H
H R
H R H
H
O O H
OH O H
R O Al O H
H3O R H
4 H O Al O H R
H R
R H
H H R H H
O

R H
H
Reduction of Acids and Esters to alcohols:
O O
LAH + R'
LAH R OH OH
R OH R OR'
R OH
Acid Ester

Reduction of Azides, Nitriles and Nitro Compounds: The azides, nitriles and nitro compounds are reduced to the
corresponding amines in presence of LAH. The aromatic nitro compounds do not give the desired amines

R N3
Or
LAH
R C N R NH2
Or

R NO2

Sodium Borohydride (NaBH4)

The sodium borohydride is an ideal reducing agent for the reduction of aldehydes and ketones to give the
corresponding alcohols. Unconjugated ketones and aldehydes are rapidly reduced, usually in preference to a
conjugated carbonyl group that may be present elsewhere in the molecules. The reactions are performed in polar
solvents such as THF, DME, diglyme, hydroxyl solvent and water but the ethanol is the solvent of choice
 19

O O OH OH
NaBH4
Or Or
R H R R Ethanol R H R R
R= alkyl R= alkyl

Diel Alder Reaction (Cyclo-Addition Reaction):

Cyclo-addition reactions are one of the most important reactions of conjugated dienes. Cyclo-addition
involvesthe combination between a conjugated diene (4π-electron system) and a compound containing a double
bond(2π-electron system) called dienophile which means a diene loving or attracting molecule. As a result, a
sixmembered ring gets formed and the reaction is therefore known as cyclo-addition reaction. It is quite oftentermed as
(4 +2) cyclo-addition reaction because four 4π-electron system adds to a two 2π electron system.The reactions of this
type are known as: Diel Alder Reaction.

1,3-Butadiene alkene Cyclohexene

Diene Dienophile

 Electron-donating substituents in the diene accelerate the reaction; electron-withdrawinggroups retard it.
 For the dienophile it is just the reverse: donatinggroups decrease the rate, and withdrawing groups increase it.
 The diene must be in the cisoid (s-cis) conformation.
 With respect to the dienophile, the addition is stereo-specifically syn, withvery few exceptions. This means that
groups that are cis in the alkene willbe cis in the cyclohexene ring, and groups that are trans inthe alkene will be
trans in the cyclohexene ring.
CO2CH3 CO2CH3
+
CO2CH3 CO2CH3

Diene Dienophile cis-

CO2CH3 CO2CH3
+
H3CO2C CO2CH3
Diene Dienophile trans-
 20

Conformational isomerism:
The different arrangements of atoms in space that result from the free rotation around C-C bond axis
are called conformations or conformers. The phenomenon is called conformational isomerism.
H
H

H H C
H
H H
H
H
C H
H
H

Here θ (60°) is dihedral angle, angle between two planes.

Conformations of Butane [CH3—CH2—CH2—CH3]: Butane is four-member carbon alkane with molecular
formula C4H10. In butane we will define dihedral angle θ as angle between the two methyl groups.
To analyze the different conformations that result from rotation about C-2 and C-3 bond rotation of
one carbon atom in 60o increments either clockwise or anti-clockwise, while keeping the other carbon fixed.
Continue until you return to the original conformation.
Although each 60o about rotation converts a staggered conformation into an eclipsed conformation or
vice-versa, neither all the staggered conformations nor all the eclipsed conformations are the same.
In butane, torsional strain results from steric hindrance between the terminal methylgroups and
hydrogen atoms at C-2 and C-3. These interactions result in six important conformers of butaneshown as I–
VI below.
CH3 CH3
CH3 CH3 H CH3
H CH3 H H

H H H H H CH3 H H
H H H
H CH3
I Eclipsed II Gauche III Partial ecliped IV Anti
0o 60o 120o 180o
CH3
CH3 H
H3C H

H H H CH3
H H
H
VI Gauche V Partial ecliped
300
o 240o

 The anti-conformation (I) does not have torsional strain from steric hindrance because the groups are
staggered and the methyl groups are far apart. The anti-conformation is the most stable.
 The methyl groups in the gauche conformations III and V are close enough to each other that the
dispersion forces between them are repulsive; the electron clouds of the two groups are so close that they
 21

repel each other. This repulsion causes the gauche conformations to have approximately 3.8 kJ mol-1
more energy than the anti-conformation.
 The eclipsed conformations (II, IV, and VI) represent energy maxima in the potential energy diagram
(Fig. 2). Eclipsed conformations II and VI have repulsive dispersion forces arising from the eclipsed
methyl groups and hydrogen atoms. Eclipsed conformation IV has the greatest energy of all because of
the added large repulsive dispersion forces between the eclipsed methyl groups as compared to II and VI.
 Mainly three conformational isomers of butane and their stability order is
Anti ˃ Gauche (Skew) ˃ Eclipsed
 Although the barriers to rotation in a butane molecule are larger than those of an ethane molecule
(Section 4.8), they are still far too small to permit isolation of the gauche and anti-conformations at
normal temperatures. Only at extremely low temperatures would the molecules have insufficient energies
to surmount these barriers.

Fig. 2. Potential energy diagram of conformers of n-butane

 1

TECHNOLOGY OF WATER
Introduction:
Water is the most essential compound for all living matter on the earth. It plays an important
role in human living and industries.
Sources of water:
The two important sources of water are (1) surface water and (2) underground water.
Surface water:
The water available on the earth's surface is called as surface water. Surface water includes
rainwater, river water, lake water and seawater.
Underground water:
Underground water includes water present between the rocks in the earth crust, spring water,
well water etc.
Types of impurities present in water:
There are three types of impurities present in water. They are (i) Suspended and colloidal impurities.
(ii) Dissolved salts. (iii) Micro-organisms.
Hardness of water:
The water which does not produce lather with soap solution readily, but forms white scum or
precipitate, is called hard water. The reaction of soap (sodium stearate) with calcium chloride and
magnesium sulphate are depicted as follows.
2C17H35COONa + CaCl2 (C17H35COO)2Ca +2NaCl
Sodium stearate hardness Calcium stearate (insoluble)
2C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4
Magnesium stearate (insoluble)
Water which lathers easily on shaking with soap solution, called soft water.
There are two types of hardness in water. They are:
(i) Temporary Hardness: (Carbonate hardness) It is due to the presence of calcium bicarbonate
[Ca(HCO3)2] and magnesium bicarbonate [Mg(HCO3)2]. Temporary Hardness can be removed by
boiling of water.
(ii) Permanent Hardness: (Non-Carbonate hardness) It is due to the presence of chloride and
sulphate salts of calcium and magnesium. (CaCl2, CaSO4, MgCl2, MgSO4).It cannot be removed by
boiling. Hence it is known as permanent hardness.
Disadvantages of hard water:
 Hard water cannot be used for drinking purpose.
 It cannot be used for cooking purposes.
 It cannot be used for bathing and washing purposes as it does not give lather with soap.
 Hard water cannot be used in laboratories as it gives unwanted chemical reactions.
 Hard water cannot be used in boilers for steam generation.
 It cannot be used in sugar and paper industries.
 Hard water cannot be used in textile and leather industries.
 2

