For More Material Join: @JEEAdvanced_2024

Contents
The Solid State ........................................................................................................................... 1

Solutions ................................................................................................................................. 22

Electrochemistry ...................................................................................................................... 31

Chemical Kinetics .................................................................................................................... 43

Surface Chemistry.................................................................................................................... 52

General Principles and Processes of Isolation of Elements .................................................... 73

The p-Block Elements ............................................................................................................. 85

The d-and f-Block Elements .................................................................................................. 106

Coordination Compounds ..................................................................................................... 115

Haloalkanes and Haloarenes .................................................................................................. 126

Alcohols, Phenols and Ethers ................................................................................................ 142

Aldehydes, Ketones and Carboxylic Acids ........................................................................... 158

Amines .................................................................................................................................. 169

Biomolecules.......................................................................................................................... 180

Polymers ................................................................................................................................ 194

Chemistry in Everyday Life ................................................................................................... 203

For More Material Join: @JEEAdvanced_2024

 The Solid State

⮚ General Characteristics of Solid State

i. Have definite mass, volume and shape, incompressible and rigid.
ii. Intermolecular distances are short.
iii. Intermolecular forces are strong.
iv. Constituent particles have fixed positions and can only oscillate about their mean
positions.
v. They are incompressible and rigid.

⮚ Amorphous and Crystalline Solids

● The word amorphous is derived from the Greek word amorphos which means no
form.
● Glass, rubber and plastics are typical examples of amorphous solids.
● Amorphous solids soften over a range of temperatures and can be moulded and blown
into various shapes. On heating they become crystalline at some temperature.
● Some glass objects from ancient civilisations are found to become milky in
appearance because of some crystallisation.
● Like liquids, amorphous solids have a tendency to flow, though very slowly.
Therefore, sometimes these are called pseudo solids or super cooled liquids.
● Glass panes fixed to windows or doors of old buildings are invariably found to be
slightly thicker at the bottom than at the top. This is because the glass flows down
very slowly and makes the bottom portion slightly thicker.
● Amorphous silicon is one of the best photovoltaic material available for conversion of
sunlight into electricity.
Distinction between Crystalline and Amorphous Solids

1
For More Material Join: @JEEAdvanced_2024
 Two-dimensional structure of (a) quartz and (b) quartz glass
⮚ Classification of Crystalline Solids
● All the metallic elements like iron, copper and silver; non – metallic elements like
sulphur, phosphorus and iodine and compounds like sodium chloride, zinc sulphide and
naphthalene form crystalline solids.
● Crystalline solids can be classified on the basis of nature of intermolecular forces
operating in them into four categories viz., molecular, ionic, metallic and covalent
solids.
Different Types of Solids

2
For More Material Join: @JEEAdvanced_2024
⮚ Crystal Lattices and Unit Cells
● A regular three-dimensional arrangement of points in space is called a crystal lattice.
● There are only 14 possible three-dimensional lattices. These are called Bravais Lattices
The following are the characteristics of a crystal lattice:
(a) Each point in a lattice is called a lattice point or lattice site.
(b) Each point in a crystal lattice represents one constituent particle which may be an
atom, a molecule (group of atoms) or an ion.
(c) Lattice points are joined by straight lines to bring out the geometry of the lattice.
● Unit cell is the smallest portion of a crystal lattice which, when repeated in different
directions, generates the entire lattice.

A portion of a three-dimensional cubic lattice and its unit cell.

● A unit cell is characterised by:
(i) Its dimensions along the three edges, a, b and c.
(ii) Angles between the edges, α (between b and c) β (between a and c) and γ (between
a and b). Thus, a unit cell is characterised by six parameters, a, b, c, α, β and γ.

Illustration of parameters of a unit cell

⮚ Primitive and Centred Unit Cells

a. Primitive Unit Cells - When constituent particles are present only on the corner
positions of a unit cell. In all, there are seven types of primitive unit cells.

3
For More Material Join: @JEEAdvanced_2024
b. Centred Unit Cells - When a unit cell contains one or more constituent particles
present at positions other than corners in addition to those at corners.
Centred unit cells are of three types:
i. Body-Centred Unit Cells: Such a unit cell contains one constituent particle (atom,
molecule or ion) at its body-centre besides the ones that are at its corners.
ii. Face-Centred Unit Cells: Such a unit cell contains one constituent particle present at
the centre of each face, besides the ones that are at its corners.
iii. End-Centred Unit Cells: In such a unit cell, one constituent particle is present at the
centre of any two opposite faces besides the ones present at its corners.
Seven primitive unit cells and their Possible Variations as Centred unit cells

4
For More Material Join: @JEEAdvanced_2024
⮚ Unit Cells of 14 Types of Bravais Lattices
1. Cubic crystal system -

2. Tetragonal crystal system -

3. Orthorhombic crystal system –

4. Hexagonal crystal system -

5
For More Material Join: @JEEAdvanced_2024
 5. Rhombohedral or trigonal crystal system -

6. Monoclinic crystal system -

7. Triclinic crystal system -

⮚ Number of Atoms in a Unit Cell

❖ Primitive Cubic Unit Cell
- Primitive cubic unit cell has atoms only at its corner.
- Each atom at a corner is shared between eight adjacent unit cells.
- Everyone shares ⅛ of its part and there are 8 in total. That’s why we can say 1 is
the effective number of atoms.

A primitive cubic unit cell (a) open structure (b) space-filling structure
(c) actual portions of atoms belonging to one unit cell.

6
For More Material Join: @JEEAdvanced_2024
 ❖ Body Centred Cubic Unit Cell
o A body-centred cubic (bcc) unit cell has an atom at each of its corners and also one
atom at its body centre.
o 8 corners × ⅛ per corner atom = 1 atom
o 1 body centre atom = 1 × 1 = 1 atom
o Total number of atoms per unit cell = 2 atoms

A body-centred cubic unit cell (a) open structure (b) space filling structure
(c) actual portions of atoms belonging to one unit cell.
❖ Face Centred Cubic Unit Cell
o A face-centred cubic (fcc) unit cell contains atoms at all the corners and at the centre
of all the faces of the cube.
o 8 corners × ⅛ per corner atom = 1 atom
o 6 face centres × ½ per face centre atom = 6 × 0.5 = 3 atom
o Total number of atoms per unit cell = 4 atoms

A face-centred cubic unit cell (a) open structure (b) space filling structure
(c) actual portions of atoms belonging to one unit cell.
⮚ Close Packed Structures
(a) Close Packing in One Dimension
- Each sphere is in contact with two of its neighbours.
- Number of nearest neighbours of a particle is called its coordination number.
- In one dimensional close packed arrangement, the coordination number is 2.

Close packing of spheres in one dimension

7
For More Material Join: @JEEAdvanced_2024
(b) Close Packing in Two Dimensions
Structure can be generated by stacking (placing) the rows of close packed spheres. This
can be done in two different ways -
(i) Square close packing in two dimensions (AAAA) -
● Second row may be placed in contact with the first one such that the spheres of the
second row are exactly above those of the first row.
● The spheres of the two rows are aligned horizontally as well as vertically.
● If the first row is termed as ‘A’ type row, the second row being exactly the same as
the first one, is also of ‘A’ type. Similarly, we may place more rows to obtain AAA
type of arrangement.
● Coordination no. 4, named as two-dimensional square close packing.

(ii) Hexagonal close packing of spheres in two dimensions (ABAB) -

● The second row may be placed above the first one in a staggered manner such that
its spheres fit in the depressions of the first row.
● If the arrangement of spheres in the first row is called ‘A’ type, the one in the second
row is different and may be called ‘B’ type.
● When the third row is placed adjacent to the second in a staggered manner, its
spheres are aligned with those of the first layer.
● Hence this layer is also of ‘A’ type. The spheres of similarly placed fourth row will
be aligned with those of the second row (‘B’ type).
● Hence this arrangement is of ABAB type.
● In this arrangement there is less free space and this packing is more efficient than
the square close packing.
● Coordination no 6, named as two-dimensional hexagonal close packing.

8
For More Material Join: @JEEAdvanced_2024
(c) Close Packing in Three Dimensions
● All real structures are three-dimensional structures.
● Can be obtained by stacking two dimensional layers one above the other.
(i) Three-dimensional close packing from two dimensional square close-packed
layers (AAA... type)
● Three-dimensional close packing from two dimensional square close-packed
layers.
● While placing the second square close-packed layer above the first we follow the
same rule that was followed when one row was placed adjacent to the other.
● The second layer is placed over the first layer such that the spheres of the upper
layer are exactly above those of the first layer.
● In this arrangement spheres of both the layers are perfectly aligned horizontally as
well as vertically. Thus this lattice has a AAA.... type pattern.
● The lattice thus generated is the simple cubic lattice, and its unit cell is the primitive
cubic unit cell.

(ii) Three-dimensional close packing from two dimensional hexagonal close packed
layers: Three-dimensional close packed structure can be generated by placing layers
one over the other.
(a) Placing the second layer over the first layer.
● A two-dimensional hexagonal close packed layer ‘A’ and place a similar layer
above it such that the spheres of the second layer are placed in the depressions of
the first layer.
● Since the spheres of the two layers are aligned differently, we call the second layer
as B.
● It can be observed from fig. that not all the triangular voids of the first layer are
covered by the spheres of the second layer.

9
For More Material Join: @JEEAdvanced_2024
 ● Wherever a sphere of the second layer is above the void of the first layer (or vice
versa) a tetrahedral void is formed. These voids are called tetrahedral voids because
a tetrahedron is formed when the centres of these four spheres are joined. Have
been marked as ‘T’ in Fig. One such void has been shown separately -

● At other places, the triangular voids in the second layer are above the triangular
voids in the first layer, and the triangular shapes of these do not overlap.
● One of them has the apex of the triangle pointing upwards and the other downwards.
These voids have been marked as ‘O’ in above fig. Such voids are surrounded by
six spheres and are called octahedral voids. One such void has been shown
separately -

● The number of these two types of voids depend upon the number of close packed
spheres. Let the number of close packed spheres be N, then:
The number of octahedral voids generated = N
The number of tetrahedral voids generated = 2N
(b) Placing the third layer over the second layer: When the third layer is placed over the
second, there are two possibilities:
(i) Covering Tetrahedral Voids:
● Tetrahedral voids of the second layer may be covered by the spheres of the third
layer. Spheres of the third layer are exactly aligned with those of the first layer.
● Thus, the pattern of spheres is repeated in alternate layers.
● This pattern is often written as ABAB ....... pattern.
● This structure is called hexagonal close packed (hcp) structure.
● This sort of arrangement of atoms is found in many metals like magnesium and
zinc.

10
For More Material Join: @JEEAdvanced_2024
(ii) Covering Octahedral Voids:
● The third layer may be placed above the second layer in a manner such that its
spheres cover the octahedral voids.
● When placed in this manner, the spheres of the third layer are not aligned with those
of either the first or the second layer.
● This arrangement is called ‘C’ type. Only when the fourth layer is placed, its
spheres are aligned with those of the first layer as shown in Figs. 1.18 and 1.19.
● This pattern of layers is often written as ABCABC ...........
● This structure is called cubic close packed (ccp) or face-centred cubic (fcc)
structure. Metals such as copper and silver crystallise in this structure.

11
For More Material Join: @JEEAdvanced_2024
 ● Both these types of close packing are highly efficient and 74% space in the crystal
is filled.
● In either of them, each sphere is in contact with twelve spheres. Thus, the
coordination number is 12 in either of these two structures.
⮚ Formula of a Compound and Number of Voids Filled
● In ionic solids, the bigger ions (usually anions) form the close packed structure and the
smaller ions (usually cations) occupy the voids.
● If the latter ion is small enough then tetrahedral voids are occupied, if bigger, then
octahedral voids.
● Not all octahedral or tetrahedral voids are occupied.
● In a given compound, the fraction of octahedral or tetrahedral voids that are occupied,
depends upon the chemical formula of the compound.
⮚ Locating Tetrahedral and Octahedral Voids in ccp arrangement
(a) Tetrahedral Voids
● If a cube is divided into 8 equal parts, then each small part will have one tetrahedral
void as shown -

(b) Octahedral Voids

● These are present at all edge centres (¼th belongs to each unit cell) and at the body
center.

12
For More Material Join: @JEEAdvanced_2024
⮚ Packing Efficiency
Packing efficiency is the percentage of total space filled by the particles.

⮚ Calculations Involving Unit Cell Dimensions

● In case of cubic crystal:

Z = atomic number, M = Molecular Mass, a = edge length. NA = Avogadro number,

d = density
● Edge length of a unit cell of a cubic crystal determined by X-ray diffraction.
● The density of the unit cell is the same as the density of the substance.

⮚ Imperfections in Solids
● The defects are basically irregularities in the arrangement of constituent particles.
● Defects are of two types -
o Point defects - the irregularities or deviations from ideal arrangement around a point
or an atom in a crystalline substance
o Line defects - the irregularities or deviations from ideal arrangement in entire rows
of lattice points. These irregularities are called crystal defects.

13
For More Material Join: @JEEAdvanced_2024
⮚ Types of Point Defects
(a) Stoichiometric Defects -
● These are the point defects that do not disturb the stoichiometry of the solid. They are
also called intrinsic or thermodynamic defects.
● These are of two types, vacancy defects and interstitial defects.
(i) Vacancy Defect:
- Lattice sites are vacant, the crystal is said to have vacancy defects.
- Results in a decrease in density of the substance.
- Can develop when a substance is heated.

(ii) Interstitial Defect -

- Constituent particles (atoms or molecules) occupy an interstitial site.
- Increases the density of the substance.

Vacancy and interstitial defects as explained above can be shown by non-ionic solids.
Ionic solids must always maintain electrical neutrality. They show Frenekel and
Schottky defect instead of simple vacancy and interstitial defects
(iii)Frenkel Defect:
- Shown by ionic solids. The smaller ion (usually cation) is dislocated from its normal
site to an interstitial site. It creates a vacancy defect at its original site and an
interstitial defect at its new location.
- Also called dislocation defect.
- Does not change the density of the solid.
- Shown by ionic substances in which there is a large difference in the size of ions,
for example, ZnS, AgCl, AgBr and AgI due to the small size of Zn2+ and Ag+ ions.

14
For More Material Join: @JEEAdvanced_2024
(iv) Schottky Defect:
- A vacancy defect in ionic solids.
- In order to maintain electrical neutrality, the number of missing cations and anions
are equal.
- Decreases the density of the substance.
- Number of such defects in ionic solids is quite significant.
- In NaCl there are approximately 106 Schottky pairs per cm3 at room temperature.
In 1 cm3 there are about 1022 ions. Thus, there is one Schottky defect per 1016 ions.
- Shown by ionic substances in which the cation and anion are of almost similar sizes.
Example: NaCl, KCl, CsCl and AgBr.
- AgBr shows both, Frenkel as well as Schottky defects.

Schottky defects
(b) Impurity Defects
- If molten NaCl containing a little amount of SrCl2 is crystallised, some of the sites
of Na+ ions are occupied by Sr2+.

Introduction of cation vacancy in NaCl by substitution of Na+ by Sr2+

- Each Sr2+ replaces two Na+ ions. It occupies the site of one ion and the other site
remains vacant. The cationic vacancies thus produced are equal in number to that
of Sr2+ ions.
- Another example is the solid solution of CdCl2 and AgCl.
(c) Non-Stoichiometric Defects-
A large number of nonstoichiometric inorganic solids are known which contain the
constituent elements in non-stoichiometric ratio due to defects in their crystal
structures. These defects are of two types:

15
For More Material Join: @JEEAdvanced_2024
 (i) Metal Excess Defect -
(a) Metal excess defect due to anionic vacancies:
● Alkali halides like NaCl and KCl show this type of defect.
● When crystals of NaCl are heated in an atmosphere of sodium vapour, the sodium
atoms are deposited on the surface of the crystal. The Cl– ions diffuse to the surface
of the crystal and combine with Na atoms to give NaCl. This happens by loss of
electrons by sodium atoms to form Na+ ions. The released electrons diffuse into the
crystal and occupy anionic sites. As a result the crystal now has an excess of
sodium.

● The anionic sites occupied by unpaired electrons are called F-centres (from the
German word Farbenzenter for colour centre). They impart yellow colour to the
crystals of NaCl.
● The colour results from excitation of these electrons when they absorb energy from
the visible light falling on the crystals.
● excess of lithium makes LiCl crystals pink and excess of potassium makes KCl
crystals violet (or lilac)
(b) Metal excess defect due to the presence of extra cations at interstitial sites:
● Zinc oxide is white in colour at room temperature. On heating it loses oxygen and
turns yellow.
1
ZnO ⎯⎯⎯ heating
→ Zn 2+ + O2 + 2e −
2
● Now there is excess of zinc in the crystal and its formula becomes Zn1+xO.
● The excess Zn2+ ions move to interstitial sites and the electrons to neighbouring
interstitial sites.
(ii) Metal Deficiency Defect
● There are many solids which contain less amount of the metal as compared to the
stoichiometric proportion.
● A typical example of this type is FeO which is mostly found with a composition of
Fe0.95O. It may actually range from Fe0.93O to Fe0.96O.
● In crystals of FeO some Fe2+ cations are missing and the loss of positive charge is made
up by the presence of the required number of Fe3+ ions.

16
For More Material Join: @JEEAdvanced_2024
⮚ Electrical Properties
(i) Conductors The solids with conductivities ranging between 104 to 107 ohm–1m–1 are
called conductors. Metals have conductivities in the order of 107 ohm–1m–1 are good
conductors.
(ii) Insulators: These are the solids with very low conductivities ranging between 10–20 to
10–10 ohm–1m–1.
(iii) Semiconductors : These are the solids with conductivities in the intermediate range
from 10–6 to 104 ohm–1m–1.

⮚ Conduction of Electricity in Metals

● Metals conduct electricity in solid as well as molten state.
● Conductivity of metals depends upon the number of valence electrons available per
atom.
● The atomic orbitals of metal atoms form molecular orbitals which are so close in energy
to each other as to form a band. If this band is partially filled or it overlaps with a higher
energy unoccupied conduction band, then electrons can flow easily under an applied
electric field and the metal shows conductivity
● If the gap between filled valence band and the next higher unoccupied band (conduction
band) is large, electrons cannot jump to it and such a substance has very small
conductivity and it behaves as an insulator

⮚ Conduction of Electricity in Semiconductors

● In the case of semiconductors, the gap between the valence band and conduction band
is small. Thus, some electrons may jump to the conduction band and show some
conductivity.

17
For More Material Join: @JEEAdvanced_2024
 ● Electrical conductivity of semiconductors increases with rise in temperature, since
more electrons can jump to the conduction band.
● Substances like silicon and germanium show this type of behaviour and are called
intrinsic semiconductors.
● Conductivity of these intrinsic semiconductors is too low to be of practical use.
● Their conductivity is increased by adding an appropriate amount of suitable impurity.
This process is called doping.
● Doping can be done with an impurity which is electron rich or electron deficient as
compared to the intrinsic semiconductor silicon or germanium. Such impurities
introduce electronic defects in them.
(a) Electron – rich impurities
● Silicon and germanium belong to group 14 of the periodic table and have four valence
electrons each. In their crystals each atom forms four covalent bonds with its
neighbours.

● When doped with a group 15 element like P or As, which contains five valence
electrons, they occupy some of the lattice sites in silicon or germanium crystal.

18
For More Material Join: @JEEAdvanced_2024
 ● Four out of five electrons are used in the formation of four covalent bonds with the four
neighbouring silicon atoms.
● The fifth electron is extra and becomes delocalised. These delocalised electrons
increase the conductivity of doped silicon (or germanium).
● Here the increase in conductivity is due to the negatively charged electron. Hence,
silicon doped with electron-rich impurity is called n-type semiconductor.
(b) Electron – deficient impurities
● Silicon or germanium can also be doped with a group 13 element like B, Al or Ga which
contains only three valence electrons. Place where the fourth valence electron is missing
is called electron hole or electron vacancy.

● An electron from a neighbouring atom can come and fill the electron hole, but in doing
so it would leave an electron hole at its original position. If it happens, it would appear
as if the electron hole has moved in the direction opposite to that of the electron that
filled it.
● Under the influence of electric field, electrons would move towards the positively
charged plate through electronic holes, but it would appear as if electron holes are
positively charged and are moving towards negatively charged plate.
● This type of semiconductors are called p-type semiconductors.

19
For More Material Join: @JEEAdvanced_2024
⮚ Applications of n-type and p-type semiconductors
● Various combinations of n-type and p-type semiconductors are used for making
electronic components.
● Diode is a combination of n-type and p-type semiconductors and is used as a rectifier.
● Transistors are made by sandwiching a layer of one type of semiconductor between two
layers of the other type of semiconductor. npn and pnp type of transistors are used to
detect or amplify radio or audio signals.
● The solar cell is an efficient photo-diode used for conversion of light energy into
electrical energy.
● Germanium and silicon are group 14 elements and therefore, have a characteristic
valence of four and form four bonds as in diamond. A large variety of solid state
materials have been prepared by combination of groups 13 and 15 or 12 and 16 to
simulate average valence of four as in Ge or Si.
● Typical compounds of groups 13 – 15 are InSb, AlP and GaAs. Gallium arsenide
(GaAs) semiconductors have very fast response and have revolutionised the design of
semiconductor devices.
● ZnS, CdS, CdSe and HgTe are examples of groups 12 – 16 compounds. In these
compounds, the bonds are not perfectly covalent and the ionic character depends on the
electronegativities of the two elements.
● It is interesting to learn that transition metal oxides show marked differences in
electrical properties. TiO, CrO2 and ReO3 behave like metals. Rhenium oxide, ReO3 is
like metallic copper in its conductivity and appearance. Certain other oxides like VO,
VO2, VO3 and TiO3 show metallic or insulating properties depending on temperature.

⮚ Magnetic Properties
● Every substance has some magnetic properties associated with it. The origin of these
properties lies in the electrons.
● Each electron in an atom behaves like a tiny magnet. Its magnetic moment originates
from two types of motions -
(i) its orbital motion around the nucleus
(ii) its spin around its own axis

● Electrons being a charged particle and undergoing these motions can be considered as
a small loop of current which possesses a magnetic moment. Thus, each electron has a
permanent spin and an orbital magnetic moment associated with it.
● Magnitude of this magnetic moment is very small and is measured in the unit called
Bohr magneton, μB. It is equal to 9.27 × 10–24 A m2. On the basis of their magnetic
properties, substances can be classified into five categories:

20
For More Material Join: @JEEAdvanced_2024
(i) Paramagnetism:
- weakly attracted by a magnetic field. They are magnetised in a magnetic field in the
same direction. They lose their magnetism in the absence of magnetic field.-
- Paramagnetism is due to the presence of one or more unpaired electrons which are
attracted by the magnetic field. O2, Cu+2, Fe3+, Cr3+ are some examples of such
substances.
(ii) Diamagnetism:
- Weakly repelled by a magnetic field. H2O, NaCl and C6H6 are some examples of such
substances. They are weakly magnetised in a magnetic field in the opposite direction.
- Shown by those substances in which all the electrons are paired and there are no
unpaired electrons. Pairing of electrons cancels their magnetic moments and they lose
their magnetic character
(iii) Ferromagnetism:
- Substances like iron, cobalt, nickel, gadolinium and CrO2 are attracted very strongly by
a magnetic field. Such substances are called ferromagnetic substances.
- These substances can be permanently magnetised. In solid state, the metal ions of
ferromagnetic substances are grouped together into small regions called domains.
- Thus, each domain acts as a tiny magnet. In an unmagnetised piece of a ferromagnetic
substance the domains are randomly oriented and their magnetic moments get
cancelled. When the substance is placed in a magnetic field all the domains get oriented
in the direction of the magnetic field and a strong magnetic effect is produced.
- This ordering of domains persists even when the magnetic field is removed and the
ferromagnetic substance becomes a permanent magnet.

Schematic alignment of magnetic moments in ferromagnetic substance

(iv) Antiferromagnetism:
- Substances like MnO showing antiferromagnetism have domain structure similar to
ferromagnetic substance, but their domains are oppositely oriented and cancel out each
other's magnetic moment

Schematic alignment of magnetic moments in antiferromagnetic substance

(v) Ferrimagnetism:
- Observed when the magnetic moments of the domains in the substance are aligned in
parallel and antiparallel directions in unequal numbers.
- Weakly attracted by magnetic fields as compared to ferromagnetic substances. Fe3O4
(magnetite) and ferrites like MgFe2O4 and ZnFe2O4 are examples of such substances.
These substances also lose ferrimagnetism on heating and become paramagnetic.

Schematic alignment of magnetic moments in ferrimagnetic substance

21
For More Material Join: @JEEAdvanced_2024
 Solutions

Introduction
● Solutions are homogeneous mixtures of two or more than two components.
● The component that is present in the largest quantity is known as solvent.
● One or more components present in the solution other than solvent are called solutes.
● FACT - 1 part per million (ppm) of fluoride ions in water prevents tooth decay, while
1.5 ppm causes the tooth to become mottled and high concentrations of fluoride ions
can be poisonous (for example, sodium fluoride is used in rat poison.

Types of Solutions

Expressing Concentration of Solutions

1.

2.

3.

4.

22
For More Material Join: @JEEAdvanced_2024
 As in the case of percentage, concentration in parts per million can also be expressed
as mass to mass, volume to volume and mass to volume. The concentration of
pollutants in water or atmosphere is often expressed in terms of µg mL–1 or ppm.

5.
In a given solution sum of all the mole fractions is unity, i.e.,
X1 + X2 + X3 + …… = 1

6.

7.

Solubility
● Solubility of a substance is its maximum amount that can be dissolved in a specified
amount of solvent at a specified temperature.
● It depends upon the nature of solute and solvent as well as temperature and pressure.
● A solute dissolves in a solvent if the intermolecular interactions are similar in the two
or we may say ‘like dissolves like’.
● The solution which is in dynamic equilibrium with undissolved solute is the saturated
solution and contains the maximum amount of solute dissolved in a given amount of
solvent.
● An unsaturated solution is one in which more solute can be dissolved at the same
temperature.

Type of solution Effect of temperature Effect of pressure

Solid in Liquid ● If ΔH > 0, solubility no significant effect

increases with
temperature.
● If ΔH < 0, solubility
decreases with
temperature.

Gas in a Liquid Solubility of gases in liquids Solubility ∝ Pressure

decreases with rise in (Henry’s law)
temperature

23
For More Material Join: @JEEAdvanced_2024
 ❖ Henry’s Law: p = KH X
● KH: Henry’s law constant.
● Higher the value of KH at a given pressure, the lower is the solubility of the gas in
the liquid.
● KH values increase with increase of temperature.

❖ Applications of Henry’s law:

● To increase the solubility of CO2 in soft drinks and soda water.
● To avoid bends, as well as, the toxic effects of high concentrations of nitrogen in the
blood, the tanks used by scuba divers are filled with air diluted with helium (11.7%
helium, 56.2% nitrogen and 32.1% oxygen).
● At high altitudes the partial pressure of oxygen is less which leads to low
concentrations of oxygen in the blood and tissues of people living at high altitudes
or climbers which causes climbers to become weak and unable to think clearly,
symptoms of a condition known as anoxia.

Vapour Pressure of Liquid Solutions

According to Raoult’s law, for solution containing volatile components

● Raoult law is a special case of Henry’s law

● According to Dalton’s law of partial pressures, the total pressure (ptotal) over the solution
phase in the container will be the sum of the partial pressures of the components of the
solution and is given as: ptotal = p1 + p2

24
For More Material Join: @JEEAdvanced_2024
Ideal and Non-ideal Solutions
Ideal Solution Non-ideal solution

Follows Raoult’s law Positive Deviation from Negative Deviation from

(PT = PA + PB) Raoult’s law Raoult’s law
(PT > PA + PB) (PT < PA + PB)

∆mixH = 0, ∆mixV = 0 ∆mixH > 0, ∆mixV > 0 ∆mixH > 0, ∆mixV > 0

Intermolecular attractive Intermolecular attractive Intermolecular attractive

forces: A-A and B-B = A-B forces: A-A and B-B > A-B forces: A-A and B-B < A-B

Examples: n-hexane and Examples: ethanol and Example: chloroform and

n-heptane, bromoethane and acetone, carbon disulphide acetone, Nitric acid and
chloroethane, benzene and and acetone, ethanol-water water, phenol and aniline.
toluene. mixture

No azeotrope formed. Form minimum boiling Form maximum boiling

azeotrope at a specific azeotrope at a specific
composition. composition.
Azeotropic composition for Azeotropic composition for
ethanol-water mixture: nitric acid-water mixture:
approximately 95% by 68% nitric acid and 32%
volume of ethanol. water by mass, with a
boiling point of 393.5 K.

Colligative Properties
● Colligative: from Latin: co means together, ligare means to bind.
● Properties depend on the number of solute particles irrespective of their nature relative
to the total number of particles present in the solution.

25
For More Material Join: @JEEAdvanced_2024
Relative Lowering of Vapour Pressure
● Relative lowering of vapour pressure and is equal to the mole fraction of the solute.

Here n1 and n2 are the number of moles of solvent and solute respectively present in the
solution.
● For dilute solutions:

Here w1 and w2 are the masses and M1 and M2 are the molar masses of the solvent and
solute respectively.

Elevation of Boiling Point

❖ ∆Tb = Kb m
● ∆Tb is known as the elevation of boiling point.
● Kb is Boiling Point Elevation Constant or Molal Elevation Constant (Ebullioscopic
Constant). The unit of Kb is K kg mol–1.

❖
● R = Gas constant, M = Molar mass of solvent
● Tb = boiling point of pure solvent
● ∆vapH = enthalpy for the vapourisation.

26
For More Material Join: @JEEAdvanced_2024
Depression of Freezing Point

❖ ∆Tf = Kf m
● ∆Tf is known as the depression of freezing point.
● Kb is Freezing Point Depression Constant or Molal Depression Constant or
Cryoscopic Constant. The unit of Kf is K kg mol–1.

❖
● R = Gas constant, M = Molar mass of solvent
● Tf = freezing point of pure solvent
● ∆fusH = enthalpy for the vaporisation

27
For More Material Join: @JEEAdvanced_2024
Osmosis and Osmotic Pressure

❖ Semipermeable membrane: It allows small molecules (solvent generally) to pass

through. Example - pig’s bladder, parchment, cellophane (synthetic).
❖ The process of flow of the solvent from solution of low concentration to a solution of
high concentration is called osmosis.
❖ The pressure that just stops the flow of solvent is called osmotic pressure of the
solution.
❖ π=CRT
● π = Osmotic pressure, C = Molar concentration, R = Gas constant, T = Absolute
temperature.
❖ Measurement of osmotic pressure is widely used to determine molar masses of
proteins, polymers and other macromolecules. As compared to other colligative
properties, its magnitude is large even for very dilute solutions.
❖ For two different solutions-
● if πA = πB, solution is isotonic
● If πA < πB, A is hypotonic wrt. B and B is hypertonic wrt. A.
❖ Osmosis in daily life -
● raw mangoes shrivel when pickled in brine (salt water)
● wilted flowers revive when placed in freshwater
● blood cells collapse when suspended in saline water
● When placed in water containing less than 0.9% (mass/ volume) salt, blood cells
swell due to flow of water in them by osmosis. The resulting puffiness or swelling
is called edema.
● The preservation of meat by salting and of fruits by adding sugar. A Bacterium on
salted meat or candied fruit loses water, shrivels and dies.
● Water movement from soil into plant roots and subsequently into the upper portion
of the plant is partly due to osmosis.

28
For More Material Join: @JEEAdvanced_2024
 ❖ Reverse Osmosis:
● Pure solvent flows out of the solution through the semipermeable membrane if a
pressure larger than the osmotic pressure is applied to the solution side. This
phenomenon is called reverse osmosis.

● Reverse osmosis is used in desalination of seawater. Cellulose acetate is used as

SPM which is permeable to water but impermeable to impurities and ions present
in seawater.

Abnormal Molar Masses

❖ i = van’t Hoff factor

❖ In the case of association, the value of i is less than unity while for dissociation it is
greater than unity.
❖ Inclusion of van’t Hoff factor modifies the equations for colligative properties as
follows:

29
For More Material Join: @JEEAdvanced_2024
❖ Molecules of ethanoic acid (acetic acid) dimer in benzene due to hydrogen bonding.
This normally happens in solvents of low dielectric constant.

30
For More Material Join: @JEEAdvanced_2024
 Electrochemistry

Electrochemical Cells
● Galvanic Cell or voltaic cell: Electrochemical cell that converts the chemical energy
of a spontaneous redox reaction into electrical energy.
● Electrolytic cell: A device for using electrical energy to carry non-spontaneous
chemical reactions

Galvanic Cells
● It is made up of two half cells – oxidation half (anode is a part of this half) and
reduction half (cathode is a part of this half)
● Daniel cell is a common example -

● A potential difference that develops between the electrode and the electrolyte which is
called electrode potential.
● When the concentration of all the species involved in a half-cell is unity then the
electrode potential is known as standard electrode potential.
● According to IUPAC convention, standard reduction potentials are now called
standard electrode potentials.
● The potential difference between the two electrodes of a galvanic cell is called the cell
potential and is measured in volts. We keep the anode on the left and the cathode on
the right while representing the galvanic cell.

31
For More Material Join: @JEEAdvanced_2024
Standard Hydrogen Electrode (SHE)

● Represented by Pt(s) | H2(g) | H+(aq)

● It is assigned a zero potential at all temperatures.

● The pressure of hydrogen gas is one bar and the concentration of hydrogen ion in the
solution is one molar.
● The potential of other half-cells is measured using SHE.
1. A negative E° means that the redox couple is a stronger reducing agent than the
H+/H2 couple.
2. A positive E° means that the redox couple is a weaker reducing agent than the
H+/H2 couple.

Electrochemical Series
● Arrangement of different elements in increasing order of SRP is known as
electrochemical series or activity series.
● The table below shows reverse electrochemical series:

32
For More Material Join: @JEEAdvanced_2024
 ● Applications:
● Greater the reduction potential of a substance, strong is the oxidising agent.
● In ECS reactivity of metals decreases from top to bottom.
● In ECS reactivity of nonmetals decreases from top to bottom.
● More reactive metals/non-metals displace less reactive metals/non-metals in
their solution.
● Metals above H2 displaces H2 from acids.

Nernst Equation

● For the electrode reaction:

R is gas constant, F is Faraday constant (96487 C mol–1), T is temperature in kelvin

and [Mn+] is the concentration of the species.
● For a general electrochemical reaction of the type:

● Equilibrium Constant from Nernst Equation:

● Electrochemical Cell and Gibbs Energy of the Reaction:

33
For More Material Join: @JEEAdvanced_2024
 ● For a given reaction to be spontaneous, must be positive. When the cell reaction

attains equilibrium, .

Conductance of Electrolytic Solutions

● The electrical resistance of any object is directly proportional to its length, l, and
inversely proportional to its area of cross section, A.

ρ (Greek, rho), is called resistivity (specific resistance). Its SI units are ohm metre (Ω
m) and quite often, ohm centimetre (Ω cm) is also used.
● The inverse of resistance, R, is called conductance, G

The SI unit of conductance is siemens, represented by the symbol ‘S’ and is equal to
ohm–1 (also known as mho) or Ω–1.
● The inverse of resistivity, called conductivity (specific conductance) is represented by
the symbol, κ (Greek, kappa). The conductivity of a solution at any given
concentration is the conductance of one unit volume of solution kept between two
platinum electrodes with unit area of cross section and at a distance of unit length.
● The SI units of conductivity are S m–1 but quite often, κ is expressed in S cm–1.

Conductors, insulators and semiconductors

The values of Conductivity of some Selected Materials at 298.15 K

● Metals and their alloys have very large conductivity and are known as conductors.
Certain non-metals like carbon-black, graphite and some organic polymers are also
electronically conducting.
● Substances like glass, ceramics, etc., having very low conductivity are known as
insulators.

34
For More Material Join: @JEEAdvanced_2024
 ● Substances like silicon, doped silicon and gallium arsenide having conductivity
between conductors and insulators are called semiconductors and are important
electronic materials.
● Certain materials called superconductors by definition have zero resistivity or infinite
conductivity. Earlier, only metals and their alloys at very low temperatures (0 to 15 K)
were known to behave as superconductors, but nowadays a number of ceramic
materials and mixed oxides are also known to show superconductivity at temperatures
as high as 150 K.

Factors affecting the conductance through metals and ionic solutions

● Electrical conductance through metals is called metallic or electronic conductance and
is due to the movement of electrons. The electronic conductance depends on
(i) the nature and structure of the metal
(ii) the number of valence electrons per atom
(iii) temperature (it decreases with increase of temperature).
● As the electrons enter at one end and go out through the other end, the composition of
the metallic conductor remains unchanged.

● The conductance of electricity by ions present in the solutions is called electrolytic or

ionic conductance. The conductivity of electrolytic (ionic) solutions depends on:
(i) the nature of the electrolyte added
(ii) size of the ions produced and their solvation
(iii) the nature of the solvent and its viscosity
(iv) concentration of the electrolyte
(v) temperature (it increases with the increase of temperature).
● Passage of direct current through ionic solution over a prolonged period can lead to
change in its composition due to electrochemical reactions

Measurement of the Conductivity of Ionic Solutions

● A conductivity cell (shown above) is connected to an AC source of power with other

resistances such that a wheatstone bridge is formed.

35
For More Material Join: @JEEAdvanced_2024
 Here, Unknown resistance
● The quantity l/A is called cell constant denoted by the symbol, G*. Using the
measured resistance and cell constant, conductivity can be calculated as -

Molar conductivity
● Conductivity of a solution containing 1 mole of electrolyte.
Λm = κ V (volume containing 1 mole of electrolyte)
● Different formulas can be used based on the units of conductivity and concentration:

1)
κ is expressed in S m–1 and the concentration, c in mol m–3, the units of Λm are
in S m2 mol–1.

2)
● 1 S m2 mol–1 = 104 S cm2 mol–1

Variation of Conductivity and Molar Conductivity with Concentration

● Conductivity always decreases with decrease in concentration both, for weak and
strong electrolytes because the number of ions per unit volume that carry the current
in a solution decreases on dilution. This can be explained by the fact that the number
of ions per unit volume that carry the current in a solution decreases on dilution.
● Λm = κ V (volume containing 1 mole of electrolyte)
● Molar conductivity increases with decrease in concentration. This is because the total
volume, V, of solution containing one mole of electrolyte also increases.
● When concentration approaches zero, the molar conductivity is known as limiting
molar conductivity and is represented by the symbol Λm°.

36
For More Material Join: @JEEAdvanced_2024
 ● For weak electrolytes, the molar conductivity increases rapidly with dilution as the
number of ions also increases on dilution (ostwald’s law).
● For strong electrolytes, the molar conductivity does not increase at much rate as weak
electrolytes. The relationship between molar conductivity and √C for strong
electrolytes is given by equation:
Λm = Λ m° – A√C
The value of the constant ‘A’ for a given solvent and temperature depends on the type
of electrolyte, i.e., the charges on the cation and anion produced on the dissociation of
the electrolyte in the solution. All electrolytes of a particular type have the same value
for ‘A’.
● NaCl, CaCl2, MgSO4 are known as 1-1, 2-1 and 2-2 electrolytes respectively

Kohlrausch law of independent migration of ions

● Limiting molar conductivity of an electrolyte can be represented as the sum of the
individual contributions of the anion and cation of the electrolyte.
Λm° (AaBb) = a × Λm° (Ab+) + b × Λm° (Ba–)
● For weak electrolytes, Λm° cannot be obtained by extrapolation of Λm to zero
concentration. It is obtained by using Kohlrausch law of independent migration of
ions
● For weak electrolytes, the degree of dissociation can be determined using limiting
molar conductivity as-

Using this, dissociation constants can also be calculated, for example for acetic acid,

Electrolytic Cell and Electrolysis

● Many metals like Na, Mg, Al, etc. are produced on large scale by electrochemical
reduction of their respective cations where no suitable chemical reducing agents are
available for this purpose.

37
For More Material Join: @JEEAdvanced_2024
 ● Sodium and magnesium metals are produced by the electrolysis of their fused
chlorides and aluminium is produced by electrolysis of aluminium oxide in presence
of cryolite.

Faraday’s Laws of Electrolysis

(i) First Law:

Weight of substance liberated Quantity of electricity passed.

W Q or W = ZQ = Z × I × t (Z = electrochemical equivalent)
(ii) Second Law:
According to Faraday’s second law of electrolysis, for the same quantity of electricity
passed through solutions of different electrolytes, (e.g. CuSO4 and AgNO 3)

Deciding the products of electrolysis

● If the electrode is inert (e.g., platinum or gold), it does not participate in the chemical
reaction and acts only as source or sink for electrons.
● On the other hand, if the electrode is reactive, it participates in the electrode reaction.
● Some of the electrochemical processes although feasible, are so slow kinetically that
at lower voltages these do not seem to take place and extra potential (called
overpotential) has to be applied, which makes such process more difficult to occur
● Species having more standard reduction potential are reduced at cathode.
● Species having less standard reduction potential are oxidised at anode.
● Electrolysis of molten NaCl: Na obtained at cathode, Cl2 obtained at anode.
● Electrolysis of aqueous NaCl: H2 obtained at cathode, Cl2 obtained at anode(on
account of overpotential of oxygen).
● During the electrolysis of sulphuric acid, the following processes are possible at the
anode:

…(i)

…(ii)
For dilute sulphuric acid, reaction (i) is preferred but at higher concentrations of
H2SO4, reaction (ii) is preferred.

Batteries
● For a battery to be of practical use it should be reasonably light, compact and its
voltage should not vary appreciably during its use.

38
For More Material Join: @JEEAdvanced_2024
Primary Batteries
● In the primary batteries, the reaction occurs only once and after use over a period of
time the battery becomes dead and cannot be reused again.
1. Dry cell (known as Leclanche cell after its discoverer)

● Used commonly in transistors and clocks.

● The electrode reactions are complex, but they can be written approximately as
follows:

● Ammonia produced in the reaction forms a complex with Zn2+ to give [Zn(NH3)4]2+
● The cell has a potential of nearly 1.5 V.
2. Mercury cell

● Suitable for low current devices like hearing aids, watches, etc.
● Anode - Zinc – mercury amalgam
Cathode - a paste of HgO and carbon
Electrolyte - a paste of KOH and ZnO.
● The electrode reactions:

● The overall reaction:

39
For More Material Join: @JEEAdvanced_2024
 ● The cell potential is approximately 1.35 V and remains constant for lifetime as the
overall reaction does not involve any ion in solution.
Secondary Batteries
● A secondary cell after use can be recharged by passing current through it in the
opposite direction so that it can be used again.
● A good secondary cell can undergo a large number of discharging and charging
cycles.