Degree of hardness (expression of hardness):

Hardness of water is expressed in terms of CaCO3 equivalents, because
1. It is highly insoluble in water
2. Its molecular weight is 100 that make the calculation easier
3. Most of the hardness causing substances is removed as CaCO3 precipitates.
The method of calculating degree of hardness from the following formula:
Hardness of the hardness causing salt in terms of
Mass of hardness causing salt × Molecular mass of CaCO
Calcium carbonate equivalents =
Molecular mass of hardness causing salt
Units for measuring hardness:
1. Milligram per litre (mg/L):
The number of milligrams of CaCO3equivalent hardness present per litre of water. Thus,
1mg/L = 1mg of CaCO3 eq.hardness per 1lit of water
But 1lit of water weighs = 1kg = 1,000g = 1000× 1000mg = 106mg
1mg/L = 1mg of CaCO3 eq. per 106 mg of water
= 1 part of CaCO3eq.per 106parts of water = 1ppm
2.Parts per million (ppm):
The parts of calcium carbonate equivalent hardness per 106 parts of water
i.e. 1ppm = 1part of CaCO3eq. hardness in 106 parts of water.
3. Degree Clarke (0Cl):
The number of grains of CaCO3equivalent hardness per gallon of water. Or it is the parts of
CaCO3 equivalent hardness per 70,000parts of water.
Thus:10 Cl = 1grain of CaCO3 eq. hardness per gallon of water.
10 Cl = 1part of CaCO3 eq. hardness per 70,000parts of water.
4. Degree French (0Fr):
Itis theparts of CaCO3 eq. hardness per105 parts of water.
Thus:10 Fr = 1part of CaCO3 eq. hardness per 105 parts of water.
Relationship between various units of hardness:
1ppm = 1mg/L = 0.10Fr = 0.070Cl

Numerical problems:
1. A sample of water gives on analysis 13.6 mg/L of CaSO4, 7.3mg/L of Mg(HCO3)2. Calculate the
total hardness and permanent hardness.
Sol:
Hardness causing Quantity of Molecular weight Equivalent ofCaCO3(mg/L)
salt(H.C.S) H.C.S(mg/L) of H.C.S
CaSO4 13.6 136 13.6 × 100
= 10
136
Mg(HCO3)2 7.3 146 7.3 × 100
=5
146
 3

The total hardness of water = 10+5 = 15mg/L

Permanent hardness = 10mg/L
2. Calculate the total hardness of 1000 litre of a sample of water containing the following impurities
16.2mg/L of Ca(HCO3)2, 11.1mg/L of CaCl2, 60mg/L of MgSO4 and 19mg/L of MgCl2.
Sol:
Hardness causing Quantity of Molecular weight of Equivalent of
salt(H.C.S) H.C.S(mg/L) H.C.S CaCO3(mg/L)
Ca(HCO3)2 16.2 162 16.2 × 100
= 10
162
CaCl2 11.1 111 11.1 × 100
= 10
111
MgSO4 60 120 60 × 100
= 50
120
MgCl2 19 95 19 × 100
= 20
95

Total hardness of water = 10+10+50+20 = 90mg/L

Total hardness of water for 1000 litres = 90× 1000 = 90,000mg/1000L
3. A sample of hard water contains the following dissolved salts per litre.CaCl2 = 111mgs, CaSO4 =
1.36mgs, Ca(HCO3)2 =16.2mgs, Mg(HCO3)2 = 14.6mgs, silica = 40mgs, turbidity = 10mgs.
Calculate the temporary, permanent and total hardness of water in ppm, degree Clarke and
degree French.
Sol:
Hardness Quantity of Molecular weight of Equivalent of
causing H.C.S(mg/L) H.C.S CaCO3(mg/L)
salt(H.C.S)
CaCl2 111 111 111 × 100
= 100
111
CaSO4 1.36 136 1.36 × 100
=1
136
Ca(HCO3)2 16.2 162 16.2 × 100
= 10
162
Mg(HCO3)2 14.6 146 14.6 × 100
= 10
146
Silica and turbidity must not be considered because they do not cause hardness to water.

Total hardness of water = 100+1+10+10 = 121mg/L

Temporary hardness of water = hardness of Ca (HCO3)2 + Mg (HCO3)2 in terms of CaCO3 equivalents.

10+10 = 20mg/L
 4

Permanent hardness of water = hardness of CaCl2+CaSO4 in terms of CaCO3 equivalents.

100+1 = 101 mg/L
Conversion of hardness:
1ppm = 1mg/L =0.070Cl = 0.10Fr
Total hardness of water = 121mg/L =121ppm = 121× 0.07 = 8.470Cl = 121× 0.1 = 12.10Fr
Temporary hardness = 20mg/L = 20ppm = 1.40Cl = 20Fr
Permanent hardness = 101mg/L =101ppm =7.070Cl = 10.10Fr
4. A ground water sample is analyzed as: Ca2+ = 150mg/L and Mg2+ =60mg/L. Calculate the total
hardness in ppm, mg/L.
Sol:
Hardness causing Amount of Mol.wt.of the H.C.S Equivalent of
salt(H.C.S) H.C.S(mg/L) CaCO3(mg/L)
2+ 150 × 100
Ca 150 40
= 375
40
Mg2+ 60 24 60 × 100
= 250
24

Total hardness of water = 375+250 = 625mg/L

625mg/L = 625ppm (1mg/L = 1ppm)
Specifications of industrial water:
Surface and ground water is normally used for industrial and domestic purposes. Each industry
has its own specifications for water and the treatment of water depends on the purpose for which it is
to be used.
Purpose Specification Remarks
Beverages Should not be alkaline Alkalinity in water tends to neutralize
the acids derived from fruits and
destroys the taste.
Dairies and allied Water should be colorless, tasteless and
industries free from pathogenic organisms
Laundries Water should be free from metals like Fe Hardness increases the consumption
and Mn and should be colorless of soaps. The salts of Fe and Mn
salts cause colorationof the fabric.
Paper industry Water should be free from hardness, Iron salts affect the color of the
alkalinity and metals paper.
Sugar industries Should be free from sulphates, nitrates Water containing sulphates, nitrates
and alkalinity and alkali carbonates if present
causes difficulties in crystallization of
sugar and the sugar so produced
may be deliquescent.
Potable water (water for drinking/municipal water)
Municipal water is mainly used for drinking purposes and for cleaning, washing and other
domestic purposes. The water that is fit for drinking purposes is called potable water.
 5

Specifications of potable water:

1. It should be clear, colorless and odorless.
2. It should be free from turbidity and other suspended impurities.
3. It should be free from dissolved gases and pH should be between 6.5 and 8.5.
4. It should be free from heavy metals like lead, arsenic, chromium, and manganese.
5. It should have low hardness (less than 300ppm).
6. It should be free from pathogenic bacteria.
Treatment of municipal water involves the following steps:
1. Screening: water is allowed to pass through the mesh screens whereby large floating materials
are removed.
2. Sedimentation: is a process of allowing water to stand undisturbed for 2-6 hours in big tanks,
when most of the suspended particles settle down at the bottom, due to gravity. The clear water is
then drawn from tank with the help of pumps.
3. Coagulation: is a process of removing fine suspended and colloidal impurities by adding
coagulants such as Al2(SO4)3, NaAlO2 etc. which produces gelatinous precipitate is called
flocculent, which absorbs smaller particles and converted into bigger particles. They can be easily
removed by filtration.
4. Filtration: colloidal matter, fine solid particles are removed. Water is passed through a large area
sand bed.
5. Disinfection/sterilization: the process of destroying or killing the disease producing bacteria,
micro organisms in the water and making it safe for use is called disinfection.
The chemicals used for killing bacteria are called disinfectants.Disinfection of water can be
carried out by following methods:
a) Boiling: water boiled for 10-15min, where most of the pathogenic bacteria are killed.
b) Ozonization:ozone is an unstable molecule which readily breaks
down, liberating one atom of oxygen. This nascent oxygen is very
powerful oxidizing agent and is capable of destroying the harmful
bacteria in addition to oxidation of organic matter.
Ozone is made by passing oxygen through ultraviolet light or a
cold electrical discharge. To use ozone as a disinfectant, it must be
created onsite and added to the water by bubble contact.
O3 O2 + [O]
c) Chlorination:Chlorination of water is the process of adding chlorine so as to make it fit for human
consumption as drinking water. Among halogens, chlorine is the most efficient disinfectant and is
added to public water supplies to kill disease-causing pathogens such as bacteria, viruses, and
protozoans that commonly grow in water supply reservoirs. Chlorine is a gas at atmospheric
pressures but liquefies under pressure. The liquefied gas is transported and used as such. As a
strong oxidizing agent, it kills pathogens via the oxidation of organic molecules. Chlorine and its
hydrolysis product hypochlorous acid readily penetrate the negatively charged surface of
 6

pathogens and are able to disintegrate the lipids that compose the
cell wall and react with intracellular enzymes and proteins,
making them nonfunctional. As a result, microorganisms either
die or no longer are able to multiply. Hypochlorous aid is a weak
acid and it dissociates at higher pH (above 6.5) to form H+ and
hypochlorite (OCl-) ions which cannot combine with enzymes
inside the cells of microorganisms. Thus, chlorine acts at its
optimum efficiency at a pH below 6.5. In pH range 6.5-8.5, both
these species HOCl and OCl- remains present in water and are commonly referred to as free or
available chlorine.
Cl2 + H2O HOCl + HCl
d) Addition of bleaching powder: Bleaching powder contains 80% chlorine. When bleaching
powder is used as disinfectant, this is method also called hypo-chlorination because disinfection is
due to hypochlorous acid (HOCl).
CaOCl2 + H2O Ca(OH)2 + Cl2
Cl2 + H2O HOCl + HCl
(Disinfectant)
e) UV-radiation:Ultraviolet water purification is the most effective method for disinfecting bacteria
from the water. Ultraviolet (UV) rays penetrate harmful pathogens in water and destroy
disease-causing microorganisms by attacking their genetic core (DNA). This is extremely
efficient in eliminating their ability to reproduce. Disinfecting your water with Ultraviolet light is
exceptionably simple, effective and environmentally safe. UV systems destroy 99.99% of harmful
microorganisms without adding chemicals or changing water’s taste or odor. This UV energy
(wavelength of 240-280 nm) is also naturally found in sunlight in very small quantities. The same
energy is produced in stronger intensities with help of high mercury discharge lamps, commonly
known as UV lamps.UV water purification is usually used with other forms of filtration such as
reverse osmosis systems or carbon block filters.
Ultraviolet Purification Advantages
 Chemical Free: UV purification does not use any chemicals like chlorine or leave any
harmful by products.
 Taste & Odor Free: UV does not add any chemical taste or odor to the water.
 Extremely Effective: One of the most effective ways to kill disease-causing microbes by
destroying 99.99%.
 Low Maintenance: Set and forget type of system, just change UV bulb annually.
Limitations in UV Water Systems: Ultraviolet purification itself is not enough to purify water down
to drinking water purposes. This is because the UV radiation is only effective for treating bacteria and
viruses. UV light does not work to eliminate contaminants such as chlorine, heavy metals and VOC’s
(Volatile Organic Compounds). UV systems are often paired with Reverse Osmosis Systems to provide
a complete purification process for the safest drinking water.
 7