1. Lead storage battery

● The cell reactions when the battery is in use are given below:

● Overall reaction while discharging:

● On charging the battery the reaction is reversed and PbSO4(s) on anode and cathode is
converted into Pb and PbO2, respectively.

2. Nickel-cadmium cell

● A jelly roll arrangement and separated by a layer soaked in moist sodium or

potassium hydroxide.
● The overall reaction during discharge is:

40
For More Material Join: @JEEAdvanced_2024
Fuel Cells
● Galvanic cells that are designed to convert the energy of combustion of fuels like
hydrogen, methane, methanol, etc. directly into electrical energy are called fuel cells.
Hydrogen-oxygen fuel cell

● Hydrogen and oxygen are bubbled through porous carbon electrodes into concentrated
aqueous sodium hydroxide solution. Catalysts like finely divided platinum or
palladium metal are incorporated into the electrodes for increasing the rate of
electrode reactions.
● The electrode reactions are given below:

Overall reaction:

● The cell was used for providing electrical power in the Apollo space programme and
the water vapour produced was condensed and used in the drinking water supply.
● Fuel cells produce electricity with an efficiency of about 70 % compared to thermal
plants whose efficiency is about 40%.
● Fuel cells are pollution free.

Corrosion

41
For More Material Join: @JEEAdvanced_2024
 ● The rusting of iron, tarnishing of silver, development of green coating on copper and
bronze are some of the examples of corrosion.
● In corrosion, a metal is oxidised by loss of electrons to oxygen and formation of
oxides.
● Rust is hydrated ferric oxide (Fe2O3.xH2O)

Method of Prevention of corrosion

● Covering the surface with paint or by some chemicals (e.g. bisphenol).
● Covering the surface by other metals (Sn, Zn, etc.) that are inert or react to save the
object.
● Provide a sacrificial electrode of another metal (like Mg, Zn, etc.) which corrodes
itself but saves the object.

42
For More Material Join: @JEEAdvanced_2024
 Chemical Kinetics

● Along with feasibility and extent, it is equally important to know the rate and the factors
controlling the rate of a chemical reaction for its complete understanding. The branch of
chemistry which deals with the study of reaction rates and their mechanisms is called
chemical kinetics. Thermodynamics tells only about the feasibility of a reaction whereas
chemical kinetics tells about the rate of a reaction.
● The word kinetics is derived from the Greek word ‘kinesis’ meaning movement.
● Kinetic studies not only help us to determine the speed or rate of a chemical reaction but
also describe the conditions by which the reaction rates can be altered.
● The factors such as concentration, temperature, pressure and catalyst affect the rate of a
reaction.
● Thermodynamic data indicate that diamond shall convert to graphite but in reality, the
conversion rate is so slow that the change is not perceptible at all.

➢ Rate of a Chemical Reaction

● Example of fast reaction - precipitation of silver chloride occurs instantaneously by
mixing of aqueous solutions of silver nitrate and sodium chloride.
● Example of a moderate reaction - inversion of cane sugar and hydrolysis of starch.
● Example of a slow reaction - rusting of iron in the presence of air and moisture.
● The speed of a reaction or the rate of a reaction can be defined as the change in
concentration of a reactant or product in unit time.
● To be more specific, it can be expressed in terms of:
(i) the rate of decrease in concentration of any one of the reactants.
(ii) the rate of increase in concentration of any one of the products.
● For a general reaction: R → P
decrease in concentration on of R −R
Rate of disappearance of R = =
time taken t
increase in concentration of P P
Rate of appearance of P = =
time taken t
These expressions give an average rate of reaction.

● Units of rate: mol per litre per second or atm per second.

43
For More Material Join: @JEEAdvanced_2024
 ● To express the rate at a particular moment of time we determine the instantaneous rate.
mathematically for an infinitesimally small dt instantaneous rate is given by
−d  R  d  P 
rinst = =
dt dt
● Instantaneous can be determined graphically by drawing a tangent at time t on either of
the curves for concentration of R and P vs time t and calculating its slope.

Instantaneous rate of hydrolysis of butyl chloride(C4H9Cl)

● For expressing the rate of such a reaction where stoichiometric coefficients of reactants
or products are not equal to one, rate of disappearance of any of the reactants or the rate
of appearance of products is divided by their respective stoichiometric coefficients.
aA+bB → cC +dD

● For a gaseous reaction at constant temperature, concentration is directly proportional to

the partial pressure of a species and hence, rate can also be expressed as rate of change
in partial pressure of the reactant or the product.

➢ Factors Influencing Rate of a Reaction

● Dependence of Rate on Concentration
o The rate of a chemical reaction at a given temperature may depend on the
concentration of one or more reactants and products. The representation of rate of
reaction in terms of concentration of the reactants is known as rate law. It is also
called the rate equation for rate expression.
● Rate Expression and Rate Constant
o Consider a general reaction aA + bB → cC + dD where a, b, c and d are the
stoichiometric coefficients of reactants and products.
o The rate expression for this reaction is Rate ∝ [A]x [B]y where exponents x and y
may or may not be equal to the stoichiometric coefficients (a and b) of the reactants.
o Above equation can also be written as Rate = k [A]x [B]y, k is called rate constant.
o Rate law is the expression in which reaction rate is given in terms of molar
concentration of reactants with each term raised to some power, which may or may

44
For More Material Join: @JEEAdvanced_2024
 not be the same as the stoichiometric coefficient of the reacting species in a
balanced chemical equation.
o Rate law for any reaction cannot be predicted by merely looking at the balanced
chemical equation, i.e., theoretically but must be determined experimentally.
● Order of a Reaction
o The sum of powers of the concentration of the reactants in the rate law expression
is called the order of that chemical reaction. Order of a reaction can be 0, 1, 2, 3
and even a fraction.
o The reactions taking place in one step are called elementary reactions. When a
sequence of elementary reactions (called mechanism) gives us the products, the
reactions are called complex reactions.
o Units of rate constant
Reaction Order Units of rate constant
Zero order reaction 0 mol L−1 1
 = mol L−1 s −1
( mol L )
− 0
s 1

First order reaction 1 mol L−1 1

 = s −1
( mol L−1 )
1
s
Second order reaction 2 mol L−1 1
 = mol−1 L s −1
( mol L )
− 2
s 1

● Molecularity of a Reaction
o The number of reacting species (atoms, ions or molecules) taking part in an
elementary reaction, which must collide simultaneously in order to bring about a
chemical reaction is called molecularity of a reaction.
o Example of unimolecular reaction - NH4NO2 → N2 + 2H2O
o Example of bimolecular reaction - 2HI → H2 + I2
o Example of trimolecular reaction - 2NO + O2 → 2NO2
o The probability that more than three molecules can collide and react simultaneously
is very small. Hence, reactions with the molecularity three are very rare and slow
to proceed.
o Complex reactions involving more than three molecules in the stoichiometric
equation must take place in more than one step.
o KClO3 + 6FeSO4 + 3H2SO4 → KCl + 3Fe2(SO4)3 + 3H2O - seems like a tenth order
reaction but actually is a second order reaction.
o The overall rate of the reaction is controlled by the slowest step in a reaction called
the rate determining step.
o The decomposition of hydrogen peroxide which is catalysed by iodide ion in an
alkaline medium takes place in two steps, of which first is slow-
1. H 2 O2 + I − → H 2 O + IO −
2. H 2 O2 + IO − → H 2 O + I − + O2
o The overall reaction and rate law for above reaction is given as-

45
For More Material Join: @JEEAdvanced_2024
 −
2 H 2 O2 ⎯⎯⎯⎯⎯ I
Alkaline medium
→ 2 H 2 O + O2
−d  H 2 O2 
Rate = = k  H 2 O2   I − 
dt
o Order of a reaction is an experimental quantity. It can be zero and even a fraction
but molecularity cannot be zero or a non integer.
o Order is applicable to elementary as well as complex reactions whereas
molecularity is applicable only for elementary reactions. For complex reactions
molecularity has no meaning.
o For complex reactions, order is given by the slowest step and the molecularity of
the slowest step is the same as the order of the overall reaction.

➢ Integrated Rate Laws

● Examples of zero order reactions -

○ Some enzyme catalysed reactions
○ Reactions which occur on metal surfaces
○ The decomposition of gaseous ammonia on a hot platinum surface is a zero-order
reaction at high pressure.

In this reaction, platinum metal acts as a catalyst. At high pressure, the metal surface
gets saturated with gas molecules. So, a further change in reaction conditions is
unable to alter the amount of ammonia on the surface of the catalyst making the
rate of the reaction independent of its concentration.
○ The thermal decomposition of HI on the gold surface.
● Examples of first order reactions -
○ Hydrogenation of ethene
○ All natural and artificial radioactive decay of unstable nuclei take place by first
order kinetics.
○ Decomposition of N2O5 and N2O
● Half-life of a reaction -
○ The half-life of a reaction is the time in which the concentration of a reactant is
reduced to one half of its initial concentration. It is represented as t1/2.
○ t1/2 for a zero-order reaction is directly proportional to the initial concentration of
the reactants and inversely proportional to the rate constant.
○ For a first order reaction, the half-life period is constant, i.e., it is independent of
initial concentration of the reacting species.

46
For More Material Join: @JEEAdvanced_2024
 ● Integrated Rate Laws for the Reactions of Zero and First Order –

Graph of zero order reaction

Graphs of 1st order reaction

● Pseudo First Order Reaction

o The order of a reaction between two substances is sometimes altered when one
reactant is present in large excess. The reaction behaves as a first order reaction.
Such reactions are called pseudo first order reactions.
o Examples -
▪ Hydrolysis of ethyl acetate.
▪ Inversion of cane sugar.

➢ Temperature Dependence of the Rate of a Reaction

● In a mixture of potassium permanganate (KMnO4) and oxalic acid (H2C2O4), potassium
permanganate is decolourised faster at a higher temperature than that at a lower
temperature.

47
For More Material Join: @JEEAdvanced_2024
● Temperature Coefficient: for a chemical reaction with rise in temperature by 10°, the
rate constant is nearly doubled.
● Arrhenius' equation was first proposed by Dutch chemist, J.H. van’t Hoff but Swedish
chemist Arrhenius provided its physical justification and interpretation.
● Arrhenius equation:

where A is the Arrhenius factor or the frequency factor. It is also called a pre-
exponential factor. It is a constant specific to a particular reaction. R is gas constant and
Ea is activation energy measured in joules/mole (J mol-1).
● Activation energy is given by the energy difference between activated complex and the
reactant molecules.

● All the molecules in the reacting species do not have the same kinetic energy. Since it
is difficult to predict the behaviour of any one molecule with precision, Ludwig
Boltzmann and James Clark Maxwell used statistics to predict the behaviour of a large
number of molecules. According to them, the distribution of kinetic energy may be
described by plotting the fraction of molecules (NE/NT) with a given kinetic energy (E)
vs kinetic energy. Here, NE is the number of molecules with energy E and NT is the
total number of molecules.

● The peak of the curve corresponds to the most probable kinetic energy, i.e., kinetic
energy of the maximum fraction of molecules. There are a decreasing number of
molecules with energies higher or lower than this value.

48
For More Material Join: @JEEAdvanced_2024
 ● When the temperature is raised, the maximum of the curve moves to the higher energy
value and the curve broadens out, i.e., spreads to the right such that there is a greater
proportion of molecules with much higher energies. The area under the curve must be
constant since total probability must be one at all times.

● Increasing the temperature of the substance increases the fraction of molecules, which
collide with energies greater than Ea.
● In the Arrhenius equation,the factor e–Ea/RT corresponds to the fraction of molecules that
have kinetic energy greater than Ea.
● Thus, increasing the temperature or decreasing the activation energy will result in an
increase in the rate of the reaction and an exponential increase in the rate constant.
● Logarithmic form of Arrhenius equation –
E
ln k = − a + ln A
RT
k2 Ea  1 1 
log =  − 
k1 2.303R  T1 T2 

➢ Effect of Catalyst
● A catalyst is a substance which increases the rate of a reaction without itself undergoing
any permanent chemical change.
● Presence of a catalyst lowers the activation energy by providing an alternate path for
the reaction.

49
For More Material Join: @JEEAdvanced_2024
 ● The word inhibitor is used when the added substance reduces the rate of reaction.
● Intermediate complex theory - A catalyst participates in a chemical reaction by
forming temporary bonds with the reactants resulting in an intermediate complex. This
has a transitory existence and decomposes to yield products and the catalyst.
● It is believed that the catalyst provides an alternate pathway or reaction mechanism by
reducing the activation energy between reactants and products and hence lowering the
potential energy barrier

Effect of catalyst on activation energy

● A small amount of the catalyst can catalyse a large amount of reactants
● A catalyst does not alter Gibbs energy, ΔG of a reaction. It catalyses spontaneous
reactions but does not catalyse nonspontaneous reactions.
● It is also found that a catalyst does not change the equilibrium constant of a reaction
rather, it helps in attaining the equilibrium faster, that is, it catalyses the forward as well
as the backward reactions to the same extent so that the equilibrium state remains same
but is reached earlier.

➢ Collision Theory of Chemical Reactions

● Though Arrhenius' equation is applicable under a wide range of circumstances,
collision theory, which was developed by Max Trautz and William Lewis in 1916 -18,
provides a greater insight into the energetic and mechanistic aspects of reactions. It is
based on the kinetic theory of gases.
● The reactant molecules are assumed to be hard spheres and reaction is postulated to
occur when molecules collide with each other. The number of collisions per second per
unit volume of the reaction mixture is known as collision frequency (Z).
● For a bimolecular reaction A → B
Rate = ZABe Ea/RT
where ZAB represents the collision frequency of reactants, A and B and e–Ea /RT
represents the fraction of molecules with energies equal to or greater than Ea.
● The above equation predicts the value of rate constants fairly accurately for the
reactions that involve atomic species or simple molecules but for complex molecules
significant deviations are observed.
● The reason could be that all collisions do not lead to the formation of products.
● The collisions in which molecules collide with sufficient kinetic energy (called
threshold energy) and proper orientation, so as to facilitate breaking of bonds between

50
For More Material Join: @JEEAdvanced_2024
 reacting species and formation of new bonds to form products are called effective
collisions.
o Threshold energy = Activation Energy + energy possessed by reacting species.
● The proper orientation of reactant molecules leads to bond formation whereas improper
orientation makes them simply bounce back and no products are formed.

Diagram showing molecules having proper and improper orientation

● To account for effective collisions, another factor P, called the probability or steric
factor is introduced. It takes into account the fact that in a collision, molecules must be
properly oriented i.e.,
Ea / RT
Rate = PZ AB e
● Thus, in collision theory activation energy and proper orientation of the molecules
together determine the criteria for an effective collision and hence the rate of a chemical
reaction.
● Collision theory also has certain drawbacks as it considers atoms/ molecules to be hard
spheres and ignores their structural aspect.

51
For More Material Join: @JEEAdvanced_2024
 Surface Chemistry

• Surface chemistry deals with phenomena that occur at the surfaces or interfaces.
• The interface or surface is represented by separating the bulk phases by a hyphen or a slash.
• For example, the interface between a solid and a gas may be represented by solid-gas or
solid/gas.
• Many important phenomena, noticeable amongst these being corrosion, electrode
processes, heterogeneous catalysis, dissolution and crystallisation occur at interfaces.
• Under very high vacuum of the order of 10–8 to 10–9 pascal, it is now possible to obtain
ultra clean surface of the metals. Solid materials with such clean surfaces need to be stored
in vacuum otherwise these will be covered by molecules of the major components of air
namely dioxygen and dinitrogen.

➢ Adsorption:
The accumulation of molecular species at the surface rather than in the bulk of a solid or
liquid is termed adsorption.
● Adsorbate: The substance, which accumulates at the surface.
● Adsorbent: The material on the surface of which the adsorption takes place. Solids,
particularly in finely divided state, have large surface area and therefore, charcoal, silica
gel, alumina gel, clay, colloids, metals in finely divided state, etc. act as good adsorbents.
● Examples of adsorption –
1. If a gas like O2, H2, CO, Cl2, NH3 or SO2 is taken in a closed vessel containing
powdered charcoal, it is observed that the pressure of the gas in the enclosed vessel
decreases. The gas molecules concentrate at the surface of the charcoal, i.e., gases
are adsorbed at the surface.
2. In a solution of an organic dye, say methylene blue, when animal charcoal is added
and the solution is well shaken, it is observed that the filtrate turns colourless. The
molecules of the dye, thus, accumulate on the surface of charcoal, i.e., are adsorbed.
3. Aqueous solution of raw sugar, when passed over beds of animal charcoal, becomes
colourless as the colouring substances are adsorbed by the charcoal.
4. The air becomes dry in the presence of silica gel because the water molecules get
adsorbed on the surface of the gel.
Desorption: The process of removing an adsorbed substance from a surface on which it
is adsorbed.
❖ Distinction between Adsorption and Absorption
Adsorption Absorption

● The substance is concentrated only ● The substance is uniformly distributed

at the surface and does not penetrate throughout the bulk of the solid.
through the surface.

● When a chalk stick is dipped in ink, ● When a chalk stick is dipped in ink,
the surface retains the colour of the the solvent of the ink goes deeper into

52
For More Material Join: @JEEAdvanced_2024
 ink due to adsorption. the stick due to absorption.

● Water vapours are adsorbed by silica ● Water vapours are absorbed by

gel. anhydrous calcium chloride.

Sorption: Both adsorption and absorption can take place simultaneously also. The term
sorption is used to describe both the processes.

❖ Mechanism of Adsorption: Reason for adsorption: the surface particles are not in the
same environment as the particles inside the bulk.
● Inside the adsorbent all the forces acting between the particles are balanced.
● On the surface the particles are not surrounded by the particles of their kind on all
sides, and hence they possess unbalanced attractive forces.
● These forces are responsible for attracting the adsorbate particles on its surface.
❖ Some important points to note about adsorption
● At a given temperature and pressure, the extent of adsorption increases with the
increase of surface area per unit mass of the adsorbent.
● During adsorption, there is a decrease in surface energy which appears as heat. So,
∆H of adsorption is always negative.
● When a gas is adsorbed, the freedom of movement of its molecules becomes
restricted. So, ∆S is negative.
● For a process to be spontaneous, the thermodynamic requirement is that, at constant
temperature and pressure, ∆G must be negative.
❖ Types of Adsorptions
● Physisorption: If accumulation of gas on the surface of a solid occurs on account
of weak van der Waals’ forces, the adsorption is termed as physical adsorption or
physisorption.
● Chemisorption: When the gas molecules or atoms are held to the solid surface by
chemical bonds, the adsorption is termed chemical adsorption or chemisorption.
● A physical adsorption at low temperature may pass into chemisorption as the
temperature is increased. For example, dihydrogen is first adsorbed on nickel by van
der Waals’ forces. Molecules of hydrogen then dissociate to form hydrogen atoms
which are held on the surface by chemisorption.

❖ Comparison between physisorption and chemisorption

Physisorption Chemisorption

1. It arises because of van der Waals' 1. It is caused by chemical bond formation.

forces.

2. It is not specific in nature. 2. It is highly specific in nature.

3. It is reversible in nature. 3. It is irreversible.

53
For More Material Join: @JEEAdvanced_2024
 4. It depends on the nature of gas. More 4. It also depends on the nature of gas.
easily liquefiable gases are adsorbed Gases which can react with the adsorbent
readily. show chemisorption.

5. Enthalpy of adsorption is low (20-40 kJ 5. Enthalpy of adsorption is high (80-240 kJ

mol-1) in this case. mat-1) in this ease.

6. Low temperature is favourable for 6. High temperature is favourable for

adsorption. It decreases with increase of adsorption. It increases with the increase of
temperature. temperature.

7. No appreciable activation energy is 7. High activation energy is sometimes

needed. needed.

8. It depends on the surface area. It 8. It also depends on the surface area. It too
Increases with an increase of surface area. increases with an increase of surface area.

9. It results into multimolecular layers on 9. It results into unimolecular layer.

adsorbent surface under high pressure.

❖ Adsorption Isotherms: It is the plot of the amount of gas adsorbed by the adsorbent
with pressure at constant temperature.

➢ Freundlich adsorption isotherm:

1.

where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure P, k
and n are constants which depend on the nature of the adsorbent and the gas at a
particular temperature.

x 1
2. log = log k + log p
m n

54
For More Material Join: @JEEAdvanced_2024
 Points to remember on Freundlich isotherm equation -
1. The factor 1/n can have values between 0 and 1.
2. When 1/n = 0, x/m = constant, the adsorption is independent of pressure.
3. When 1/n = 1, x/m = k p, i.e. x/m ∝ p, the adsorption varies directly with pressure.
4. The experimental isotherms always seem to approach saturation at high pressure.
This cannot be explained by Freundlich isotherm. Thus, it fails at high pressure.

➢ Adsorption from Solution Phase

Examples
• When a solution of acetic acid in water is shaken with charcoal, a part of the acid is
adsorbed by the charcoal and the concentration of the acid decreases in the solution.
• The litmus solution when shaken with charcoal becomes colourless.
• The precipitate of Mg(OH)2 attains blue colour when precipitated in presence of
magneson reagent. The colour is due to adsorption of magneson.

Features-
• The extent of adsorption decreases with an increase in temperature.
• The extent of adsorption increases with an increase of surface area of the adsorbent.
• The extent of adsorption depends on the concentration of the solute in solution.
• The extent of adsorption depends on the nature of the adsorbent and the adsorbate.
Freundlich’s equation approximately describes the behaviour of adsorption from solution
with a difference that instead of pressure concentration is used:

On taking logarithm of the above equation, we have

55
For More Material Join: @JEEAdvanced_2024
➢ Applications of Adsorption
1) Production of high vacuum: the remaining traces of air can be adsorbed by charcoal.
2) In gas masks: device which consists of activated charcoal or mixture of adsorbents,
used for breathing in coal mines to adsorb poisonous gases.
3) For Controlling humidity: Silica and aluminium gels are used as adsorbents.
4) For the removal of colouring matter from solutions: Animal charcoal is used as
adsorbent
5) In heterogeneous catalysis: Manufacture of ammonia using iron as a catalyst,
manufacture of H2SO4 by contact process and use of finely divided nickel in the
hydrogenation of oils are excellent examples of heterogeneous catalysis.
6) For separation of inert gases: Due to the difference in degree of adsorption of gases by
charcoal, a mixture of noble gases can be separated by adsorption on coconut charcoal
at different temperatures.
7) In curing diseases: Several drugs are used to kill germs by getting adsorbed on them.
8) In froth floatation process: Used for concentration of sulphide ores.
9) As adsorption indicators: Surfaces of certain precipitates such as silver halides have
the property of adsorbing some dyes like eosin, fluorescein, etc. and thereby producing
a characteristic colour at the end point.
10) In chromatographic analysis: Chromatographic analysis finds a number of
applications in analytical and industrial fields.

➢ Catalysis
• Potassium chlorate, when heated strongly decomposes slowly giving dioxygen. The
decomposition occurs in the temperature range of 653-873 K.
2KClO3 → 2KCl + 3O2
However, when a little of manganese dioxide is added, the decomposition takes place
at a considerably lower temperature range, i.e., 473-633 K and also at a much-
accelerated rate.
• Berzelius gave the term catalyst.
• Catalyst and Catalysis: Substances, which accelerate the rate of a chemical reaction
and themselves remain chemically and quantitatively unchanged after the reaction, are
known as catalysts, and the phenomenon is known as catalysis.
• Promoters and poisons: Promoters are substances that enhance the activity of a
catalyst while poisons decrease the activity of a catalyst. in Haber’s process for
manufacture of ammonia, molybdenum acts as a promoter for iron which is used as a
catalyst.

➢ Catalysis can be broadly divided into two groups:

(i) Homogeneous catalysis: When the reactants products and the catalyst are in the same
phase (i.e., liquid or gas), the process is said to be homogeneous catalysis.

56
For More Material Join: @JEEAdvanced_2024
 Examples of homogeneous catalysis:

(ii) Heterogeneous catalysis: The catalytic process in which the reactants and the
catalyst are in different phases is known as heterogeneous catalysis.
Examples of heterogeneous catalysis:

2SO2 ( g ) ⎯⎯⎯
( )
→ 2SO3 ( g )
Pt s

N2 ( g ) + 3H 2 ( g ) ⎯⎯⎯
( )
→ 2 NH3 ( g ) ( Haber's process )
Fe s

4 NH3 ( g ) + 5O2 ( g ) ⎯⎯⎯ → 4 NO ( g ) + 6H 2 O ( g ) (Ostwald’s process)

Pt ( s )

Vegetable oils(1) + H 2 ( g ) ⎯⎯⎯

Ni ( s )
→ Vegetable ghee(s)

➢ Adsorption Theory of Heterogeneous Catalysis

This theory explains the mechanism of heterogeneous catalysis. The mechanism involves
five steps:
1) Diffusion of reactants to the surface of the catalyst
2) Adsorption of reactant molecules on the surface of the catalyst.
3) Occurrence of chemical reaction on the catalyst’s surface through formation of an
intermediate.
4) Desorption of reaction products from the catalyst surface, and thereby, making the
surface available again for more reaction to occur.
5) Diffusion of reaction products away from the catalyst’s surface.

57
For More Material Join: @JEEAdvanced_2024
 Drawback of this theory is that it does not explain the action of catalytic promoters and
catalytic poisons.

➢ Important features of solid catalysts:

● Activity:
• By activity of a catalyst, we mean its capacity to increase the speed of chemical
reaction.
• The activity depends on the strength of chemisorption.
• The adsorption should be reasonably strong but not so strong that the adsorbed
molecules become immobile, and no space is available for other reactants to get
adsorbed.
• For hydrogenation reaction, the catalytic activity increases from Group 5 to Group 11
metals with maximum activity being shown by groups 7-9 elements of the periodic
table
● Selectivity: By selectivity of a catalyst, we mean its ability to direct the reaction to
form particular products excluding others e.g.,

➢ Shape Selective Catalysis by Zeolites

• The catalytic reaction that depends upon the pore structure of the catalyst and the size
of the reactant and product molecules is called shape-selective catalysis.
• Zeolites are good shape-selective catalysts because of their honeycomb-like
structures. They are microporous aluminosilicates with three-dimensional network of
silicates in which some silicon atoms are replaced by aluminium atoms giving Al–O–
Si framework.
• The reactions taking place in zeolites depend upon the size and shape of reactant and
product molecules as well as upon the pores and cavities of the zeolites.
• An important zeolite catalyst used in the petroleum industry is ZSM-5. It converts
alcohols directly into gasoline (petrol) by dehydrating them to give a mixture of
hydrocarbons.

➢ Enzyme Catalysis
• Enzymes are complex nitrogenous organic compounds which are produced by living
plants and animals.
• They catalyse numerous reactions, especially those connected with natural processes.
• The enzymes are termed as biochemical catalysts and the phenomenon is known as
biochemical catalysis.

58
For More Material Join: @JEEAdvanced_2024
➢ Example of few enzyme catalysed reactions are given below:
S.No. Reaction Enzyme Source
(i) Inversion of cane sugar Invertase Yeast
C12 H 22O11 (aq) + H 2O(I) ⎯⎯⎯ ⎯
Invertase
→ C6 H12O6 (aq)+ C6 H12O6 (aq)
Glu cose Fructose

(ii) Conversion of glucose into ethyl alcohol Zymase Yeast

C6 H12O6 (aq) ⎯⎯⎯→ 2C2 H5OH(aq) + 2CO2 (g)
Zymase

(iii) Conversion of starch into maltose Diastase Malt

2(C6 H10O5 )n (aq) + nH 2O(I) ⎯⎯⎯→ nC12 H 22O11 (aq)
Diastase

Maltose

(iv) Conversion of maltose into glucose Maltase Yeast

C12 H 22O11 (aq) + H 2O(I) ⎯⎯⎯→ 2C6 H12O6 (aq)
Maltase

Glu cose

(v) Manufacture of acetic acid from ethyl alcohol Mycoder Old

CH3CH2 OH(l) + O2 (g) → CH3COOH(I) + H2 O(I) ma aceti vinegar
(vi) Decomposition of urea into NH3 and CO2 Urease Soyabean
NH2CONH2 (aq) + H 2O(I) ⎯⎯⎯→ NH3 (g) + CO2 (g)
Urease

(vii) Conversion of proteins into peptides in the stomach Pepsin Stomach

(viii) Conversion of proteins into amino acids by hydrolysis in Trypsin Intestine
intestine
(ix) Conversion of milk into curd Lactobac Curd
illi

➢ Characteristics of enzyme catalysis

(i) Efficiency: One molecule of an enzyme may transform one million molecules of the
reactant per minute.
(ii) Specificity: Each enzyme catalysis only one reaction, so highly specific in nature. The
enzyme urease catalyses the hydrolysis of urea only. It does not catalyse hydrolysis of
any other amide.
(iii) Optimum temperature and pH: The optimum temperature range for enzymatic activity
is 298-310 K whereas optimum pH range is 5-7.
(iv) Increasing activity in presence of activators and co-enzymes: The enzymatic activity
is increased in the presence of certain substances, known as co-enzymes. Activators
are generally metal ions such as Na+ , Mn2+, Co2+, Cu2+, etc. These metal ions, when
weakly bonded to enzyme molecules, increase their catalytic activity. Example:
Enzyme, Amylase in presence of sodium chloride i.e., Na+ ions are catalytically very
active.
(v) Influence of inhibitors and poisons: The activity of enzyme is slowed down in the
presence of certain substances called inhibitors or poison. The inhibitors interact with
the active functional groups on the enzyme surface and often reduce or completely
destroy the catalytic activity of the enzymes.

59
For More Material Join: @JEEAdvanced_2024
➢ Mechanism of enzyme catalysis
The most accepted mechanism of enzyme- catalysed reaction is known as lock and key
mechanism:

The enzyme-catalysed reactions may be considered to proceed in two steps:

Step 1: Binding of enzyme to substrate to form an activated complex. There are a number
of cavities present on the surface of colloidal particles of enzymes. These cavities are of
characteristic shape and possess active groups such as -NH2, -COOH, -SH, -OH, etc. These
are the centres on the surface of enzyme particles. The molecules of the reactant (substrate),
which have complementary shape, fit into these cavities just like a key fit into a lock.
E + S → ES
Step 2: Decomposition of the activated complex to form product. Because of the presence
of active groups, an activated complex is formed which then decomposes to yield the
products.
ES → E + P

➢ Catalysts in Industry
Process Catalyst

1. Haber’s process for the manufacture of Finely divided iron, molybdenum as

ammonia promoter: conditions: 200 bar pressure and
N2(g) + 3H2(g) → 2NH3(g) 723-773 temperature. Now-a-days, a
mixture of iron oxide, potassium oxide and
alumina are used.

2. Ostwald’s process for the manufacture Platinised asbestos:

of nitric acid. temperature 573K.
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
2NO(g) + O2(g) → 2NO2(g)
4NO2(g) + 2H2O(l) + O2(g) → 4HNO3(aq)

3. Contact process for the manufacture of Platinised asbestos or vanadium pentoxide

sulphuric acid. (V2O5):
2SO2(g) + O2(g) → 2SO3(g) temperature 673-723K
SO2(g) + H2SO4(aq) → H2S2O7(l)
oleum
H2S2O7(l) + H2O(l) → 2H2SO4(aq)

60
For More Material Join: @JEEAdvanced_2024
➢ Colloids: A colloid is a heterogeneous system in which one substance is dispersed
(dispersed phase) as very fine particles in another substance called dispersion medium.

True solution Colloids Suspension

Size of solute particles < 1 Size of particle between Size of particle > 1000 nm
nm 1nm to 1000 nm

Homogeneous Heterogeneous Heterogeneous

Particle pass through Particle pass through Particle cannot pass through
ordinary filter paper and ordinary filter paper but not ordinary filter paper and
animal membrane through animal membrane animal membrane

Example - Sugar solution, Example- Fog, mist Example- Muddy water,

Salt solution Smoke in the air

➢ Classification of Colloids
❖ Classification Based on Physical State of Dispersed Phase and Dispersion
Medium
Dispersed Dispersion Type or Examples
phase medium colloid

Solid Solid Solid sol Some coloured glasses and gemstones

Solid Liquid Sol Paints, cell fluids
Solid Gas Aerosol Smoke, dust
Liquid Solid Gel Cheese, jellies
Liquid Liquid Emulsion Milk, hair cream, butter
Liquid Gas Aerosol Fog, mist, cloud, insecticide sprays
Gas Solid Solid sol Pumice stone, foam rubber
Gas Liquid Foam Froth, whipped cream, soap lather

❖ Classification Based on Nature of Interaction between Dispersed Phase and

Dispersion Medium
Lyophilic colloids Lyophobic colloids

These are easily formed by direct mixing These are formed by special method

Reversible in nature Irreversible in nature

Vert stable Unstable, require stabilizers

The particles are heavily hydrated due to The particles of colloids are not

61
For More Material Join: @JEEAdvanced_2024
 the attraction for the solvent. appreciably hydrated

Precipitated by high conc. of electrolyte. Precipitated by low conc. of electrolyte.

E.g. gum, gelatine, starch, rubber, etc., E.g. Metal solution, gold etc.
with a suitable liquid

❖ Classification Based on Type of Particles of the Dispersed Phase, Multimolecular,

Macromolecular and Associated Colloids
● Multimolecular colloids: On dissolution, a large number of atoms or smaller
molecules of a substance aggregate together to form species having size in the
colloidal range (1–1000 nm). The species thus formed are called multimolecular
colloids. For example, a gold sol may contain particles of various sizes having many
atoms. Sulphur sol consists of particles containing a thousand or more of S8 sulphur
molecules.
● Macromolecular colloids: Macromolecules in suitable solvents form solutions in
which the size of the macromolecules may be in the colloidal range. Such systems
are called macromolecular colloids. Examples of naturally occurring macromolecules
are starch, cellulose, proteins and enzymes; and those of man-made macromolecules
are polythene, nylon, polystyrene, synthetic rubber, etc.
● Associated colloids (Micelles): There are some substances which at low
concentrations behave as normal strong electrolytes, but at higher concentrations
exhibit colloidal behaviour due to the formation of aggregates. The aggregated
particles thus formed are called micelles. These are also known as associated colloids.
❖ Kraft temperature and critical micelle concentration (CMC)
The formation of micelles takes place only above a particular temperature called Kraft
temperature (Tk) and above a particular concentration called critical micelle
concentration (CMC).

➢ Mechanism of micelle formation

● Mechanism can be explained with the help of soap solution:

62
For More Material Join: @JEEAdvanced_2024
 63
For More Material Join: @JEEAdvanced_2024
➢ Cleansing action of soaps

➢ Preparation of Colloids
● Chemical methods

● Electrical disintegration or Bredig’s Arc method

➔ This process involves dispersion as well as condensation.
➔ Colloidal sols of metals such as gold, silver, platinum, etc., can be prepared by this
method.
➔ In this method, an electric arc is struck between electrodes of the metal immersed
in the dispersion medium. The intense heat produced vapourises the metal, which
then condenses to form particles of colloidal size.

64
For More Material Join: @JEEAdvanced_2024
 ● Peptization
➔ The process of converting a precipitate into colloidal sol by shaking it with dispersion
medium in the presence of a small amount of electrolyte.
➔ The electrolyte used for this purpose is called peptizing agent.
➔ This method is applied, generally, to convert a freshly prepared precipitate into a
colloidal sol.

➢ Purification of Colloidal Solutions

The process used for reducing the amount of impurities to a requisite minimum is known
as purification of colloidal solution.
● Dialysis:

● Electro-dialysis: Ordinarily, the process of dialysis is quite slow. It can be made

faster by applying an electric field if the dissolved substance in the impure colloidal
solution is only an electrolyte. The process is then named electrodialysis.

65
For More Material Join: @JEEAdvanced_2024
 ● Ultrafiltration:

➢ Properties of Colloidal Solutions

i) Colligative properties:

ii) Tyndall effect:

● The Tyndall effect is due to the fact that colloidal particles scatter light in all directions
in space.
● This scattering of light illuminates the path of the beam in the colloidal dispersion.
● The bright cone of the light is called the Tyndall cone.
● Tyndall effect is observed only when the following two conditions are satisfied:
(i) The diameter of the dispersed particles is not much smaller than the wavelength of
the light used.
(ii) The refractive indices of the dispersed phase and the dispersion medium differ
greatly in magnitude.
• Tyndall effect can be observed during the projection of picture in the cinema hall due
to scattering of light by dust and smoke particles present there.
Ultramicroscope
• Tyndall effect can be observed during the projection of picture in the cinema hall due
to scattering of light by dust and smoke particles present there.
• Ultramicroscope does not render the actual colloidal particles visible but only observe
the light scattered by them. Thus, ultramicroscope does not provide any information
about the size and shape of colloidal particles.
iii) Colour:
● The colour of colloidal solution depends on the wavelength of light scattered by the
dispersed particles.
● The wavelength of light further depends on the size and nature of the particles.

66
For More Material Join: @JEEAdvanced_2024
● The colour of colloidal solution also changes with the manner in which the observer
receives the light.
● For example:
➢ a mixture of milk and water appears blue when viewed by the reflected light and red
when viewed by the transmitted light.
➢ Finest gold sol is red in colour; as the size of particles increases, it appears purple,
then blue and finally golden.
iv) Brownian movement:
● When colloidal solutions are viewed under a powerful ultramicroscope, the
colloidal particles appear to be in a state of continuous zig-zag motion all over the
field of view. This motion is known as the Brownian movement.
● This motion was first observed by the British botanist, Robert Brown.
● This motion is independent of the nature of the colloid but depends on the size of
the particles and viscosity of the solution. Smaller the size and lesser the viscosity,
faster is the motion.

v) Charge on colloidal particles:

● Colloidal particles always carry an electric charge and may be either positive or
negative.
Positively charged sols Negatively charged sols

Hydrated metallic oxides. e.g., Metals. e.g.. copper. silver. gold sols.
Al2O3.xH2O, CrO3.xH2O and
Fe2O3.xH2O, etc.

Basic dye stuffs, e.g., methylene blue sol. Metallic sulphides, e.g., As2S, Sb2S3. Cds
sols.

Haemoglobin (blood) Acid dye stuffs, e.g.. eosin. congo red

sols.

Oxides, e.g., TiO2 sol. Sols of starch, gum, gelatin, clay,

charcoal, etc.

● The charge on the sol particles can be due to any of the following reasons:
➔ due to electron capture by sol particles during electro dispersion of metals
➔ due to preferential adsorption of ions from solution
➔ due to preferential adsorption of ions from solution
● Development of charge on sol particles by preferential adsorption of ions is described
below:
➔ The sol particles acquire positive or negative charge by preferential adsorption of
positive or negative ions.

67
For More Material Join: @JEEAdvanced_2024
 ➔ When two or more ions are present in the dispersion medium, preferential
adsorption of the ion common to the colloidal particle usually takes place.
➔ For example:
(a) When a highly diluted solution of silver nitrate is added to a highly diluted
potassium iodide solution, the precipitated silver iodide adsorbs iodide ions from
the dispersion medium and negatively charged colloidal sol results. However,
when KI solution is added to AgNO3 solution, positively charged sol results due
to adsorption of Ag+ ions from dispersion medium.
AgI / I − AgI / Ag +
Negatively charged Positively charged
(b) If FeCl3 is added to the excess of hot water, a positively charged sol of hydrated
ferric oxide is formed due to adsorption of Fe3+ ions. However, when ferric
chloride is added to NaOH solution a negatively charged sol is obtained with
adsorption of OH– ions.

➔ Having acquired a positive or a negative charge by selective adsorption on the

surface of a colloidal particle as stated above, this layer attracts counter ions from
the medium forming a second layer, as shown below.
AgI / I− K+ AgI / Ag + I−
➔ The combination of the two layers of opposite charges around the colloidal particle
is called the Helmholtz electrical double layer.
➔ The first layer of ions is firmly held and is termed fixed layer while the second
layer is mobile which is termed diffused layer.

Formation of double layer

➔ The charges of opposite signs on the fixed and diffused parts of the double layer result
in a difference in potential between these layers in the same manner as potential
difference is developed in a capacitor.

68
For More Material Join: @JEEAdvanced_2024
 ➔ This potential difference between the fixed layer and the diffused layer of opposite
charges is called the electrokinetic potential or zeta potential.
The presence of equal and similar charges on colloidal particles is largely responsible
in providing stability to the colloidal solution
vi) Electrophoresis:
● The movement of colloidal particles under an applied electric potential is called
electrophoresis.
● Positively charged particles move towards the cathode
● Negatively charged particles move towards the anode

● When electrophoresis, i.e., movement of particles is prevented by some suitable means,

it is observed that the dispersion medium begins to move in an electric field. This
phenomenon is termed electroosmosis.

vii) Coagulation or precipitation:

• The process of aggregation of colloidal particles into an insoluble precipitate by the
addition of some suitable electrolyte.
• The stability of the lyophobic sols is due to the presence of charge on colloidal particles
• If, somehow, the charge is removed, the particles will come nearer to each other to form
aggregates (or coagulate) and settle down under the force of gravity.
• By electrophoresis: Colloidal particles move towards oppositely charged electrodes,
get discharged and precipitated.
• By mixing two oppositely sols: neutralize their charges and get partially or completely
precipitated.
Example: Positively charged Fe(OH)3 and negatively charged As2S3 colloidal particle
containing sol on mixing get coagulated.
• By boiling: Increased collisions between sol particle and the water molecule removed
the adsorbed electrolytes.
Example: Sol of sulphur and silver halide

69
For More Material Join: @JEEAdvanced_2024
 • By persistent dialysis: Traces of the electrolyte present in the sol are removed almost
completely and the colloids become unstable and ultimately coagulate.
• By addition of electrolyte: When excess of an electrolyte is added, the colloidal
particles are precipitated. A negative ion causes the precipitation charged sol and vice
versa.
Hardy-Schulze Rule: The greater the valence of the flocculating ion added, the greater is
its power to cause precipitation.
• In the coagulation of a negative sol, the flocculating power is in the order.
Al3+ > Ba2+ > Na+
• In the coagulation of a positive sol, the flocculating power is in the order.
[Fe(CN)6]4- > PO43- > SO42- > Cl-
Coagulation value: The minimum concentration of an electrolyte in millimoles per litre
required to cause precipitation of a sol in two hours is called coagulating value.
• The smaller the quantity needed, the higher will be the coagulating power of an ion.

➢ Coagulation of lyophilic sols

There are two factors which are responsible for the stability of lyophilic sols. These
factors are the charge and solvation of the colloidal particles. When these two factors are
removed, a lyophilic sol can be coagulated. This is done
(i) by adding an electrolyte and
(ii) by adding a suitable solvent.
When solvents such as alcohol and acetone are added to hydrophilic sols, the dehydration
of dispersed phase occurs. Under this condition, a small quantity of electrolyte can bring
about coagulation.