Boiler troubles:
In the industries, water is used in boilers to produce steam. When a sample of hard water is
used in boiler to produce steam, the following problems will occur.
1) Sludge and Scale formation
1) Sludge and scale formation: The water evaporates continuously in boilers. The concentration of
dissolved salts increases progressively, when the concentration reaches saturation point, they are
thrown out in the form of precipitates (Sludge and scale).
Sludge: A loose and slimy precipitate formed within the boiler is called sludge.
Sludge’s can be formed by substances which have greater solubilities in hot water than in cold
water.
Salts like MgCO3, MgSO4, MgCl2, CaCl2 etc., are responsible for sludge formation in boilers.
Disadvantages: 1) Sludge is bad conductor of heat, hence, it wastes a portion of heat supplied. 2)
Excessive sludge formation reduces the efficiency of the boiler.
Prevention: 1) Frequent blow-down operation should be carried out 2) By using well-softened water.
Scale: A hard adhering coating on the inner walls of the boiler is called scale.
Salts like CaSO4 and Ca(HCO3)2 are responsible for scale formation in boilers.
Disadvantages: 1) Scale acts as a bad conductor of heat. 2) Scale formation can reduce the
efficiency of a boiler. 3) At high temperature scale formation can lead to explosion.
Removal of scale: 1) by thermal shocks 2) with the help of a wire brush, wood piece or scraper 3)
carbonate scales can be removed by 5-10 % HCl. 4) CaSO4 scale can be removed by EDTA solution.
Softening of water (External treatment):
The process of removing hardness producing salts from water is known as softening of
water.The treatment of boiler feed water given out side of the boiler.
In the industry, main three methods employed for softening of water are 1) Lime-soda process
2) Zeolite-permutit process 3) Ion exchange or demineralization process.
lon-Exchange Process: This is also known as de-mineralization process. Ion-exchange resins are
insoluble, cross-linked, long chain organic polymers(Fig. 4a). The functional groups attached to
the chains can exchange hardness producing cations and anions present in water.

Fig. 4a Ion-exchange resins

Fig. 4b lon-Exchange Process
 8

Process: The process involves the following

Step (a): The first chamber is packed with cation exchange resin (RH+).These resins are mainly
styrene-divinyl benzene copolymers, phenol-sulphonic acid formaldehyde resins. Such resins have
acidic functional groups like –SO3H, -COOH, capable of exchanging the cationic portion of minerals by
their hydrogen ions. When the hard water is passed through a bed of cation exchange resin it
exchanges hydrogen ions with Ca+2, Mg+2, K+, Na+ etc. of hard water (Fig. 4b).
2RH+ + Mg+2 R2Mg+2 + 2H+
2RH+ + Ca+2 R2Ca+2 +2H+
Thus hardness causing cations (Ca+2, Mg+2, etc.) are removed.
Step (b):The second chamber is packed with anion exchange resin (R'OH-).These resins are styrene-
divinyl benzene or amine-formaldehyde copolymers that contain basic functional groups like amino or
quaternary ammonium (-+NR3) or quaternary phosphonium or tertiary sulphonium groups an integral
part of the resin matrix. These resins after treatment with dilute NaOH solution, become capable of
exchanging their OH-ions with anions in water and therefore known as anion exchangers.The water
coming out of the first chamber contains H+, Cl-, SO4-2 and CO3-2; ions. It is now passed through anion
exchange resin bed which can exchange OH- ions with anions like Cl- , SO4-2 and CO3-2.
R'OH+ Cl- R'Cl+ OH-
2R'OH + SO4-2 R2’SO4 + 2OH-
2R'OH +CO3-2 R2'CO3+ OH-
Thus, hardness producing anions like Cl-, SO4-2 and HCO3- are removed.
The H+ ions produced from first chamber combine with OH- ions produced from second
chamber to form water
H+ + OH- H2O
Hence, the water produced from ion-exchange process is completely free from all cations and
anions of salts.
Regeneration of Resins:When used for a long period the resin bed getsexhausted and can be
regenerated.
(a) The exhausted cation exchange resin can be regenerated by passing dil. HCl.
R2Mg +2H+ 2RH + Mg+2
R2Ca + 2H+ 2RH + Ca+2
(b) The exhausted anion exchange resin can be regenerated by passing dil. NaOH.
R'Cl + OH- R'OH + Cl-
R2’SO4 + 2OH- 2R'OH+ SO4-2
After treatment, the columns are washed by de-ionized water. The resins are now ready for
use.
Advantages:
(a) The softened water by this method is completely free from all salts and fit for use in boilers.
(b) It produces very low hardness nearly 2 ppm.
(c) Highly acidic or alkaline water can be treated by this process.
 9

Mixed bed ion-exchanger:

This contains of a single ion-exchange column containing and
intimate mixture of strongly acidic and basic ion exchangers (Fig. 5). The
operational principle is same as discussed as above.
The water is allowed to pass through the mixed bed resin. Both
cations and anions present in water will be exchanged to give de-
mineralized water.
To regenerate such a bed deionizer, at first it is necessary to
separatethe two resins. These resins are then generated separately. Such a
mixed bed deionizer is convenient to use but comparatively more
expensive. Fig. 5. Mixed-bed
Desalination of brackish water: ion exchanger

It involves the removal salts from water. The salinity of water is

mostly due to dissolved sodium chloride and to a smaller extent of other inorganic salts. Sea water
containing an average of about 3.5% salts comes under this category (brackish water). This water is
totally unfit for drinking and other domestic purposes. Reverse osmosis method is commonly used for
desalination of brackish water.
(1) Reverse osmosis Method: when a semi-permeable
membrane separates two solutions of different
concentrations and the flow of solvent takes place from
'less concentrated' to a region of 'more concentrated’
due to osmosis. The semi-permeable membranes are
cellulose acetate, polymethyl methaacrylate and
polyamide polymers. Semi-permeable membrane can
allow only solvent (water) but not solute (salts) particles.
If more pressure, which is higher than osmotic pressure,
is applied then, reverse osmosis takes place, i.e., flow of
Fig. 6Reverse osmosis
solvent from higher concentration to less concentration
(Fig. 6). Using this principle drinking water is obtained
from brackish (sea water/ salt water). In this method, a pressure in the range of 15-40 kg/cm2 is
applied on the brackish water. The water molecules pass through the membrane while the salt gets
concentrated in the effluent stream which can be removed.
 1

Nano-Materials
Nano materials are defined as a set of substances where at least one dimension is less
than approximately 100 nanometers. A nanometer is a billionth of a meter. Nanomaterials are of
interest because at this scale unique optical, magnetic, electrical, and other properties emerge.
These emergent properties have the potential for great impacts in electronics, medicine, and
other fields.
Synthesis of Nanomaterials:
Sol-gel process: The sol-gel process, involves the evolution of inorganic networks through the
formation of a colloidal suspension (sol) and gelation of the sol to form a network in a
continuous liquid phase (gel). The precursors for synthesizing these colloids consist usually of a
metal or metalloid element surrounded by various reactive ligands. The starting material is
processed to form a dispersible oxide and forms a sol in contact with water or dilute acid.
Removal of the liquid from the sol yields the gel, and the sol/gel transition controls the particle
size and shape. Calcination of the gel produces the oxide.
Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based precursors
such as Si(OEt)4 (tetraethyl orthosilicate, or TEOS). The reactions involved in the sol-gel
chemistry based on the hydrolysis and condensation of metal alkoxides M(OR) can be described
as follows:
MOR + H2O → MOH + ROH (hydrolysis)
MOH + ROM → M-O-M + ROH (condensation)
Sol-gel method of synthesizing nanomaterials is very popular amongst chemists and is
widely employed to prepare oxide materials. The sol-gel process can be characterized by a series
of distinct steps.

1. Formation of different stable solutions of the alkoxide or solvated metal precursor.

2. Gelation resulting from the formation of an oxide- or alcohol- bridged network (the gel) by a
polycondensation reaction that results in a dramatic increase in the viscosity of the solution.
 2

3. Aging of the gel during which the polycondensation reactions continue until the gel transforms
into a solid mass, accompanied by contraction of the gel network and expulsion of solvent from
gel pores. The aging process of gels can exceed 7 days and is critical to the prevention of cracks
in gels that have been cast.
4. Drying of the gel, when water and other volatile liquids are removed from the gel network.
5. Dehydration, during which surface- bound M-OH groups are removed, there by stabilizing the
gel against rehydration. This is normally achieved by calcining at temperatures up to 800 0C.
6. Densification and decomposition of the gels at high temperatures (T>800 0C). The pores of
the gel network are collapsed, and remaining organic species are volatilized. The typical steps
that are involved in sol-gel processing are shown in the schematic diagram above.
Carbon nanotubes:
Carbon nano tubes (CNTs) which are hollow fibres. CNTs are extended tubes of rolled
graphene sheets (a planner network of inter connected planar hexagonal rings of carbon atoms)
which are typically closed at their ends by semi-fullerene-like structures. Defects in the
structures result in bends and transitions overall. The diameter of carbon nanotube remains in
the order of one nanometer but can go up to several microns to centimeters long. There are two
forms of CNTs namely:
1) Single-walled carbon nanotubes (SWCNT):
These are different types depending on the matter in which the graphene sheets are
rolled. The basic varities being zigzag, armchair, and chiral. Identification of a particular variety
can be made by following the pattern across the diameter of the tube and analyzing their cross-
sectional structure.
2) Multi-walled carbon nanotubes (MWCNT) :
It consists of several concentric Single-walled carbon nanotubes (SWCNT) with different
diameters. The forms are more complex here as each SWCNT can have different structures
resulting in a variety of sequential arrangements.
The simplest form being the one in which the concentric layers are identical but of
different diameters. In other varieties, two or more types of concentric SWCNTs remain arranged
in a different orders. These can have either regular layeres or random layeres.
Characteristics:
1) These materials have high thermal and electrical conductivity. Here, motion of electrons
fall under the regime of ballistic transport. It is the transport of electrons in a medium
with negligible electrical resistivity due to scattering. Ballistic transport is observed when
 3

the mean free path of the electron (the average length that the electron can travel freely,
i.e, before hitting against the walls.
2) Their mechanical strength is very high
3) Stable at high temperature
4) Stable against strong acids and other chemicals present in atmosphere.
Applications:
1) In conducting polymerscreens,
2) In electronics such as memory, semiconductor components and transparent conducting
films for touch screens, displays and solar cells.
3) To build ultra-capacitors in which energy storage capacity is much higher than the
traditional capacitors.
4) Used for preparation of structural materials such as
a) Textiles: CNT is used to make waterproof and tear-resistant fabrics
b) Body armor: Bullet proof jackets can be made using CNT fibres
c) Concrete: CNT in concrete increases its tensile strength and halt crack propagation.
d) Sports equipment: Stronger and lighter tennis rackets, bicycle parts etc.
Applications of nanomaterials:
Nanomaterials having wide range of applications in the field of electronics, fuel cells,
batteries, agriculture, food industry, and medicines, etc. It is evident that nanomaterials split
their conventional counterparts because of their superior chemical, physical, and mechanical
properties.
1) As materials: Nano tubes of MoS2 and WS2 are used as solid lubricants and NbSe2
becomes super conductor at low temperature.
2) Carbon nano tubes (CNT) are use full in lithium batteries, fluorescent displays, in
computers.
3) As sensors: Nanomaterials can be used as sensors for gases such as NO2 and NH3.
4) In Chemistry: Nano particles are used as catalysts in chemical industry due to the high
surface area, nano-catalysts tend to have exceptional surface activity.
5) In Medicine: Nano materials find applications in the field of medicine such as disease
diagnosis, drug delivery and molecular imaging, Longer-Lasting Medical Implants
6) Nanocoatings: Surface coating with nanometre thickness of nanomaterial can be used to
improve properties like wear and scratch-resistant, hydrophobic properties.
 4