➢ Protection of colloids
• Lyophilic sols are more stable than lyophobic sols due to extensively solvated
• Lyophobic sols can easily precipitate by addition of small amount of an electrolyte.
• Lyophobic sol can be prevented from coagulation by addition of some lyophilic colloid
by formation of protective layer by lyophilic sols outside lyophobic sols.
• Such lyophilic colloidal are called protective sols
Example: Gelatin, Sodium caseinate, Egg albumin, Gum arabic, Potato starch etc.
➢ Emulsions
● These are liquid-liquid colloidal systems.
● If a mixture of two immiscible or partially miscible liquids is shaken, a coarse
dispersion of one liquid in the other is obtained which is called emulsion.
● There are two types of emulsions:
(i) Oil dispersed in water (O/W type): Examples of this type of emulsion are milk and
vanishing cream
(ii) Water dispersed in oil (W/O type): Examples of this type are butter and cream
● Emulsions of oil in water are unstable and sometimes they separate into two layers on
standing.

70
For More Material Join: @JEEAdvanced_2024
 ● For stabilisation of an emulsion, a third component called emulsifying agent is usually
added.
● The emulsifying agent forms an interfacial film between suspended particles and the
medium.
● The principal emulsifying agents for O/W emulsions are proteins, gums, natural and
synthetic soaps, etc.
● The principal emulsifying agents for W/O, heavy metal salts of fatty acids, long chain
alcohols, lampblack, etc.
● Emulsions can be diluted with any amount of the dispersion medium. On the other hand,
the dispersed liquid when mixed, forms a separate layer.
● The droplets in emulsions are often negatively charged and can be precipitated by
electrolytes.
● They also show Brownian movement and Tyndall effect.
● Emulsions can be broken into constituent liquids by heating, freezing, centrifuging, etc.

➢ Colloids Around Us
(i) Blue colour of the sky: Dust particles along with water suspended in air scatter blue
light which reaches our eyes and the sky looks blue to us.
(ii) Fog, mist and rain: When a large mass of air containing dust particles, is cooled below
its dew point, the moisture from the air condenses on the surfaces of these particles
forming fine droplets. These droplets being colloidal in nature continue to float in air
in the form of mist or fog. Clouds are aerosols having small droplets of water suspended
in air. On account of condensation in the upper atmosphere, the colloidal droplets of
water grow bigger and bigger in size, till they come down in the form of rain.
Sometimes, the rainfall occurs when two oppositely charged clouds meet. It is possible
to cause artificial rain by throwing electrified sand or spraying a sol carrying charge
opposite to the one on clouds from an aeroplane.
(iii) Food articles: Milk, butter, halwa, ice creams, fruit juices, etc., are all colloids in one
form or the other.
(iv) Blood: It is a colloidal solution of an albuminoid substance. The styptic action of alum
and ferric chloride solution is due to coagulation of blood forming a clot which stops
further bleeding.
(v) Soils: Fertile soils are colloidal in nature in which humus acts as a protective colloid.
On account of colloidal nature, soils adsorb moisture and nourishing materials.
(vi) Formation of delta: River water is a colloidal solution of clay. Sea water contains a
number of electrolytes. When river water meets the sea water, the electrolytes present
in sea water coagulate the colloidal solution of clay resulting in its deposition with the
formation of delta.

➢ Applications of colloids
(i) Electrical precipitation of smoke: Smoke is a colloidal solution of solid particles such
as carbon, arsenic compounds, dust, etc., in air. The smoke, before it comes out from
the chimney, is led through a chamber containing plates having a charge opposite to
that carried by smoke particles. The particles on coming in contact with these plates

71
For More Material Join: @JEEAdvanced_2024
 lose their charge and get precipitated. The particles thus settle down on the floor of
the chamber. The precipitator is called Cottrell precipitator
(ii) Purification of drinking water: The water obtained from natural sources often contains
suspended impurities. Alum is added to such water to coagulate the suspended
impurities and make water fit for drinking purposes.
(iii) Medicines: Most of the medicines are colloidal in nature. For example, argyrol is a
silver sol used as an eye lotion. Colloidal antimony is used in curing kalaazar.
Colloidal gold is used for intramuscular injection. Milk of magnesia, an emulsion, is
used for stomach disorders. Colloidal medicines are more effective because they have
large surface area and are therefore easily assimilated.
iv) Tanning: Animal hides are colloidal in nature. When a hide, which has positively
charged particles, is soaked in tannin, which contains negatively charged colloidal
particles, mutual coagulation takes place. This results in the hardening of leather. This
process is termed as tanning. Chromium salts are also used in place of tannin.
(v) Cleansing action of soaps and detergents.
(vi) Photographic plates and films: Photographic plates or films are prepared by coating
an emulsion of the light sensitive silver bromide in gelatin over glass plates or
celluloid films.
(vii) Rubber industry: Latex is a colloidal solution of rubber particles which are negatively
charged. Rubber is obtained by coagulation of latex.
(viii) Industrial products: Paints, inks, synthetic plastics, rubber, graphite lubricants,
cement, etc., are all colloidal solutions.

72
For More Material Join: @JEEAdvanced_2024
 General Principles and Processes of Isolation of Elements

➢ General points:
● Minerals: Naturally occurring chemical substances in the earth’s crust obtainable by
mining.
● Ores: Minerals which are viable to be used as a source of the metal.
● Gangue: Ores are contaminated with undesired minerals called gangue
● Metallurgy: Entire scientific and technological process used for isolation of the metal
from its ores.
● Pyrometallurgy: Use of high temperatures to extract and purify metals
● Isolation and extraction should be chemically feasible and commercially viable.

➢ Occurrence of metals:
● Abundance in earth crust
⮚ 2nd most abundant: Fe.
❖ Extracted from oxide ores which do not produce polluting gases (Eg: SO2 is
produced when Fe is extracted from iron pyrites)
❖ Has great importance in biological substances
⮚ 3rd most abundant: Al.
❖ Extracted from bauxite
❖ Found in mica, clay.
❖ Gemstones contain Al2O3 with impurities like Cr(in ruby), Co(in sapphire)).
➢ Metal, its ores and its uses:

Metal Ore Uses

Al 1. Al foils - In wrappers for chocolates

2. Al fine dust - In paints, lacquers
Kaolinite [Al2(OH)4. Si2O5] 3. In extraction of Cr, Mn from their oxides
4. In wires as it is good conductor of electricity
5. Al alloys light in weight and highly useful

Fe Haematite Fe2O3 1. Cast iron - Casting stoves, gutter pipes, toys,

Magnetite Fe3O4 railway sleepers.
Siderite FeCO3 2. Wrought iron - Anchors, wires, bolts, chains,
Iron pyrites FeS2 agricultural implements

Cu Copper pyrites - CuFeS2 1. In electric wires, water and steam pipes

Malachite - CuCO3.Cu(OH)2 2. Alloys - Brass (with Zn), bronze (with tin),
Cuprite Cu2O coinage alloy (with Ni). They are stronger than
Copper glance Cu2S metal itself.

73
For More Material Join: @JEEAdvanced_2024
 3. In steel manufacturing.
4. Nickel steel - cables, automobiles and
aeroplane parts, pendulum, measuring tapes
5. chrome steel - Cutting tools. crushing
machines.
6. stainless steel - Cycles, automobiles,
utensils, pens.

Zn 1. Galvanising iron
2. In batteries
3. In alloys- brass (Cu 60%, Zn 40%) and
german silver (Cu 25-30%, Zn 25-30%,
Ni 40–50%)
4. Reducing agent - In manufacture of dye-
stuffs and paints

➢ Steps in metallurgical process:

1. Crushing: Ores are graded and crushed to reasonable size.
2. Concentration or Dressing or Benefaction of ore: Removal of unwanted materials
(eg: sand, clay) from ore.
3. Extraction of crude metal from concentrated ore
4. Refining or purification of the crude metal

➢ Concentration of ore:
Selection of method of concentration depends on the difference in the physical properties
between gangue and the metal.
Few important procedures include:

Type Principle used Procedure and examples

Hydraulic Difference in the gravities Upstream of running water is passed through the
washing of ore and gangue powdered ore, washing off the lighter gangue
particles.

Magnetic Difference in magnetic Powdered ore is carried on a conveyor belt which

separation properties of the ore and passes over a magnetic roller. Based on the
the gangue. magnetic properties of ore and gangue, one of
them gets attracted towards the magnetic roller
separating ore from the gangue.
Eg: Iron ores

74
For More Material Join: @JEEAdvanced_2024
Froth Ore are wetted by oils and Powdered ore is suspended in water and collectors
floatation gangue particles are and froth stabilisers are added. Collectors like pine
wetter by water oil, fatty acids, xanthates etc enhance non-
wettability and froth stabilisers like Cresols,
aniline etc stabilise froth.

Minerals become wet by oils and gangue by water.

Froth carrying mineral particles is formed due to
agitation by a rotation paddle which draws in air.
Froth is separated by skimming and dired to
recover ore.

Eg: Sulphide based ores

NOTE: 2 sulphide ores can be separated by

adjusting proportion of oil and water or by using
depressants. Eg: In ore with ZnS and PbS,
depressant NaCN is added which prevents ZnS
moving into froth which PbS moves into froth

Leaching Ore is soluble in the Solvent is added externally to leach out the ore as
suitable solvent while a soluble compound leaving the impurities
gangue remains insoluble insoluble. Then the leached out soluble compound
is further converted back to the respective ore.

Eg:
1. Alumina from bauxite: Leachant: NaOH

75
For More Material Join: @JEEAdvanced_2024
 NOTE: Bauxite has SiO2, TiO2 and iron oxides as
impurities. When NaOH is added SiO2 is also
leached out as sodium silicate along with sodium
aluminate. But when CO2 is passed sodium silicate
being non reactive to CO2 remains in water, while
sodium aluminate from a precipitate of
Al2O3.xH2O

2. Silver and gold from their ores: Leachant:

NaCN

➢ Extraction of crude metal from concentrated ore:

● Pyrometallurgy: Using thermodynamic principles of reduction of oxides
● Electrometallurgy: Using electrochemical principles
● Hydrometallurgy: Using displacement reaction by dissolving ore in a suitable solution

1. Pyrometallurgy:
Oxides are easy to reduce. Thus in general 2 steps involved in extraction are:
● Conversion to oxides
● Reduction of oxides to respective metals
Conversion to oxides: Via Calcination or roasting

Calcination Roasting

Heating in absence of air below melting point. Heating in presence of air below
Volatile materials evaporate leaving the metal oxide melting point of metal
in the furnace

Eg: Eg: Sulphide ores

NOTE: On roasting copper matte

(Cu2S + FeS) in a reverberatory
furnace lined with silica, FeO and
Cu2O are formed. FeO combines
with silica and is removed as iron
silicate, also called slag.

76
For More Material Join: @JEEAdvanced_2024
NOTE: Flux is the external compound that is added to remove impurities. Flux combines with
impurity to form slag which is separated out.

➢ Reduction of oxides to respective metals:

Oxides are heated with strong reducing agents like C, CO etc.

Reduction of metals not only depends on the reducing agent used but also depends on the
temperature of reduction. The temperature requirement and the reducing agent to be used
can be predicted using gibbs free energy. ΔG for the net reaction should be -ve for the
reaction to proceed forward.

➢ Ellingham diagram:
● Graphical representation of gibbs free energy. Helps in predicting feasibility of thermal
reduction of ore at a specified temperature thereby helps in choosing appropriate
reducing agents.

● Interpretation of plot:
It plots ΔfG Vs T for the formation of oxides. Relation between ΔG and T is given
below

Thus, the plot is a straight line.

Slope = - ΔS
Y-intercept = ΔH

77
For More Material Join: @JEEAdvanced_2024
 Note-1: In general ΔS of the reaction is -ve because the randomness decreases from the
reactants to products (Have a look at the reaction below to understand)

Thus, slope of the reaction becomes positive (since ΔS = -ve)

Note-2: ΔH & ΔS values for any chemical reaction remain nearly constant even on
varying temperature. Thus, the slope of the plot remains constant with change in
temperature.

However, ΔS depends on the physical state of the compound and increases if a

compound melts (s→l) or vapourises (l→g) due to increase in molecular randomness.

In the plot of ZnO and MgO, the abrupt change in slope i.e abrupt change in ΔS
indicates change in phase (s→liq or liq→g). Eg: In the ZnO plot, the change in slope
indicates melting.

● Criteria for selection of reducing agent:

○ The reducing agent and temperature should be chosen in such a way that the
combined reaction results in ΔG reaction < 0. Example calculation is given below:
○ In general, ΔG line of reducing agent should be present below the plot of metal
oxide for it to reduce the metal oxide.
○ Reducing agent selection also depends on the economic viability along with
thermodynamic feasibility. Eg: Magnesium can be used to reduce Alumina (Al2O3)
at T< 12000C as per the thermodynamic feasibility. But it is still not used because
it is uneconomic.
○ Constructing similar diagrams for sulphides and halides, helps us understand the
reason behind the difficulty in reducing sulphides and halides.

➢ Limitations of Ellingham Diagram:

● Talks only about thermodynamics of the reaction but not the kinetics of reaction.
● Assumes reactants and products are in equilibrium because the value of ΔG is
interpreted based on equilibrium constant (ΔGV = – RT lnK).

➢ Extraction of iron from iron oxide ores:

● Procedure: Iron ores are calcinated/roasted (to remove water, decompose carbonates,
oxidise sulphides) to form Fe2O3. Fe2O3 are mixed with coke and CaCO3 and fed to the
blast furnace from the top to reduce iron oxides to iron. Also note that the impurities
such as S, As, Sb etc are removed via roasting as their oxides.
● Thermodynamics and reactions in blast furnace:
1. Thermodynamics involved in reduction of iron oxide:

78
For More Material Join: @JEEAdvanced_2024
 ❖ FeO can be reduced using ‘C’ at a temperature T > 8000C or 1073K. Also note
that FeO can also be reduced using CO at specific temperature ranges (For
proof use ellingham diagram).
❖ Fe2O3 can be reduced using ‘CO’ at much lower temperature ranges in between
500-800K.
❖ Example for thermodynamic calculation of reduction of iron oxide: FeO
reduction by coke:
❖ Consider reduction of FeO using ‘C’ from ellingham diagram

At T > 1073 K:

∴ At T > 1073 K, reduction of FeO using coke is feasible.

2. Blast furnace construct and reduction reactions:

❖ In a blast furnace a temperature gradient is present from top to bottom. (Top of
the furnace is at low temperature (≅ 500K) and bottom is at high
temperature(≅ 2200K)).
❖ Generation of temperature gradient in blast furnace:
Hot air is blown at the bottom of the furnace and coke added from the top
undergoes oxidation due to hot air creating a high temperature zone. As we
move up in the furnace the temperature decreases and thereby creates a
temperature gradient along the height of the furnace.
❖ Reactions in different temperature zones of the furnace:
At low temperature zone (500-800K)

79
For More Material Join: @JEEAdvanced_2024
 At high temperature zone (900-1500K):

At very high temperature zone

C + O2 → CO2
CO2 + C →CO

❖ Impurities removal:
CaCO3 decomposes at high temperature inside the furnace forming CaO which
combines with silica impurities and forms CaSiO3 which is removed as slag.
● Types of iron:
Pig iron: The iron obtained from blast furnace is called pig iron. Consist of 4% carbon
and many impurities in smaller amounts (e.g., S, P, Si,Mn).
Cast iron: Melting pig iron with scrap iron and coke using hot air blast. Consist of 3%
of carbon and is hard and brittle
Wrought iron: Purest form of commercial iron. By oxidising impurities of cast iron in
a reverberatory furnace lined with haematite. Also limestone is added as flux which
removes S, Si, P oxides in the form of slag. Metal is then separated from slag

80
For More Material Join: @JEEAdvanced_2024
➢ Extraction of Copper from cuprous oxide:
● Thermodynamics involved:
❖ From Ellingham diagram Cu2O line is almost at the top and can be easily reduced
by C, CO at low temperatures 500-600K
● Procedure and reactions involved:
❖ Copper ores usually consist of FeS as major impurity. During roasting of the ore in
a reverberatory furnace, the conditions are maintained in such a way that majority
FeS is converted into FeO with a minor conversion of Cu2S to Cu2O. Now FeO is
removed as slag by adding SiO2 as flux.

❖ Thus from reverberatory furnace copper matte is obtained which consist of FeS
(minor) and Cu2S (major)
❖ Copper matte is charged into a converter which is lined with silica. Following
reactions take place:

The solidified copper obtained is called blister copper as it has a blistered surface
due to SO2 evolution.

➢ Extraction of Zn from Zn oxide:

● Procedure:
❖ Reduced using coke at higher temperature compared to Cu. ZnO is made into
brickettes with coke and clay and reduced. Metal is then distilled and collected by

rapid chilli
● Electrometallurgy:
❖ Molten metal salts are reduced to metal via electrolysis. For the reduction to be
possible ΔG < 0. It follows the relation:

For ΔG < 0, E0net > 0. Consider the following example

The above reaction has E0net > 0, thus Cu2+ can be reduced Fe(s).
❖ The less reactive metals move into the solution and more reactive metals move into
solution.
❖ Mn+ are reduced and deposited at the negative electrode/ cathode.
❖ Precautions should be taken so that suitable materials are chosen for electrodes in
such a way that they won't react with metal.
❖ Flux can be added to make molten mass more conducting.

81
For More Material Join: @JEEAdvanced_2024
➢ Extraction of ‘Al’ from Al2O3:
● Hall-Heroult process:
Electrolysis of Al2O3 to extract ‘Al’. Lowering of melting point of Al2O3 and increasing
conductivity is done by adding Na3AlF6 or CaF2. Fused material is electrolysed in a
steel vessel lined with carbon.
Cathode: Carbon
Anode: Graphite
Reactions

Overall reaction:

➢ Extraction of Cl2 from brine solution:

● In general extractions from ore involves reduction of the ore. But extraction of
chlorine involves oxidation (Even leaching of gold involves oxidation of Au → Au+
and then reduced to Au using Zn). For Chlorine, Brine solution is electrolysed to
obtain chlorine gas and NaOH as byproduct.

● Mathematically it requires external emf V > 2.2V because E0 of the reaction = -2.2V.
But usually it requires an excess potential to overcome some other hindering reactions
from occurring. Because of this electrolysis of molten NaCl is performed. In that case
instead of NaOH, Na metal is obtained along with chlorine gas.

➢ Hydrometallurgy:
● The ore is dissolved in a suitable solvent and then ore is converted into metal via
displacement reaction.

➢ Extraction of Cu from low grade ores.

● By treating it with scrap iron or H2.

82
For More Material Join: @JEEAdvanced_2024
 ● Instead of using scrap iron, using scrap Zn will ease out the reduction process because
Zn is present above iron in the electrochemical series. But still iron is used because the
cost associated with Zn is high.
➢ Purification of metal/ Refining:
● Different types include:
(a) Distillation (b) Liquation
(c) Electrolysis (d) Zone refining
(e) Vapour phase refining (e) Chromatographic methods
(a) Distillation:
● For low boiling point metals: Zn & Hg.
● The impure metal is evaporated to obtain the pure metal as distillate.
(b) Liquation:
● For low melting point metals: Tin
● Flown through a sloping surface and separated from higher Melting point
impurities.
(c) Electrolytic refining:
● Cathode: pure metal, Anode: impure metal, electrolytic solution: Soluble salt of
same metal
● Example: Zn refining, Cu refining using CuSO4 as electrolytic solution etc. Cu
refining reactions are shown below

● Impurities (Sb, Se, Te, Au, Ag, Pt) deposit as anode mud
(d) Zone refining:
● Principle: impurities are more soluble in melt form than in solid state
● Circular mobile heater fixed at one end of the impure metal rod is made to move
along the rod. As the heater moves the metal rod melts and pure metal crystallizes
out of the melt and impurities pass along with the heater. All the impurities get
concentrated at one end of the rod and it is cut off.
● Produces high purity of metals.
● Used for semiconductor materials like Ge, Si, B, Ga, In

83
For More Material Join: @JEEAdvanced_2024
 (e) Vapour phase refining:
● Principle: Metal is converted into a volatile compound by adding suitable reagent.
The volatile compound is decomposed again to form metal.
● Requirements: Metal should form a volatile compound when a suitable reagent is
added and volatile compound should be easily decomposable.
● Examples:
❖ Mond’s process for ‘Ni’ refining:

❖ Van arcel method for ‘Zr’ or ‘Ti’ refining: For removing impurities oxygen and
nitrogen

Note: ZrI4 being more covalent volatilises and then is heated on a tungsten filament
to 1800K to produce pure Zr
(f) Chromatographic methods:
● Principle: Difference components of mixture can be adsorbed by different
adsorbents. The impure metal mixture is put in a liquid or gaseous medium and is
moved through an adsorbent column. DIfferent components of the mixture are
adsorbed at different levels on the column. All the adsorbed components can be
removed/ eluted by adding suitable solvents called elutants.
● Column of chromatography consists of 2 phases: mobile phase and stationary
phase. Eg: Al2O3 column.
● Mobile phase - gas or liquid or a supercritical fluid, Stationary phase: Immobile
phase Eg: Al3O3 column in column chromatography. Components of both the
phases are chosen such that components of the sample will have different
solubilities in both phases.
● Mobile phase along with the metal sample is moved through the stationary phase.
Components soluble in stationary phase take longer to cross the travel, whereas
component soluble in mobile phase travels faster and moves out of the column first
thereby separating both the components.
● Depending upon the two phases and the way the sample is inserted/injected, the
chromatographic technique is named. Eg: Gas chromatography, paper
chromatography, column chromatography

Eg: Column chromatography: Stationary phase- Al2O3 is prepared in a glass tube, Mobile
phase- liquid form. Used for purification of elements available in minute quantities and not
very different in chemical properties from the element to be purified.