Composites

All the engineering materials (high polymers, metals and ceramics) possess their
outstanding characteristics as well as limitations. None of these can be properly used where very
stringent and specific requirements are required.
E.g., high temperature reactors, supersonic aircrafts, missiles, etc.
In order to meet such stringent and specific requirements, scientists and technologists
have developed a new class of materials called “composites”.
A composite may be defined as “a material system consisting a mixture of two or
more micro-constituents, which mutually insoluble, differing in form or composition
and forming distinct phases”. Such a combination, possess properties different from those of
any of its constituents.
Advantages (or) Characteristics of composites
(1) They possess higher specific strength and lower specific gravity.
(2) They possess lower electrical conductivity and thermal expansion.
(3) They possess better creep, fatigue strength, corrosion and oxidation resistance.
(4) They maintain very good strength, even up to high temperatures.
Constituents of composites: Composites consist of two important constituents.
(1) Matrix phase (or) Matrix resin (2) Dispersed phase (or) Reinforcement
1. Matrix phase (or) Matrix resin
Matrix phase is the continuous body constituent, which encloses the dispersed phase and
gives bulk form. Matrix phase may be metals, ceramics or polymers (liquid resins). Composites
using these matrixes are known as
(a) Metal Matrix Composites (MMC)
(B) Ceramic Matrix Composites (CMC)
(c) Polymer Matrix Composites (PMC) respectively.
The essential requirements of good matrix materials are:
a) It should be ductile b) The bond strength between matrix and dispersed phase must be
high for effective stress transmittance during application of load c) It should have
resistance towards corrosion.
Functions of matrix phase:
1. Binds the dispersed phase together through its cohesive and adhesive forces.
2. Acts as a medium for transmission and distribution of applied load to the dispersed phase
3. Protects the dispersed phase from chemical action
4. Prevents propagation of brittle cracks by virtue of its plasticity and softness.
 5

2. Dispersed phase (or) Reinforcement

Dispersed phase is the structural constituent, which determines the internal structure of
composite.
It is a process of improving the characteristics of the matrix by adding reinforcing agents.
The reinforcing agents may be organic or inorganic in nature. They may be in the form of
powder, flakes, fibres. These materials are characterized by high strength to weight ratio.
Excellent resistance to erosion, corrosion, etc., and ease of fabrication. For effective structural
performance, there should be a strong and adhesive bond between the matrix phase (or) matrix
resin and the dispersed phase (or) reinforcing agents.
Classification of composites: Composites are classified mainly into three types based on the
matrix material
1. Polymer Matrix composites (PMC)
2. Metal Matrix Composites (MMC)
3. Ceramic Matrix Components (CMC)
Polymer Matrix composites:
Polymer matrix composite is a material in which a polymer (resin) matrix is
combined with a fibrous reinforcing dispersed phase.
1. It possesses superior properties like higher yield strength, fracture strength and fatigue
life.
2. Since fibre prevents slip and crack propagation, the mechanical properties of FRP gets
increased.
3. It possesses high corrosion resistance and heat resistance property.
Metal Matrix Composites:
Metal matrix composite is a material in which a continuous metallic phase (the matrix) is
combined with another phase (the reinforcement) to strengthen the metal and increase high-
temperature stability.
1. Metal matrix composites exhibit extremely good thermal stability, high strength, good
stiffness and low specific weight.
2. MMCs also have other advantages like fracture toughness, ductility and enhanced elevated
temperature performance at
3. They can withstand at elevated temperatures in corrosive environment than polymer
composites.
 6

Ceramic Matrix Composites:

Ceramic Matrix Composite is a material in which ceramic fibre is embedded in a ceramic
matrix.
1. CMCs are used at temperatures above 1500 0
C, because of their good corrosion
resistance, stability at elevated temperatures and high compressive strength.
2. Ceramics provide necessary strength at high temperature with good oxidation resistance.
3. The matrixes used are glass, ceramics, carbides, nitrides, oxides and borides, the
reinforcements are Al2O3, B, C, SiC and SiO2
Composites are classified in to two groups based on the type of reinforcement:
1) Particle reinforced composites 2) Fibre reinforced composites 3) Laminate or structural
Composites
Fibre reinforced composites:
The fibres are used as dispersed phase for reinforcement of materials. Such composites
involve three components namely, filament (i.e. fibre), a matrix (i.e. encapsulating agent for the
filament) and binding agent, which ties fibre filament to the polymer.
Some important types of fibre-reinforced composites:
1. Glass fibre-reinforced polymer composite: In these type composites, glass fibres are
employed as reinforcement for improving the characteristics of composites. The glass fiber is a
material obtained by making the molten glass flow through orifices and then it solidifies and has
the flexibility to be used as fiber. Glass fibers are one of the most widely used polymer
reinforcements with nearly 90% of all FRPs made of glass fibers. Of which, the oldest and the
most popular form is the E-glass or electrical grade glass. Other types of glass fibers include A-
glass or alkali glass, C-glass or chemical resistant glass, and the high strength R-glass and/ or
S-glass.
These composites possess high tensile strength, high impact resistance and exhibit
excellent resistance to corrosion and chemicals.
Applications:
 Composites reinforced with glass fibres are good electrical and thermal insulators.
 Glass fibres are transparent to radio waves and are used in antennas and radars.
 The automobile industry the glass fibre reinforced Polymer matrix composites are used to
make external body panels, bumper beams, pultruded body panels and air ducts, engine
components, etc.
 7

 The sporting goods industry was one of the first to make use of glass-fiber-reinforced
composites. Examples include bicycle frames, tennis rackets, golf-club shafts, cricket bats,
skis, etc. Braided fibres in a resin matrix give high torsional stiffness to skis.
 Glass fibres are used without matrix as filters and fibrous blankets for thermal and
acoustical insulation.
 Glass fibres in the form of membrane is the architectural membrane made of
poly(tetrafluoroethylene) (PTFE)-coated glass fibre for ceilings of stadiums and airports.

Applications: Automobile parts, storage tanks, plastic pipes.

2. Carbon fibre-reinforced polymer composites: In such composites, high performance
carbon fibres are used as reinforcement. These are also known as advanced polymer matrix
composites or high-performance composites which are used at elevated temperatures and
corrosive environment.
Carbon fibers consist almost exclusively of carbon atoms. Almost all commercial carbon
fibers are produced by first converting a carbonaceous precursor into fiber form. Precursors for
carbon fibers include cellulosic rayon, polyacrylonitrile (PAN) and pitch. The precursor fiber then
is crosslinked in order to render it infusible. Finally, the crosslinked precursor fiber is heated at
temperatures in an inert atmosphere to drive off nearly all of the non-carbon elements,
converting the precursor to a carbon fiber.
Carbon fiber is high strength. It is low weight. It is cost-efficient. It is characterized by
high stiffness. It is conductive to electricity and is one of the most corrosion and heat resistant
materials available for commercial use.
Applications:
 Carbon fiber reinforced polymers are advanced composite materials used in a wide range
of applications, from aerospace to automotive.
 When bound with plastic polymer resin, carbon fiber creates a composite material that is
extremely strong, durable and lightweight and can be found in many forms, including
fabrics, tubes and tows.
 CFRP is now widely used in sports equipment such as in squash, tennis, and badminton
racquets, sport kite spars, high-quality arrow shafts, hockey sticks, fishing
rods, surfboards, high end swim fins, and rowing shells.
 8