84
For More Material Join: @JEEAdvanced_2024
 The p-Block Elements

Group 15 & 16
• Diversity in chemistry of p–block elements: due to their ability to react with the
elements of s–, d– and f–blocks as well as with their own.
• Group 15: nitrogen, phosphorus, arsenic, antimony, bismuth and moscovium N & P-
non-metals, As & Sb- metalloids, Bi & Mc are typical metals. (Metallic character
increases down the group).
➢ Occurrence:
• N occurs as NaNO3 (called Chile saltpetre), potassium nitrate (Indian saltpetre).
• Found in the form of proteins in plants and animals.
• P occurs in minerals of the apatite family, Ca9(PO4)6.CaX2 (X = F, Cl or OH)
• As, Sb and Bi are found mainly as sulphide minerals.
• Mc has a very short half-life and availability in very little amount.
• Refer to the following table for atomic and physical properties of group 15 elements

• All the elements of this group are polyatomic.

• Dinitrogen is a gas while all others are solids.
• Except nitrogen, all the elements show allotropy.
• Oxidation states and trends in chemical reactivity:
• Most common ox states: –3, +3 and +5.
• Bi hardly forms any compound in –3 oxidation state. The stability of +5 oxidation state
decreases down the group. The only well characterised Bi (V) compound is BiF5.
• Besides +5 oxidation state, nitrogen exhibits + 1, + 2, + 4 oxidation states also when it
reacts with oxygen.
• In the case of nitrogen, all oxidation states from +1 to +4 tend to disproportionate in
acid solution

85

For More Material Join: @JEEAdvanced_2024

• P also shows +1 and +4 oxidation states in some oxoacids. nearly all intermediate
oxidation states disproportionate into +5 and –3 both in alkali and acid
• +3 oxidation state in case of As, Sb and Bi does not disproportionation.
• Max covalency of N: 4
• Heavier elements can expand their covalency due to the presence of d orbitals.
E.g. PF–6.
• Anomalous properties of nitrogen
• small size, high electronegativity, high ionisation enthalpy and non-availability of d
orbitals.
• p𝝅 -p𝝅 multiple bonds with itself and with other elements having small size and high
electronegativity (e.g., C, O).
• P, As and Sb form single bonds as P–P, As–As and Sb–Sb while Bi forms metallic
bonds in elemental state.
• N cannot form d𝝅 –p𝝅 bond as the heavier elements can e.g., R3P = O or R3P = CH2
(R = alkyl group).
• P and As can form d𝝅 –d𝝅 bond also with transition metals when their compounds like
P(C2H5)3 and As(C6H5)3 act as ligands.
• Reactivity towards hydrogen: EH3 where E = N, P, As, Sb or Bi.
• Reducing character of the hydrides increases down the group (BiH3 is the strongest
reducing agent)
• Basicity decreases in the order NH3 > PH3 > AsH3 > SbH3 > BiH3.

• Reactivity towards oxygen: two types of oxides: E2O3 and E2O5.

• the higher oxidation state of the element is more acidic in its oxide form
• N2O3 and P2O3 are acidic..As2O3 and Sb2O3 are amphoteric, Bi2O3- basic
• Reactivity towards halogens: EX3 and EX5
• Pentahalides are more covalent than trihalides.
• Trihalides of these elements except those of nitrogen are stable.
• In the case of nitrogen, only NF3 is known to be stable.
• Trihalides except BiF3 are predominantly covalent in nature
• Reactivity towards metals: Ca3N2 (calcium nitride) Ca3P2 (calcium phosphide), Na3As
(sodium arsenide), Zn3Sb2 (zinc antimonide) and Mg3Bi2 (magnesium bismuthide).
• Dinitrogen: colourless, odourless, tasteless and non-toxic gas. b.p. 77.2 K

86

For More Material Join: @JEEAdvanced_2024

 • Preparation:

➢ Laboratory method:

• Two stable isotopes: 14N and 15N.

• N2 is inert at room temperature, however at higher temperatures, it directly combines
with some metals to form nitrides

• Haber’s Process to form ammonia:

• Dinitrogen combines with dioxygen at around 2000K tempt

• Ammonia: colourless gas with a pungent odour

Preparation: from urea

➢ Small scale production:

• Large scale production: Haber process

• Shape: trigonal pyramidal

• Highly soluble in water. Its aqueous solution is weakly basic in nature

• NH3 forms ammonium salts with acids, e.g., NH4Cl, (NH4)2 SO4, etc. As a weak base,
it precipitates the hydroxides (hydrated oxides in case of some metals) of many metals
from their salt solutions.

87

For More Material Join: @JEEAdvanced_2024

• NH3 can be used in in detection of metal ions such as Cu2+, Ag+

• Oxides of N: Refer the following table for names, formulas, preparation and physical
appearance of these oxides

• Refer to the following table for Lewis dot main resonance structures and bond
parameters of oxides:

88

For More Material Join: @JEEAdvanced_2024

 • Nitric oxide: HNO3 colourless liquid

➢ Laboratory method:
Large scale: Ostwald’s process

• Conc nitric acid is a strong oxidising agent and attacks most metals except noble metals
such as gold and platinum.
• Products of oxidation depend upon the concentration of the acid, temperature and the
nature of the material undergoing oxidation.

• Zinc reacts with dilute nitric acid to give N2O and with concentrated acid to give NO2.

89

For More Material Join: @JEEAdvanced_2024

 • Concentrated nitric acid also oxidises non–metals and their compounds.

➢ Brown Ring Test:

the ability of Fe2+ to reduce nitrates to nitric oxide, which reacts with Fe2+ to form a brown
coloured complex.

• Phosphorous: Allotropes -white, red and black.

• White phosphorus: poisonous, insoluble in water but soluble in CS2. Glows in dark
(chemiluminescence).
• It dissolves in boiling NaOH solution in an inert atmosphere giving PH3.

• White P is more reactive than red P because of angular strain in the P4 molecule (60°).
It readily catches fire in air to give dense white fumes of P4O10.-

• Red P (iron grey lustre) is obtained by heating white P at 573K in an inert atmosphere
for several days.

• Red P is odourless, nonpoisonous and insoluble in water as well as in carbon disulphide.

• Red P is much less reactive than white phosphorus.
• It does not glow in the dark
• It is polymeric, consisting of chains of P4 tetrahedra linked together
• Black phosphorus - 𝛼-black and 𝛽-black phosphorus.
• 𝛼-Black phosphorus is formed when red P is heated in a sealed tube at 803K.

90

For More Material Join: @JEEAdvanced_2024

• 𝛽-Black phosphorus is prepared by heating white P at 473 K under high pressure
• Phosphine: colourless gas with rotten fish smell and is highly poisonous
• Prepared by the reaction of calcium phosphide with water or dilute HCl.

• In the laboratory: by heating white P with conc NaOH solution in an inert atmosphere
of CO2

• Pure PH3 is obtained by adsorbing impure PH3 in HI to form phosphonium iodide

(PH4I) which on treating with KOH gives off phosphine.

• The solution of PH3 in water decomposes in presence of light giving red P and H2.
• Ph3rx with CuSO4 or HgCl2 solution produce corresponding phosphides

• Phosphorus halide: two types of halides, PX3 (X = F, Cl, Br, I) and PX5 (X = F, Cl,
Br).
• Phosphorus chloride: pyramidal shape and phosphorus is sp3 hybridised.
• Obtained by passing dry chlorine over heated white phosphorus or by the action of
thionyl chloride with white phosphorus.

• Colourless oily liquid and hydrolyses in the presence of moisture

• It reacts with organic compounds containing –OH group

• PCl5: trigonal bipyramidal structure

• yellowish white powder, prepared by the reaction of white P with excess of dry chlorine

• By the action of SO2Cl2 on phosphorus

91

For More Material Join: @JEEAdvanced_2024

 • PCl5 react with moist air to give POCl3 and finally gets converted to phosphoric acid

• When heated, it sublimes but decomposes on strong heating.

• Reacts with organic compounds containing –OH group converting them to chloro
derivatives.

• Finely divided metals on heating with PCl5 give corresponding chlorides.

•The three equatorial P–Cl bonds are equivalent, while the two axial bonds are longer
than equatorial bonds.
➢ Oxoacids of P:
• Refer the following table for the important oxoacids of phosphorus with their formulas,
methods of preparation and the presence of some characteristic bonds in their structures

92

For More Material Join: @JEEAdvanced_2024

• Orthophophorous acid (or phosphorous acid) on heating disproportionates to give
orthophosphoric acid (or phosphoric acid) and phosphine.

• Hypophosphorous acid is a good reducing agent as it contains two P–H bonds

• Group 16: chalcogens, general electronic configuration: ns2 np4

• Oxygen, sulphur, selenium, tellurium, polonium and livermorium
• O & S- non-metals, Se & Te- metalloids, Po- metal and radioactive (Half-life 13.8
days).
• Occurrence: Oxygen forms about 46.6% by mass of earth’s crust
• Refer to the following table for atomic and physical properties of group16 elements

93

For More Material Join: @JEEAdvanced_2024

• Sulphur exists primarily as sulphates such as gypsum CaSO4.2H2O, epsom salt
MgSO4.7H2O, baryte BaSO4 and sulphides such as galena PbS, zinc blende ZnS, copper
pyrites CuFeS2.
• Selenium and tellurium are also found as metal selenides and tellurides in sulphide ores
• Polonium occurs in nature as a decay product of thorium and uranium minerals.
• Livermorium is a synthetic radioactive element.
• Chemical properties:
• Oxidation state- Oxygen usually shows -2 oxidation state but +2 in OF2
• Other elements of the group exhibit + 2, + 4, + 6 oxidation states
• Bonding in +4 and +6 oxidation states is primarily covalent.
• Reactivity with hydrogen: H2E (E = O, S, Se, Te, Po).
• Refer to the following table for some properties of hydrides:

• Acidic character increases from H2O to H2Te.

• Thermal stability of hydrides decreases from H2O to H2Po.
• All the hydrides except water possess reducing property and this character increases
from H2S to H2Te.
• Reactivity with oxygen: EO2 and EO3, E = S, Se, Te or Po. Both types are acidic in
nature.
• O3 and SO2 are gases while SeO2 is solid.
• SO2 is reducing while TeO2 is an oxidising agent.
• Reactivity towards the halogens: EX6, EX4 and EX2
• Amongst hexahalides, hexafluorides are the only stable halides.
• Sulphur hexafluoride, SF6 is exceptionally stable for steric reasons
• SF4 is a gas, SeF4 a liquid and TeF4 a solid...sp3d hybridised...TBP geometry.
• The monohalides exist as dimer in nature, eg. S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2.
and undergo disproportionation

• Dioxygen: O2 is a colourless and odourless gas

94

For More Material Join: @JEEAdvanced_2024

➢ Laboratory preparation:

• H2O2 is readily decomposed to H2O and O2 (Can be catalyzed by finely divided metals
and manganese dioxide)
• On large scale it can be prepared from water or air
• Industrially, dioxygen is obtained from air
• Three stable isotopes: 16O, 17O and 18O. O2 is unique in being paramagnetic
• Oxgyen-oxygen double bond strength is high (493.4 kJ mol–1).
• Some of the reactions of dioxygen with metals, non-metals and other compounds are
given below.

➢ Simple oxides:
• An oxide that combines with water to give an acid is termed acidic oxide (e.g., SO2,
Cl2O7, CO2, N2O5). For example, SO2 combines with water to give H2SO3, an acid.
• Non-metal oxides are acidic but oxides of some metals in high oxidation state also have
acidic character (e.g., Mn2O7, CrO3, V2O5)
(metallic oxides are basic.) The oxides which give a base with water are known as basic
oxides (e.g., Na2O, CaO, BaO). For example, CaO combines with water to give
Ca(OH)2, a base.
• In general, metallic oxides are basic. Some metallic oxides exhibit a dual behaviour. Eg
Al2O3.

• Examples of neutral oxides are CO, NO and N2O.

• Ozone: ozone layer protects the earth’s surface from an excessive concentration of
ultraviolet (UV) radiations.
• Formation of ozone from oxygen is an endothermic process

95

For More Material Join: @JEEAdvanced_2024

• Pure ozone is a pale blue gas, dark blue liquid and violet-black solid
• Ozone is thermodynamically unstable with respect to oxygen. Due to the ease with
which it liberates atoms of nascent oxygen (O), it acts as a powerful oxidising agent.

• Quantitative method for estimating O3 gas: When ozone reacts with an excess of
potassium iodide solution buffered with a borate buffer (pH 9.2), iodine is liberated
which can be titrated against a standard solution of sodium thiosulphate
• Nitrogen monoxide combine very rapidly with ozone to produce NO2 and O2
• Oxygen-oxygen bond lengths in the ozone
molecule are identical (128 pm) and the
molecule is angular as expected with a
bond angle of about 117 degrees.
• Sulphur — Allotropic Forms: S8 - yellow
rhombic (𝛼-sulphur) and monoclinic (𝛃 -sulphur) forms
• Rhombic sulphur is stable at room temperature and transforms to monoclinic sulphur
when heated above 369 K.
• Rhombic sulphur: yellow in colour. Stable above 369 K It is readily soluble in CS2.
Monoclinic sulphur: prepared by melting rhombic sulphur in a dish and cooling.
• At 369 K both the forms are stable. This temperature is called transition temperature.
• At elevated temperatures (~1000 K), S2 is the dominant species and is paramagnetic
like O2.
• The S8 ring in both the forms is puckered and has a crown shape.

• Sulphur dioxide: SO2 is angular... colourless gas with

pungent smell
• Prepared when sulphur is burnt in air or oxygen
• In the laboratory: by treating a sulphite with dilute sulphuric acid

• Industrially, by-product of the roasting of sulphide ores

• Sulphur dioxide, when passed through water, forms a solution of sulphurous acid reacts
readily with sodium hydroxide solution

96

For More Material Join: @JEEAdvanced_2024

• SO2 reacts readily with sodium hydroxide solution

• Sulphur dioxide reacts with chlorine to give sulphuryl chloride, SO2Cl2.

• It is oxidised to sulphur trioxide by oxygen in the presence of vanadium(V) oxide
catalyst.
• Moist sulphur dioxide behaves as a reducing agent

• Oxoacids of Sulphur: H2SO3, H2S2O3, H2S2O4, H2S2O5, H2SxO6 (x = 2 to 5), H2SO4,

H2S2O7, H2SO5, H2S2O8

Structures of some important oxoacids of sulphur

• Sulphuric acid: manufactured by the Contact Process

• The key step in the manufacture of H2SO4 is the catalytic oxidation of SO2 with O2 to
give SO3 in the presence of V2O5 (catalyst).

• The reaction is exothermic, reversible and the forward reaction leads to a decrease in
volume.
• Low temperature and high pressure are the favourable conditions for maximum yield.
• The sulphuric acid obtained by Contact process is 96-98% pure. Plant operates at a
pressure of 2 bar and a temperature of 720 K.
• It's a colourless, dense, oily liquid
• Characteristics: (a) low volatility (b) strong acidic character (c) strong affinity for water
and (d) ability to act as an oxidising agent
• In aqueous solution, sulphuric acid ionises in two steps

• H2SO4 as a dehydrating agent..charring action on carbohydrates.

97

For More Material Join: @JEEAdvanced_2024

 • Both metals and non-metals are oxidised by concentrated sulphuric acid, which is
reduced to SO2.

Group 17 & 18
• Group 17: Halogens (salt producers), highly reactive non-metallic elements.
• Members: Fluorine, chlorine, bromine, iodine, astatine and tennessine (At & Ts are
radioactive elements)
• Occurrence: F & Cl are fairly abundant.
• F: mainly as insoluble fluorides (fluorspar CaF2, cryolite Na3AlF6 and fluoroapatite
3Ca3(PO4) 2.CaF2)
• Cl: deposits of dried up seas contain these compounds, e.g., sodium chloride and
carnallite, KCl.MgCl2.6H2O.
• Refer to the following table for the atomic and physical properties of G-17 elements

➢ Chemical properties:
• All the halogens exhibit –1 oxidation state
• Cl, Br, and I exhibit + 1, + 3, + 5 and + 7 oxidation states
• Higher oxidation states are realised mainly when the halogens are in combination with
F and O. e.g., in interhalogens, oxides and oxoacids

98

For More Material Join: @JEEAdvanced_2024

 • Halogens react with metals and non-metals to form halides. The reactivity of the
halogens decreases down the group.
• Ready acceptance of an electron cause halogen to be the strong oxidising agents
• F2 is the strongest oxidising halogen and it oxidises other halide ions in solution or even
in the solid phase

➢ The relative oxidising power of halogens: evident from their standard electrode potentials
their reactions with water
• Fluorine oxidises water to oxygen whereas chlorine and bromine react with water to
form corresponding hydrohalic and hypohalous acids. reaction of iodine with water is
nonspontaneous
• I– can be oxidised by oxygen in acidic medium

➢ Anomalous behaviour of fluorine:

• Most of the reactions of fluorine are exothermic
• It forms only one oxoacid while other halogens form a number of oxoacids.
• HF is a liquid (b.p. 293 K) due to strong hydrogen bonding
• Halogen (X) reactivity towards hydrogen: All for HX, but affinity for hydrogen
decreases from fluorine to iodine
• HX dissolve in water to form hydrohalic acids.
• Acidic strength: HF < HCl < HBr < HI.
• Stability of these halides: H–F > H–Cl > H–Br > H–I.

• Reactivity towards oxygen: Halogens form many oxides but most of them are unstable.
• Fluorine forms two oxides OF2 and O2F2. Only OF2 is thermally stable at 298 K
• Both are strong fluorinating agents. O2F2 oxidises plutonium to PuF6
• Decreasing order of stability of oxides formed by halogens, I > Cl > Br.
• Higher oxides of halogens tend to be more stable than the lower ones.

99

For More Material Join: @JEEAdvanced_2024

 • Chlorine oxides, Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive oxidising agents and
tend to explode.
• ClO2 is used as a bleaching agent
• Bromine oxides- Br2O, BrO2, BrO3 are the least stable halogen oxides and are powerful
oxidizing agents.
• Iodine oxides- I2O4, I2O5, I2O7 are insoluble solids and decompose on heating. I2O5 is
a very good oxidising agent and is used in the estimation of carbon monoxide.
• Reactivity towards metals: form metal halides
• The ionic character of the halides decreases in the order MF > MCl > MBr > MI
• Halides in higher oxidation state will be more covalent than the one in lower oxidation
state. For example, SnCl4, PbCl4, SbCl5 and UF6 are more covalent than SnCl2, PbCl2,
SbCl3 and UF4 respectively.
• Reactivity of halogens towards other halogens: interhalogens of the types XX’, XX3’,
XX5’ and XX7’ where X is a larger size halogen and X’ is smaller size halogen.
• Chlorine: discovered in 1774 (greenish yellow)
• Preparation: By heating manganese dioxide with concentrated hydrochloric acid.

• Or a mixture of common salt and concentrated H2SO4 is used in place of HCl

• By the action of HCl on potassium permanganate

➢ Manufacture of chlorine:
• Deacon’s process: By oxidation of hydrogen chloride gas by atmospheric oxygen in the
presence of CuCl2 (catalyst) at 723 K

➢ Electrolytic process:
• Chlorine is obtained by the electrolysis of brine (concentrated NaCl solution)
• Properties: It is a greenish yellow gas with pungent and suffocating odour
• 2-5 times heavier than air
• can be liquefied easily into greenish yellow liquid which boils at 239 K.
• It is soluble in water.
• Chlorine reacts with a number of metals and non-metals to form chlorides

• has great affinity for hydrogen

100

For More Material Join: @JEEAdvanced_2024

 • With cold and dilute alkalies chlorine produces a mixture of chloride and hypochlorite
but with hot and concentrated alkalies it gives chloride and chlorate.

• With dry slaked lime it gives bleaching powder.

• Chlorine reacts with hydrocarbons and gives substitution products with saturated
hydrocarbons and addition products with unsaturated hydrocarbons.

➢ Chlorine as oxidising agent:

• Chlorine is a powerful bleaching agent (permanent effect)

• Hydrogen Chloride: colourless and pungent smelling gas. Prepared by heating sodium
chloride with concentrated sulphuric acid

• HCl gas can be dried by passing through conc H2SO4.

• It is extremely soluble in water and ionises as follows:

• Aqueous solution is called hydrochloric acid.

• High value of dissociation constant (Ka) indicates that it is a strong acid in water. It
reacts with NH3 and gives white fumes of NH4Cl.
• Aqua regia: 3HCl + HNO3
It is used to dissolve noble metals, e.g., gold, platinum.

• Hydrochloric acid decomposes salts of weaker acids, e.g., carbonates,

hydrogencarbonates, sulphites, etc.