APPLICATIONS OF COMPOSITES
1. Aircraft/Military: Composites are used in commercial, pressure and military aircrafts
including components for aerospace and related applications.
2. Automotive/Transportation: It is used in the manufacturing of some products including
parts for automobiles, trucks, rail and farm applications.
3. Civil infrastructure: It is used as repair and replacement material for civil infrastructure
including buildings, roads, bridges, pilling, etc.,
4. Construction: It is used as a material for building of homes, offices and architectural
components, products including swimming pools, bathroom fixtures, wall panels, roofing,
architectural cladding.
5. Consumer: It is used in the products including sports and recreational equipment such as
golf clubs, tennis rackets, snow mobile, mobile campers, furniture, and microwave cookware.
6. Corrosion resistant equipment: Products for chemical resistant service such as tanks,
ducts and hoods, pumps, fans, grating, chemical processing pulp and paper, oil and gas.
7. Electrical: It is used in the components for both electrical and electronic applications such as
pole line hardware, sub-station equipment, microwave antennas, printing wiring boards, etc.,
8. It is used in the manufacture of products for commercial, pleasure and naval boats and ships.
CONDUCTING POLYMERS
Polymers are poor conductors of electricity and generally used as electrical insulators and
dielectric materials. However, there are polymers with improved electrical conductivity prepared
by the addition of some additives such as conducting metals like copper and silver or other
materials.
An organic polymer with highly delocalized π-electron system, having electrical
conductance on par with metallic conductor is called a conducting polymer.
For example, polyacetylene, polypyrrole, polyaniline.
 9

Classification of conducting polymers:

Conducting polymers

Intrinsic Conducting Polymers Extrinsic Conducting Polymers

The conjugated double present in the Externally added ingadients to the
polymer structure is responsible for the polymer are responsible for the
conduction of electricity conduction of electricity

Intrinsic polymers Doped conducting polymers

with conjugation Conduction is due to the +ve or -ve
Conductance is due to the charge created on polymer back bone
presence of pi-electrons in the
using oxidizing or reducing reagents.
back-bone of the polymer chain i.e., doping agents
Ex. Polyacetylene Ex. Emeraldine salt

n
Polyaniline (Emeraldine base)
N N N N
n

Conductivity element Blended conducting

filled polymer polymer
Polymer holds a conducting element Ex. Blending the
Ex. Carbon black filled polymer conducting and
non-conducting polymers
Ex. 40% polypyrrole

Intrinsic conducting Polymers:

These polymers are characterized by intensive conjugation of double bonds in their structure i.e. the backbone
of the polymer.
Again, intrinsic conducting polymers are two types as given below.
 10

1) Conducting polymers having conjugation: Such polymers having conjugated double bonds in the backbone
possess their conductivity due to л electrons. In л bonding the overlapping of the orbitals is lateral over the entire
backbone resulting in the formation of valence bands and conducting bands which were separated by a significant
Fermi energy gap. The electrical conductivity takes place in an electric field, conjugated ∏ electrons of the polymer
get excited and gets the sufficient energy to jump the gap and reach into conduction band.

Examples:

n HC CH CH CH
n
Acetylene Polyacetylene

H H
Polymerization N N
2n
N N N
H H H n
Pyrrole polypyrrole

2n NH2
Polymerization
N N N

Aniline n
Polyaniline
All the above polymers possess conductivities around 10-10 Scm-1 which is sufficient for their use in any
engineering applications.
2) Doped conducting polymers: The conducting polymers having л electrons in their backbone can easily be
oxidized or reduced because they possess low ionization potential and high electron affinities. Hence, their
conductance can be increased by introducing a positive charge or negative charge on polymer backbone by oxidation
or reduction. This process is similar to semiconductor technology and is called doping. Doping is again two types.
1. Creating a positive site on polymer backbone called p-doping
2. Creating a negative site on the polymer backbone called n-doping.
p-Doping: p-Doping is done by oxidation of a conducting polymer like polyacetylene with a Lewis acid or iodine
vapour. This is also called oxidative doping.

CH CH + 2 FeCl3 CH CH FeCl4
n n
Polyacetylene

2 CH CH + 3I2 2 CH CH I3
n n
Polyacetylene
During oxidation process the removal of ∏ electron from polymer back bone lead to the formation of a delocalized
radical ion called polaron having a hole in between valence band and conducting band as shown below.
The second oxidation of the polaron results in two positive charge carriers in each chain called bipolaron,
which are mobile because of delocalization. These delocalized charge carriers are responsible for conductance when
placed in electric field.
 11

-e
+ I2
CCl4
Polyacetylene Oxidation Polaron (radical cation)

-e
+ I2
CCl4
Polaron (radical cation) Oxidation Bipolaron (dication)

Soliton pair
p-doped polyacetylene
n-Doping: n-Doping is carried out by reduction process by the addition of an electron to polymer backbone by using
reducing agents like sodium naphthalide Na+(C10H8)-. Formation of polaron and bipolaron takes place in two steps,
followed by recombination of radicals, which yields two charge carriers on the polyacetylene chain responsible for
conduction as shown below.
The electron added to polyacetylene by reductive doping does not go into the conducting band but goes into
an intermediate electronic state within the band gap of radical anion (polaron).