101

For More Material Join: @JEEAdvanced_2024

• Uses: (i) in the manufacture of chlorine, NH4Cl and glucose (from corn starch), (ii) for
extracting glue from bones and purifying bone black, (iii) in medicine and as a
laboratory reagent.
• Oxoacids of Halogens: F forms only one oxo acid. HOF is known as fluoric (I) acid or
hypofluorous acid.
• Several oxo acids of other halogens are possible but only stable in aqueous solutions or
in the salt form.

• Interhalogen compounds: Of the types XX’, XX3’, XX5’ and XX7’ where X is a larger
size halogen and X’ is smaller size halogen.
• Iodine (VII) fluoride has maximum number of atoms as the ratio of radii between I and
F should be maximum (IF7).
• Prepared by the direct combination or by the action of halogen on lower interhalogen
compounds. The product formed depends upon some specific conditions.

102

For More Material Join: @JEEAdvanced_2024

• These are all covalent molecules and are diamagnetic in nature. Only ClF is gas.
• Refer the following table for some properties of interhalogen compounds.

• Physical properties are intermediate between those of constituent halogens except that
their m.p. and b.p. are a little higher than expected.
• Interhalogen compounds are more reactive than halogens (except fluorine).
• Undergo hydrolysis giving halide ion derived from the smaller halogen and a hypohalite
(when XX’), halite (when XX’3), halate (when XX’5) and perhalate (when XX’7)
anion derived from the larger halogen.

• Interhalogen compounds are very useful fluorinating agents. ClF3 and BrF3 are used
for the production of UF6 in the enrichment of 235U.

• Group 18: noble gases: helium, neon, argon, krypton, xenon, radon and oganesson
• All are gases and chemically unreactive.

103

For More Material Join: @JEEAdvanced_2024

• The main commercial source of helium is natural gas. Xenon and radon are the rarest
elements of the group. Radon is obtained as a decay product of 226Ra.

• Oganesson has been synthetically produced by collision of 249 Cf atoms and 48Ca ions

• Refer the following table for Atomic and Physical Properties of Group 18 Elements:

• Monoatomic, colourless, odourless and tasteless.

• Low melting and boiling points because the only type of interatomic interaction in these
elements is weak dispersion forces
• Helium has the lowest boiling point (4.2 K) of any known substance.
• The first ionisation enthalpy of molecular oxygen (1175 kJmol–1) was almost identical
with that of xenon (1170 kJ mol–1).
• A number of xenon compounds mainly with most electronegative elements like fluorine
and oxygen, have been synthesised.
• Only the difluoride (KrF2) has been studied in detail.
• Xenon-fluorine compounds: Xenon forms three binary fluorides, XeF2, XeF4 and XeF6
XeF6 can also be prepared by the interaction of XeF4 and O2F2 at 143K.

• XeF2, XeF4 and XeF6 are colourless crystalline solids and sublime readily at 298 K.
• They are powerful fluorinating agents.
• Readily hydrolysed even by traces of water. For example, XeF2 is hydrolysed to give
Xe, HF and O2.

104

For More Material Join: @JEEAdvanced_2024

• XeF2 and XeF4 have linear and square planar structures respectively.
• XeF6 has seven electron pairs (6 bonding pairs and one lone pair)- distorted octahedral
structure.

• Xenon fluorides react with fluoride ion acceptors to form cationic species and fluoride
ion donors to form fluoroanions.

• Xenon-oxygen compounds:
Hydrolysis of XeF4 and XeF6 with water gives XeO3.

• Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2.

• XeO3 is a colourless explosive solid and has a pyramidal molecular structure.

• XeOF4 is a colourless volatile liquid and has a square pyramidal molecular structure.

105

For More Material Join: @JEEAdvanced_2024

 The d & f block Elements
d - BLOCK elements
➢ General properties:
● Location: Group 3-12 (Total 10 groups), Period 4- 7 (Total 4 periods)
● Transition elements: Element with incompletely filled d orbitals in its ground state or
in any one of its oxidation states.
● Named transition becoz they are flanked in between s and p block
● Zn, Cd, Hg are d-block elements but not transition elements.
3d series Sc to Zn

4d series Y to Cd

5d series La to Hg (Omitting Ce to Lu)

6d series Ac to - (Incomplete)
● d- orbitals are easily influenced by surrounding atoms and molecules compared to s or
p
● Show horizontal similarities in the properties in contrast to s & p block elements

➢ Electronic configuration:
● General electronic configuration: (n-1)d1–10ns1–2.
● General electronic configuration has exceptions due to little energy difference between
(n-1)d and ns. Eg: Cr, Cu
● Outer electronic configuration of d- block elements

106
For More Material Join: @JEEAdvanced_2024
➢ Physical properties:
Metallic structures:
● Metallic lustre, ductile, malleable, high thermal and electrical conductivity
● More than one typical metallic structures at normal temperatures except Zn, Cg, Hg,
Mn.
● Different lattice structures:

● All elements are hard due to high metallic bonding except Zn, Cd, Hg.

➢ Enthalpy of atomisation:
● Higher ΔHa ⇒ More noble the metal
● More number of unpaired valence e- ⇒ More number of e- participating in metallic
bonding⇒ stronger metallic bonding ⇒ High ΔHa (Except Mn, Tc due to their half
filled stability)
● ΔHa (2nd, 3rd series) > ΔHa (1st series), due to more frequent metal-metal bonding
in 2nd, 3rd series elements.

➢ Melting and boiling points:

● High MP & BP, low volatility.
● MP:
More unpaired electrons ⇒ stronger metallic bonding ⇒ higher MP.
MP rises to max at d5 (except Mn, Tc due to half filled stability and low metallic
bonding) and then decreases.
● BP:
High ΔHa ⇒ High BP.

➢ Atomic and ionic size:

● Period:
❖ It decreases till Fe, remains constant till Ni, increases till Zn. This is due to interplay
between screening effect and nuclear charge.
● Group:
❖ 3d to 4d => increase

107
For More Material Join: @JEEAdvanced_2024
 ❖ 4d to 5d => Constant due to filling of 4f electrons => Increase in Zeff => Regular
decrease in radii compensates for the increase in size due to new shell addition.
❖ Lanthanide contraction: Regular decrease in radii due to increase in Zeff becoz of
intervention of 4f electrons.
❖ Net result of lanthanide contraction: 4d, 5d series same size (Eg: Zr, Hf) and very
similar physical and chemical properties.

➢ Density (d = mass/volume) :
● Increases along the period i.e increase in mass dominates over the size (except Zn).

➢ Ionisation enthalpy:
● IE1 < IE2 < IE3
● The magnitude of increase in 2nd and 3rd IE for the successive elements is much
higher.
● IE1: Increases from left to right with irregularities. Low IE of Cr can be attributed to
half filled stability and high IE of Zn can be attributed to isonisation from 4s
● Unipositive ions have dns0 configuration. By removing 1e-, the relative energies
change and this leads to transferring of electron from 4s to 3d.
● The energy associated with the transfer of electron is called reorganization energy.
NOTE: Although IE’s give some idea about relative stabilities of oxidation states but it is
much more complex and cannot be generalised

➢ Oxidation state (OS):

● Variable oxidation states.
● Maximum OS shown = sum of d and s electrons (Till Mn)
● OS of 3d series:

Most common ones are in bold.

● Maximum OS stability decreases from Mn to Zn
● Variability of OS: Transition elements :By 1, Non transition elements :By 2
● Unlike p block elements, in transition elements (group 4 to 10) higher O.S are favoured
for heavier elements
● Low OS are found in complexes where ligands have π-acceptor character in addition to
the σ-bonding. Eg: Ni(CO)4 and Fe(CO)5, OS of both Ni, Fe are 0

➢ Standard electrode potential:

M2+/M:
● Plot:

108
For More Material Join: @JEEAdvanced_2024
 ● Unique behaviour of Copper:
❖ Cu2+/Cu has positive E0 value unlike others.
❖ Cu2+ cannot liberate H2 from non oxidising acids such as HCl. It reacts only with
oxidising acids like HNO3, hot concentrated H2SO4.

M3+/M2+:
● Values (Sc to Zn):

❖ low value by Sc is due to Sc3+ noble gas configuration.

❖ Highest values by Zn, Mn due to d10, d5 stability.
❖ Comparatively low value of V is due to stability of V2+ has half filled t2g level

➢ Stability of higher oxidation states:

Halides:
● Stable halides of 3d series and their oxidation states are given below:

● Usually fluorine forms the highest OS due to its high lattice energy to high bond
enthalpy.

109
For More Material Join: @JEEAdvanced_2024
➢ Oxides:
● Stable halides of 3d series and their oxidation states are given below:

➢ Magnetic properties:
Can be diamagnetic, paramagnetic, ferromagnetic (extreme of paramagnetic. They show
magnetic properties even when magnetic field is removed)
Magnetic moment:

n= number of unpaired electrons

➢ Coloured compounds:
Due to excitation of electrons from low energy d orbital to higher they are coloured. 3d0,
3d10 configurations are colourless whereas other ions are coloured

➢ Complex compounds:
Forms complexes due to small size, high charge and availability of d orbitals for bond
formation.

➢ Catalytic properties:
Good adsorption tendency and ability to change oxidation state makes them have
catalytic properties. Eg: Ni, Pd, V etc can act as catalysts

➢ Interstitial compounds:
Small atoms like H,C, N are trapped inside the crystal lattices making them have high
MP, retain metallic conductivity and are chemically inert. THey are usually non
stoichiometric.
TiC, Mn4N. Fe3H, VH0.56 and TiH1.7,

➢ Alloy:
● Homogeneous solid solutions.
● The metal constituents should be of similar radii i.e within 15% of each other
● Eg: Brass (Cu+Zn), bronze (Cu + tin)

110
For More Material Join: @JEEAdvanced_2024
➢ Chemical properties:
Oxides and oxyanions:
● Highest oxidation in oxides coincides with group number till group 7. Beyond group 7
no higher oxides above Fe2O3 are found
Eg: Sc2O3 oxidation state = +3
Mn2O7 oxidation state = +7
● As the oxidation state of oxide increases the acidic nature increases.
Example: Acidic nature order: MnO < Mn3O4 < Mn2O7 , Cr2O3 < CrO3, V2O3 (Basic)
< V2O4 < V2O5 (amphoteric)
● Acidic oxides give acids in aqueous solution. Eg: Mn2O7 gives HMnO4 and CrO3
gives H2CrO4
● V2O5, CrO3 have low MP

➢ Potassium dichromate:
● Preparation: From chromite (FeCr2O4)

● Chromate and dichromate are interconvertible based on solution pH

● Strong oxidising agent and used in volumetric analysis

Ex: In acidic medium it converts to Cr3+

● Chromyl chloride test:

Used to test for Cl- ions. K2Cr2O7 with solid KCl and few drops of H2SO4 produces
red vapours of chromyl chloride (CrO2Cl2)

➢ Potassium permanganate:
● Preparation:
1. From MnO2

2. Commercial preparation (Electrolytic oxidation)

3. In laboratory:

● Properties: Intense purple color and temperature dependent paramagnetism

● Oxidising agent: pH of the solutions play an important role in influencing the
reaction
❖ In acidic medium it converts into Mn2+
Examples:

111
For More Material Join: @JEEAdvanced_2024
 Note: Titrations with KMnO4 are not performed in HCl as it would be oxidised to
Cl2 gas

❖ In weakly basic medium it converts to MnO2

Examples:

❖ In strong basic medium it form MnO42-

f - BLOCK elements

➢ General properties:
● Location: Group 3 (Taken out and placed below), Period 6- 7 (Total 2 periods)
● Inner transition elements:
Lanthanoids (4f series) La to Lu

Actinoids (5f series) Ac to Lr

➢ Lanthanides:
Electronic configuration: 4f(1-14) 5d(0-1) 6s2

➢ Oxidation state:
● Commonly show +3 oxidation state. Occasionally +2 and +4 are shown.
● Usually +3 and +4 oxidation states tend to be converted to common oxidation state
i.e. +3. Thus Eu2+ acts as a strong reducing agent and Ce4+ act as a good oxidizing
agent
● Ce is well known to exhibit +4 state due to noble gas configuration.

➢ Atomic and ionic size:

● Overall decrease in size from La to Lu is due to lanthanide contraction
● Trend for atomic radii: Atomic size decreases from La to Lu except Eu which has the
highest size in lanthanides.
● Trend for M3+ ions: Has a regular trend and the size from La3+ to Lu3+ decreases
gradually.
● Due to lanthanide contraction the size of 4d and 5d series are almost equal and are
difficult to separate.

112
For More Material Join: @JEEAdvanced_2024
➢ Properties:
● Silvery white soft metals and tarnish rapidly in air.
● Good conductors of heat and electricity
● Hardness increases as atomic number increases
● High Melting points. Highest MP is shown by Eu.
● Density and other properties vary smoothly except Eu and Yb
● Colour: M3+ ions are coloured due to f-f transition. La3+ and Lu3+ do not show colour
due to f0 and f14 configuration.
● Magnetic property: Their ions are paramagnetic except f0 (La3+ and Ce4+)and f14 (Yb2+
and Lu3+) types Highest paramagnetism is seen in neodymium.

➢ Chemical properties:
● Earlier members of the series behave similar to ‘Ca’ and later behave more like ‘Al’.

● Their oxides being basic form hydroxides when treated with water.

➢ Uses:
● In alloy steels for plates and pipes. Eg: Mischmetall has 95% lanthanides and 5% iron
and traces of S,C, Ca, Al. Mischmetall with Mg alloy used in bullets and lighter flint.
● Mixed oxides used as catalysts in petroleum cracking.
● Ln based oxides are used in TV screens and fluorescing surfaces

➢ Actinoides:
Electronic configuration: 5f(1-14) 6d(0-1) 7s2

➢ Oxidation state:
● Large number of oxidation states (+3 to +7) are shown unlike lanthanoides because of
5f, 6d, 7s comparable energies.
● Commonly show +3 state except Th which shows +4

113
For More Material Join: @JEEAdvanced_2024
➢ Size:
● Gradual decrease in the size of atoms or M3+ ions is referred to as actinoid
contraction. The contraction is greater from element to element than in lanthanides
due to poor shielding of 5f electrons.
➢ Properties:
● Silvery in appearance.
● The structural variability due to irregularities in metallic radii is greater than
lanthanides
● Highly reactive
● Magnetic properties are complex than lanthanides
● IE of actinoides are less than lanthanoids

➢ Uses:
● In nuclear reactors, Treatment of cancer etc

➢ Applications of d and f block elements:

● Iron, steel are important construction materials.
● Nickel, V2O5, Pt, Pd etc have a huge application as catalysts
● Photographic development relies on light sensitive properties of AgBr

114
For More Material Join: @JEEAdvanced_2024
 Coordination Compounds

● Double salt: Dissociate into simple ions completely in water

Eg: Carnallite - KCl.MgCl2.6H2O,
Mohr’s salt - FeSO4.(NH4)2SO4.6H2O
potash alum - KAl(SO4)2.12H2O
● Coordination complex: Do Not dissociate completely in water
Eg: K4 [Fe(CN)6] → 4K+ + [Fe(CN)6]4–
● Examples of coordination compounds: Chlorophyll (Mg), Haemiglobin (Fe)
Vitamin B12 (Co)
⮚ Terminology:
● Coordination entity: Central metal atom or ion bonded to a fixed number of ions or
molecules.
Ex: [Ni(CO)4], [PtCl2(NH3)2], [Fe(CN)6]4–, [Co(NH3)6]3+ .
● Central atom/ ion: The ion/ atom to which one or more molecules form a coordinate
bond. In general they are referred to as lewis acids
● Ligands: Ions/ molecules bound to central atom via coordinate bond
❖ Classification based on charge: Negative, neutral or positive ligand (rare)
❖ Classification based on number of donor sites:
▪ Monodentate/ Unidentate: One donor atom. Eg: Cl–, H2O, NH3 etc
▪ Bidentate: Two donor sites. Eg: H2NCH2CH2NH2 - Ethane-1,2-diamine,
C2O42– - Oxalate.
▪ Polydentate: Multiple donor sites. Eg: Ethylenediaminetetraacetate ion
(EDTA4–) – Hexadentate

EDTA
▪ Ambidentate ligand: Can ligate through two different atoms. Eg: NO2 –, SCN–

● Eg: K4 [Fe(CN)6] : Central atom: Fe2+

Ligands: CN-
Counter ions: K+
● Coordination sphere: Central atom and the ligands attached to it, enclosed in square
brackets. Eg: K4 [Fe(CN)6] - Coordination sphere - [Fe(CN)6]4-.

115
For More Material Join: @JEEAdvanced_2024
● Coordination polyhedron: The spatial arrangement of the ligand atoms attached to
the central atom. Common polyhedra shapes are:

● Homoleptic complexes: One kind of donor.Eg: [Co(NH3)6]3+

Heteroleptic complexes: More than one kind of ligand. Eg: [Co(NH3)4Cl2]+
● Oxidation number of central atoms: Charge the central atom would carry if all the
ligands are removed along with the electron pairs that are shared with the central atom.
It is the charge on the central atom.
● Coordination number (CN): Total number of ligand donor atoms to which metal is
directly bonded.
o CN is determined only by sigma bonds and not by pi bonds
o Coordination number = Σ number of ligands × denticity
o Eg: [Fe(C2O4)3]3– : CN = 6 (‘en’ - C2O42– is a bidentate ligand).
[PtCl6]2–: CN = 6

⮚ Werner theory:
● Reactions of a series of cobalt (III) chloride ammonia complexes with AgNO3
resulted in precipitation of different numbers of moles of AgCl.
Compound Formula Colour Moles of AgCl formed

CoCl3 .6NH3 [Co(NH3)6]3+ 3Cl– Yellow 3

CoCl3 .5NH3 [Co(NH3)5]2+ 2Cl– Purple 2

CoCl3 .4NH3 [Co(NH3)4]+ Cl– Green 1

CoCl3 .4NH3 [Co(NH3)4]+ Cl– Violet 1

● Central metal show 2 types of valences: primary and secondary
● Primary valency: Ionisable ions and satisfied by negative ions
● Secondary valency: non-Ionisable. Satisfied by neutral or negative ions. It is equal
to coordination number.
● Ions/groups attached by secondary linkages have a characteristic spatial
arrangement corresponding to different coordination numbers called coordination
polyhedra
● Most common geometrical shapes are octahedral, tetrahedra, square planar.
[Co (NH3)6]3+, [CoCl(NH3)5]2+ Octahedral
,[CoCl2(NH3)4]+

116
For More Material Join: @JEEAdvanced_2024
 [Ni (CO)4] Tetrahedral

[PtCl4]2- Square planar

⮚ Nomenclature of coordination compounds:

Formulas of Coordination entities:
a. Central atom is written first
b. Ligands including polydentate are written in alphabetical order. In abbreviated
ligands the first letter is used to determine the position.
c. The coordination entity is enclosed in square brackets. Ligands when polyatomic
are enclosed in parentheses.
d. No space between ligands and metal.
e. When written without a counte-rion, then the charge is represented as the right
superscript with the number before the sign. Eg: [Co(CN)6]3–
f. Charge on cations is balanced by charge of the anions

⮚ Naming of coordination compounds:

a. Cation is named first (both positive and negative coordination entities)
b. Ligands are named in alphabetical order before the name of the central atom/ion.
c. Anionic ligands: end with -o. Neutral and cationic ligands - same names. Except
H2O - aqua, NH3 - ammine, CO - carbonyl, NO - nitrosyl.
d. Prefix mono, di, tri etc used to indicate the number of ligands. When the names of
ligands have numerical prefixes, use bis, tris, tetrakis.
e. Oxidation state is indicated by roman numerals in parentheses.
f. Neutral or cationic complex: Metal named same as element. Eg: Co - Cobalt
Anionic complex: Mental ends with suffix -ate. Eg: Co - Cobaltate.
In a few metals latin names are used- Eg: Fe - Ferrate.

Examples:
[Cr(NH3)3(H2O)3]Cl3 triamminetriaquachromium(III) chloride

[Co(H2NCH2CH2NH2)3]2(SO4)3 tris(ethane-1,2–diamine) cobalt (III) sulphate

[Ag(NH3)2][Ag(CN)2] diamminesilver(I) dicyanidoargentate(I)

[Co(NH3)4(H2O)Cl]Cl2 Tetraammineaquachloridocobalt(III) chloride

K2[Zn(OH)4] Potassium tetrahydroxidozincate(II)

K3[Al(C2O4)3] Potassium trioxalatoaluminate(III)

[CoCl2(en)2]+ Dichloridobis(ethane-1,2-diamine) cobalt (III)

[Ni(CO)4] Tetracarbonylnickel(0)

117
For More Material Join: @JEEAdvanced_2024
Isomerism: Two or more compounds having the same chemical formula but different
arrangement of atoms.
Stereoisomerism: Same chemical formula but different spatial arrangement.
(a) Geometrical isomerism: (imp cases)
Type Number of Example
GI

[Ma2b2] 2 (cis, trans)

[Mabcd] 3

[Ma2b4 ] 2 (cis, trans)

[Ma3b3 ] 2 (facial and

meridional)

[Ma2(AA)2] 2 (cis, trans)

(AA):
bidentate

(b) Optical isomerism:

● Enantiomers: Non superimposable mirror images. These molecules or ions are
called chiral.
● Compounds are optically active if there is no element of symmetry present in it.
● Two forms: dextro (d), laevo (l)

118
For More Material Join: @JEEAdvanced_2024
 ● Observed in octahedral and tetrahedral complexes only not in square planar
complexes
● Examples: [Ma2(AA)2] (Eg: [CrCl2(ox)2]3–, [PtCl2(en)2] 2+) Cis isomer shows
optical isomerism but not trans isomer.
⮚ Structural isomerism
(a) Linkage isomerism: Due to ambidentate ligands. Eg: [Co (NH3)5(NO2)] Cl2. If NO2
is bound via oxygen then it is red form and when bound via nitrogen it is yellow form.
(b) Coordination isomerism: Due to interchange of ligands between cationic and
anionic entities of different metal ions present in a complex.
Eg: [Co (NH3)6][Cr(CN)6], [Cr(NH3)6 ][Co(CN)6]
(c) Ionisation isomerism: Counter ions and ligands interchange themselves.
[Co (NH3)5(SO4)] Br, [Co (NH3)5Br]SO4.
(d) Solvate isomerism: Differ by whether or not a solvent molecule is directly bonded to
the metal ion or merely present as free solvent molecules in the crystal lattice.
Eg: [Cr (H2O)6] Cl3 (violet), [Cr (H2O)5Cl] Cl2.H2O (grey-green)

⮚ Bonding in Coordination compounds:

VBT (Valence bond theory):
● Central atom/ ion uses its (n-1) d, ns, np or ns, np, nd orbitals for hybridisation to
yield a set of equivalent orbitals of definite geometry

● Geometry can be predicted using magnetic behaviour. Few ligands like NH3, CN- are
observed to cause pairing while others like F-, Cl- doesn't cause pairing.
[Co(NH3)6]3+ 1. Diamagnetic
2. Electrons are paired.
3. Hybridisation: d2sp3, shape: Octahedral
4. Inner orbital complex or low spin or spin paired complex.