+e
Na+ (C10H8)-
Polyacetylene Polaron (radical anion)

+e

Na+ (C10H8)-
Polaron (radical anion) Bipolaron (dianion)

Bipolaron contains electrons in the energy levels residing in the band gap. The dianion lowers its energy by
segregating into two negative solitons at the mid gap energy levels. The presence of holes in the band gap allows
facile jumps of electrons from valence band into the conduction band. This leads to the generation of conduction
pathways. As a consequence, the conductivity increases significantly.
Polyanilines exist in several oxidation states as far as electrical conductivities are concerned varying from 10-11
S/cm to > 105 S/cm. The flexible dark blue films of conducting polyaniline are made by protonic doping i.e.
protonation of amine nitrogen atoms in the backbone. Doping is a reversible process deprotonation can also be done
by treatment with alkali. Emeraldine salt is also known as synthetic metal because it possesses metallic conductivity,
metallic luster and metallic sound.
 12

N N N

n
Emeraldine Conductivity 10-10 S/cm

HCl

Cl Cl Cl
N N N

H H H n

Emeraldine salt (Conductivity 103 S/cm

Advantages of intrinsic conducting polymers:
The following are the advantages of the intrinsic conducting polymers.
1. These polymers possess good conductivity. 2) They can store a charge
3) lon-exchange is possible with these polymers. 4) They absorb visible light to give coloured products.
Extrinsically Conducting polymers:
The conductivity of these polymers is due to the presence of externally added ingredients in them. Again, the
extrinsically conducting polymers are two types.
1) Conducting element filled polymers: The polymer acting as a binder to hold the conducting element such as
carbon black, metallic fibres, metallic oxides etc. Minimum concentration of conducting filler is added so that the
polymer starts conducting. This minimum concentration of conductive filler is called percolation threshold. At this
concentration of filler, a conducting path is formed in polymeric material. The most preferred filler is the special
conducting grade C black has very high surface area, more porosity and more of filamentous properties.
Advantages of conducting element filled polymers:
1. These polymers are low cost polymers. 2) They are light in weight and mechanically durable.
3) These polymers are strong with good bulk conductivity. 4) They are fabricated very easily to any design.
Applications of conducting element filled polymers are used in hospitals and operation theatres.
The disadvantage of the conducting element filled polymers is that addition of 10% carbon black will
drastically decrease the tensile strength, elongation strength and impact strength of the polymer.
Blended conducting polymers: The conventional polymer is blended with a conducting polymer to improve
physical, chemical, electrical and mechanical properties along with the processing properties. Examples: 4O% of
polypyrrole in a conventional polymer gives higher impact strength. These blended polymers are used in
electromagnetic shielding.
Applications of conducting polymers:
1. The conducting polymers are used in rechargeable batteries, small in size (button size), producing current
density up to 50 mA/cm2.
2. Conducting polymers are also used for making analytical sensors for pH, O2, NO2, SO2, NH3 and glucose.
3. The conducting polymers are used for making ion exchangers. These membranes made of conducting
polymers show selective permeability for ions and gases hence they are used for control release of drug.
4. The conducting polymers are used making electronic displays and optical fibres.
5. They are used for electron beam lithography.
6. The conducting polymers are applicable in photovoltaic devices.
 13

Drugs
A drug (French-Drogue a dry herb) is defined as “any chemical agent which
affects living protoplasm and is intended for use in the treatment, prevention of
disease.”
Drug classes that are defined by their therapeutic use include:

 Analgesic  Antibiotic  Anticoagulant  Antidepressant

 Anticancer  Antiviral  Antidiabetic  Sedative
Aspirin: Is an analgesic or painkiller is any member of the group of drugs used to
achieve analgesia, relief from pain
Synthesis:
The synthesis of aspirin is classified as an esterification reaction. Salicylic acid is treated
with acetic anhydride, an acid derivative, causing a chemical reaction that turns salicylic
acid's hydroxyl group into an ester group (R-OH → R-OCOCH3). This process yields aspirin
and acetic acid, which is considered a byproduct of this reaction. Small amounts of sulfuric
acid (and occasionally phosphoric acid) are almost always used as a catalyst.
O OH O OH

OH O O O CH3
H2SO4
+
O O
Salicylic acid Acetic anhydride Aspirin
Physical properties
Aspirin, an acetyl derivative of salicylic acid, is a white, crystalline, weakly acidic substance, with
a melting point of 136 °C
Applications:
 Aspirin, also known as acetylsalicylic acid (ASA), is a medication used to treat pain, fever,
or inflammation. Specific inflammatory conditions in which aspirin is used include Kawasaki
disease, pericarditis, and rheumatic fever.
 Aspirin given shortly after a heart attack decreases the risk of death. Aspirin is also used
long-term to help prevent further heart attacks,
 For pain or fever, effects typically begin within 30 minutes.
Disadvantages:
 Aspirin is a nonsteroidal anti-inflammatory drug (NSAID) but also suppresses the normal
functioning of platelets.
Paracetamol: (Antipyretic is medication used to lower body temperature when a fever is
present)
 14

Synthesis:
Paracetamol is made by reacting 4-aminophenol with ethanoic anhydride (more commonly called
acetic anhydride) in the presence 3-4 drops of H2SO4. This reaction forms an amide bond and
ethanoic acid as a byproduct. When the reaction is complete the paracetamol is then isolated
and purified.
O
O O
H2SO4
HO NH2 + HO NH CH3
O
Paracetemol
4-aminophenol Acetic anhydride

 Paracetamol, also known as acetaminophen or APAP, is a medicine used to

treat pain and fever.
 It is typically used for mild to moderate pain relief. Evidence for its use to relieve fever in
children is mixed.
 It is often sold in combination with other medications, such as in many cold medications.
 In combination with opioid pain medication, paracetamol is also used for severe pain such
as cancer pain and pain after surgery.
Disadvantages:
 Paracetamol is generally safe at recommended doses. Serious skin rashes may rarely occur,
and too high a dose can result in liver failure.
Atenolol:
Synthesis:
HO HO
H2O O
CN
NH2
4-Hydroxy-benzyl cyanide 2-(4-Hydroxyphenyl)-acetamide
Cl O
epichlorohydrin

NH2 O
H3C HN O O
O O
OH
CH3 isopropylamine
NH2 NH2
Atenolol 2(4-(2,3-epoxypropoxy)-phenyl)
acetamide
 15

Applications:
 Atenolol, is a medication of the beta blockers type, primarily used to treat high blood
pressure and angina.
 Lowering high blood pressure helps prevent strokes, heart attacks, and kidney problems.
 This medication is also used to treat chest pain (angina) and to improve survival after
a heart attack. It works by slowing down the heart and reducing its workload.
 Other uses include the prevention of migraines.
 Atenolol is used for a number of conditions including hypertension, angina, long QT
syndrome, acute myocardial infarction, supraventricular tachycardia, ventricular tachycardia,
and the symptoms of alcohol withdrawal.
Disadvantages:
 Atenolol was the main β-blocker identified as carrying a higher risk of provoking type 2
diabetes.
 Antihypertensive therapy with atenolol provides weaker protective action against
cardiovascular complications