119
For More Material Join: @JEEAdvanced_2024
[CoF6]3– 1. Paramagnetic
2. Electrons aren’t paired.
3. Hybridisation: sp3d2,shape: Octahedral
4. Outer orbital or high spin or spin free complex.

[NiCl4] 2- . 1. Paramagnetic
2. Electrons aren’t paired
3. Hybridisation: sp3, shape: Tetrahedra
4. Outer orbital or high spin or spin free complex.

[Ni(CN)4 ]2– 1. Diamagnetic

2. Electrons are paired
3. Hybridisation: dsp2, shape: Square planar
4. Inner orbital complex or low spin or spin paired complex.

120
For More Material Join: @JEEAdvanced_2024
 [Ni(CO)4] 1. Diamagnetic
2. Electrons are paired
3. Hybridisation: sp3 (Because Ni oxidation state is 0)
⮚ Limitations of valence bond theory:
● No quantitative interpretation of magnetic data.
● No explanation on the colour of coordination compounds.
● No quantitative interpretation of the thermodynamic or kinetic stabilities of
coordination compounds.
● Does not explain about weak and strong ligands (ie which ligands cause pairing and
which does not).
⮚ Crystal field theory (CFT):
● Electrostatic model. Consider metal- ligand bonds to be ionic. Ligands are treated as
point charges in case of anions and dipole in case of neutral molecules.
● The degeneracy of d orbitals would be lost as the ligands asymmetrically approach the
central atoms and it results in splitting of d orbitals.
● Strong ligands mean they cause large splitting and weak ligands cause smaller splitting.
Spectrochemical series (experimentally determined based on absorption of light by
complexes) in the increasing order of field strength.
I −  Br −  SCN −  Cl −  S 2−  F −  OH −  C2 O42−  H 2 O  NCS −
 edta 4−  NH 3  en  CN −  CO
❖ Crystal field splitting in octahedral species:

d orbital splitting in an octahedral crystal field

121
For More Material Join: @JEEAdvanced_2024
 ● Say P is the pairing energy and ∆o is the octahedral splitting energy
○ If ∆o < P: 4th electron enters eg instead of causing pairing in t2g . Such ligands are
called weak field ligands and form high spin complexes
○ If ∆o > P: 4th electron enters t2g causing pairing. Such ligands are called strong
field ligands and form low spin complexes.
❖ CFT in tetrahedral complexes:
● Energy of dx2-y2 and dz2 would be less in comparison with other d orbitals

● In general, ∆t < P always. Thus, there is no pairing.

● Important relation: ∆t = (4/9) ∆0.

⮚ Magnetic moments:

For octahedral complexes the data is given below:

d electrons Availability of d electrons Magnetic behaviour

d1, d2,d3 2 vacant d orbitals Magnetic behaviour is the same as free ion.
available strong or weak
field: d2sp3

d4,d5,d6 2 vacant d orbital are Magnetic behaviour depends on ligands attached.

available only when there Eg:
is pairing of electrons [Mn(CN)6]3–, [Fe(CN)6]3– ,[Co(C2O4)3]3–: d2sp3
● Strong field: d2sp3 [MnCl6]3–, [FeF6]3–, [CoF6]3– : sp3d2
● Weak field: sp3d2

d8, d9, d10 On pairing also vacant

orbitals are unavailable
● strong or weak
field: sp3d2

122
For More Material Join: @JEEAdvanced_2024
⮚ Colour in coordination complexes:
● Transition metal complexes show a wide range of colours. The colour of the complex
is complementary to the colour absorbed. Eg: If green light is absorbed then it appears
red.

● Colour is shown due to d-d transition i.e excitation and deexcitation of electrons
amongst splitted d orbitals. Eg: [Ti(H2O)6]3+: Electron jumps from (t2g1 eg0 → t2g0 eg1 ).
● In the absence of ligands, no d orbital splitting and thus colourless.
Eg: [Ti(H2O)6]Cl3 on heating renders it colourless.
Anhydrous CuSO4 is white, but CuSO4.5H2O is blue in colour.
● Influence of ligands on the colour is shown below:
Stronger the ligand, the splitting of the d orbitals will be high, thus more energy
absorbed and wavelength absorbed becomes less.

NOTE: en (ethylene diamine) is a stronger ligand compared to water, thus as the

number of ‘en’ ligands increases, the wavelength decreases.
● Colour of gemstones: Ruby: Al2O3 containing 0.5-1% Cr3+ ions.
Emerald: Be3Al2Si6O18 containing Cr3+ ions in the octahedral sites.
⮚ Limitations of CFT:
● Assuming that ligands are point charges implies that anionic ligands should exert
greatest splitting effect but they are observed to be at the low end of the
spectrochemical series.
● Does not take into account the covalent character of the bond between ligand and the
central atom
⮚ Bonding in metal carbonyls:
● Have well defined structures - [Ni(CO)4]: Tetrahedral
[Fe(CO)5]: Trigonal bipyramidal
[Cr(CO)6]: Octahedral
[Mn2(CO)10]: Made of two square pyramidal Mn(CO)5 units joined by Mn - Mn bond
Co2(CO)8]: Made by Co-Co bridged by two CO groups

123
For More Material Join: @JEEAdvanced_2024
 ● Metal carbonyls possess both σ and π character. CO donates lone pairs to metal forming
a σ bond. Metal atom donates a pair of electrons from filled d orbital into vacant
antibonding π*orbital of carbon monoxide. This creates a synergic effect which
strengthens the bond between CO and metal.

⮚ Stability of Coordination compounds:

● Stability of complex refers to the degree of association between the two species
involved in the state of equilibrium. Equilibrium constant quantitatively expresses the
stability.

● K1, K2, etc., are referred to as stepwise stability constants. Thus, overall constant is ꞵ4.

● A pattern found for most formation constants is that the successive stability constants
decrease.

124
For More Material Join: @JEEAdvanced_2024
 ● The instability constant or the dissociation constant is reciprocal of the formation
constant.
⮚ Applications of coordination compounds:
● For quantitative and qualitative chemical analysis
Metal ions form coloured complexes with ligands and form the basis for their detection.
Eg: EDTA, DMG (dimethylglyoxime), α–nitroso–β–naphthol, cupron, etc.
● Hardness of water: By titration with Na2(EDTA). The metal ions causing hardness,
that is Ca2+ and Mg2+, form stable complexes with EDTA.
● Metal extraction and purification: Extraction of metals, such as silver and gold, is
carried out by forming their water soluble cyanide complexes with the ore (Eg:
[Au(CN)2]–). Pure gold can then be obtained from the solution by addition of zinc.
Similarly, metals can be purified by formation and then decomposition of their
coordination compounds. For example, impure Ni is purified by first converting it to
nickel carbonyl ([Ni(CO)4]) and then decomposing to form pure Ni.

● Catalysis: Used as catalysts

Zeigler-Natta catalyst TiCl4 and trialkyl aluminium Polyethylene

Wilkinson catalyst RhCl(PPh3)3 Hydrogenation of alkenes

Rhodium complexes [Rh(CO)2I2] Monsanto acetic acid

[Rh(Cl)(CO)(PPh3)2] process
[Rh(Cl)(CO)2]2
● Electroplating: a. Silver plating, K[Ag(CN)2] is used as an electrolyte
b. Gold plating, K[Au(CN)2] is used as an electrolyte
c. Copper plating, K3[Cu(CN)4] is used as an electrolyte
● Biological importance: a. Chlorophyll : Mg2+ complex (green pigment)
b. Haemoglobin: Fe2+ complex (red pigment)
c. Vitamin B12: Co3+ complex .
● Medicinal uses:
a. Treating metal poisoning: Complexing or chelating agents are used. The
coordination complex is formed between toxic metal in excess metal and the
complexing agent.
1. EDTA is used in lead poisoning. EDTA, when injected intravenously into the
bloodstream, traps lead forming a compound that is flushed out of the body with
the urine.
2. Other heavy metal (Hs, As, Al, Cr, Co, Mn, Ni, Se, Zn, Sn,Tl) poisonings that can
be treated similarly with chelation therapy
3. For Cu and Fe - chelating ligands D-penicillamine and desferrioxamine B are used
respectively.
4. New potent drugs are being created using various derivatives of metallocene.
5. Pt complex - [PtCl2(NH3)2] called cisplatin is used in treatment of cancer.

125
For More Material Join: @JEEAdvanced_2024
 Haloalkanes and Haloarenes

Haloalkanes contain halogen atom(s) attached to the sp3 hybridised carbon atom of an alkyl
group whereas haloarenes contain halogen atom(s) attached to sp2 hybridised carbon atom(s)
of an aryl group
Classification

⮚ On the Basis of Number of Halogen Atoms

mono, di, or polyhalogen (tri-,tetra-, etc.) compounds

⮚ Compounds Containing sp3 C—X Bond (X= F,Cl, Br, I)

(a) Alkyl halides or haloalkanes (R—X)
primary, secondary or tertiary

(b) Allylic halides

The Halogen atom is bonded to an sp3- hybridised carbon atom adjacent
to carbon-carbon double bond (C=C) i.e. to an allylic carbon.

(c) Benzylic halides: Halogen atom is bonded to an sp3 -hybridised carbon atom attached
to an aromatic ring.

⮚ Compounds Containing sp2 C—X Bond

(a) Vinylic halides : halogen atom is bonded to an sp2 -hybridised carbon atom

126

For More Material Join: @JEEAdvanced_2024

 (b) Aryl halides: Halogen atom is bonded to the sp2 -hybridised carbon atom of an
aromatic ring.

Nomenclature:

● The common name of haloalkanes is alkyl halides .

● Haloarenes are the common as well as IUPAC names of aryl halides.

● The dihalo-compounds having same type of halogen atoms are classified as

❖ Geminal halides (halogen atoms are present on the same carbon atom)
❖ Vicinal halides (halogen atoms are present on the adjacent carbon atoms).
● In the common name system, gem -dihalides are named as alkylidene halides and
vic-dihalides are named as alkylene dihalides.

Table : Common and IUPAC names of some Halides

127

For More Material Join: @JEEAdvanced_2024

Nature of C-X Bond

● Halogen atoms are more electronegative than carbon, the carbon-halogen bond of
alkyl halide is polarised

Methods of Preparation

⮚ From Alcohols
● Thionyl chloride is preferred because the other two products are escapable gases.
Hence the reaction gives pure alkyl halides.
● The order of reactivity of alcohols with a given haloacid is 3°>2°>1°

128

For More Material Join: @JEEAdvanced_2024

⮚ From Hydrocarbons:
(a) By free radical halogenation
● Gives a complex mixture of isomeric mono- and polyhaloalkanes, which is
difficult to separate as pure compounds.

(b) By electrophilic substitution

● Aryl chlorides and bromides can be easily prepared.

● Reactions with iodine are reversible in nature and require an oxidising agent
(HNO3,HIO4 ) to oxidise the HI formed during iodination.
● Fluoro compounds are not prepared by this method due to high reactivity of
fluorine.

(c) Sandmeyer’s reaction

● Primary aromatic amine, dissolved in cold aqueous mineral acid, is treated with
sodium nitrite, a diazonium salt is formed .
● diazonium salt with cuprous chloride or cuprous bromide results in the
replacement of the diazonium group by – Cl or –Br

129

For More Material Join: @JEEAdvanced_2024

 ● Replacement of the diazonium group by iodine does not require the presence of
cuprous halide and is done simply by shaking the diazonium salt with potassium
iodide

(d) From alkenes

(i) Addition of hydrogen halides:

● Propene yields two products, only one predominates as per Markovnikov’s rule.

(ii) Addition of halogens:

● Addition of bromine in CCl4 to an alkene resulting in discharge of reddish brown

colour of bromine constitutes an important method for the detection of double
bond in a molecule
● The addition results in the synthesis of vic-dibromides, which are colourless

⮚ Halogen Exchange
● Finkelstein reaction
R − X + NaI → R − I + NaX X =Cl , Br
● Swarts reaction.
Alkyl fluoride is easily prepared by heating an alkyl chloride/bromide in the
presence of a metallic fluoride such as AgF, Hg2F2, CoF2 or SbF3.

Physical Properties

● Alkyl halides are colourless when pure. However, bromides and iodides develop
colour when exposed to light.
⮚ Melting and boiling points:
● For same alkyl group, the boiling points of alkyl halides decrease in the order:
RI > RBr > RCl > RF.

130

For More Material Join: @JEEAdvanced_2024

 ● This is because with the increase in size and mass of halogen atom, the magnitude
of van der Waal forces increases.
● The boiling points of isomeric haloalkanes decrease with increase in branching

● Boiling points of isomeric dihalobenzenes are very nearly the same.

● The para-isomers are high melting as compared to their ortho-and meta-isomers.
It is due to symmetry of para-isomers fits in crystal lattice better as compared to
ortho- and meta-isomers

⮚ Density:
● Bromo, iodo and polychloro derivatives of hydrocarbons are heavier than water.
● The density increases with increase in number of carbon atoms, halogen atoms
and atomic mass of the halogen atoms
⮚ Solubility:
● The haloalkanes are only very slightly soluble in water.
● Haloalkanes tend to dissolve in organic solvents, because of the new
intermolecular attractions between haloalkanes and solvent molecules.
Chemical Reactions:

⮚ Reactions of Haloalkanes
1. Nucleophilic substitution:
● Substitution reaction is initiated by a nucleophile, it is called nucleophilic
substitution reaction.

Nucleophilic Substitution of Alkyl Halides

131

For More Material Join: @JEEAdvanced_2024

 ● Groups like cyanides and nitrites possess two nucleophilic centres and are called
ambident nucleophiles .

Mechanism
(a) Substitution nucleophilic bimolecular (SN2)
● The reaction between CH3Cl and hydroxide ion follows a second order kinetics,
i.e., the rate depends upon the concentration of both the reactants.

● The incoming nucleophile causes the carbon-halide bond to break while forming a
new carbon-OH bond. These two processes take place simultaneously in a single
step and no intermediate is formed
● The configuration of carbon atom under attack inverts in much the same way as
an umbrella is turned inside out, This process is called as inversion of
configuration
● Carbon atoms in the transition state are simultaneously bonded to five atoms and
therefore it is unstable.
● Tertiary halides are the least reactive because bulky groups hinder the
approaching nucleophiles. Thus the order of reactivity followed is:

132

For More Material Join: @JEEAdvanced_2024

 Primary halide > Secondary halide > Tertiary halide

Steric effects in SN2 reaction. The relative rate of SN2 reaction is given in
parenthesis

(b) Substitution nucleophilic bimolecular (SN1 )

● SN1 reactions are generally carried out in polar protic solvents (like water,
alcohol, acetic acid, etc.).
● The reaction between tert -butylbromide and hydroxide ion yields tert -butyl
alcohol and follows the first order kinetics, i.e., the rate of reaction depends
upon the concentration of only one reactant, which is tert - butyl bromide.

● It occurs in two steps.

❖ In step I, the polarised C—Br bond undergoes slow cleavage to produce a
carbocation and a bromide ion.
❖ Step I is the slowest and reversible

❖ In step II, The carbocation thus formed is then attacked by nucleophiles.

● 30 alkyl halides undergo SN1 reaction very fast because of the high stability of
30 carbocations.
● order of reactivity of alkyl halides towards SN1 and SN2 reactions as follows:

133

For More Material Join: @JEEAdvanced_2024

 ● Allylic and benzylic halides show high reactivity towards the SN1 reaction. The
carbocation thus formed gets stabilised through resonance

● For given alkyl group, the reactivity of the halide, R-X, follows the same order in
both the mechanisms
R–I > R–B > R–Cl >> R–F

(c) Stereochemical aspects of nucleophilic substitution reactions

(i) Plane polarised light and optical activity :
● Compounds which rotate the plane polarised light are called optically active
compounds.
● The angle by which the plane polarised light is rotated is measured by an
instrument called polarimeter.
● If the compound rotates the plane polarised light to the right, i.e., clockwise
direction, it is called dextrorotatory or the d-form and is indicated by
placing a positive (+) sign before degree of rotation.
● If the light is rotated towards left, the compound is said to be laevo-rotatory
or the l-form and a negative (–) sign is placed before the degree of rotation.
● Such (+) and (–) isomers of a compound are called optical isomers and the
phenomenon is termed as optical isomerism

(ii) Molecular asymmetry, chirality and enantiomers :

● If all the four substituents attached to tetrahedral carbon are different, such a
carbon is called asymmetric carbon or stereocenter.
● The asymmetry of the molecule is responsible for the optical activity
● The objects which are non-superimposable on their mirror image (like a pair
of hands) are said to be chiral and this property is known as chirality. While
the objects, which are superimposable on their mirror images are called
achiral.
● The stereoisomers related to each other as non-superimposable mirror images
are called enantiomers

134

For More Material Join: @JEEAdvanced_2024

 ● Enantiomers possess identical physical properties namely, melting point,
boiling point, solubility, refractive index, etc.They only differ with respect to
the rotation of plane polarised light.
● A mixture containing two enantiomers in equal proportions will have zero
optical rotation, as the rotation due to one isomer will be cancelled by the
rotation due to the other isomer. Such a mixture is known as racemic mixture
or racemic modification .
● A racemic mixture is represented by prefixing dl or (±) before the name, for
example (±) butan-2-ol.
● The process of conversion of enantiomer into a racemic mixture is known as
racemisation.
(iii) Retention:
● If the product will have the same general configuration of groups around the
stereocenter as that of reactant.
(iv) Inversion, retention and racemisation:
● There are three outcomes for a reaction at an asymmetric carbon atom.

● If (A) is the only compound obtained, the process is called retention of

configuration.
● If (B) is the only compound obtained, the process is called inversion of
configuration.
● If a 50:50 mixture of the above two is obtained then the process is called
racemisation and the product is optically inactive
A SN2 reaction proceeds with complete stereochemical inversion while SN1
reaction proceeds with racemisation.

2. Elimination reactions:
● When a haloalkane is heated with alcoholic solution of potassium hydroxide,
there is elimination of hydrogen atom from β-carbon and a halogen atom from the
α-carbon atom.As a result, an alkene is formed.
● Since β-hydrogen atom is involved in elimination, it is often called β-elimination.

135

For More Material Join: @JEEAdvanced_2024

 ● Saytzeff rule : “ in dehydrohalogenation reactions, the preferred product is that
alkene which has the greater number of alkyl groups attached to the doubly
bonded carbon atoms
● Thus, 2-bromopentane gives pent-2-ene as the major product

Elimination versus substitution

● A bulkier nucleophile will prefer to act as a base and abstracts a proton rather than
approach a tetravalent carbon atom (steric reasons) and vice versa.
● Primary alkyl halide will prefer a SN2 reaction,
● Secondary halide- SN2 or elimination depending upon the strength of
base/nucleophile.
● Tertiary halide- SN1 or elimination depending upon the stability of carbocation or
the more substituted alkene

3. Reaction with metals:

● Most organic chlorides, bromides and iodides react with certain metals to give
compounds containing carbon-metal bonds. Such compounds are known as
organo-metallic compounds
● An important class of organo-metallic compounds is RMgX, referred to as
Grignard Reagents.

● In the Grignard reagent, the carbon-magnesium bond is covalent but highly polar

● Grignard reagents are highly reactive and react with any source of proton (Even
water, alcohols, amines ) to give hydrocarbons.

● It is therefore necessary to avoid even traces of moisture from a Grignard reagent

⮚ Wurtz reaction
● Alkyl halides react with sodium in dry ether to give hydrocarbons

136

For More Material Join: @JEEAdvanced_2024

Reactions of Haloarenes

⮚ Nucleophilic substitution
● Aryl halides are extremely less reactive towards nucleophilic substitution reactions
due to the following reasons:
(i) Resonance effect :

● In haloarenes, C—Cl bond acquires a partial double bond character due to

resonance. As a result, the bond cleavage in haloarene is difficult than haloalkane

(ii) Difference in hybridisation of carbon atom in C— X bond:

● Haloarene, The sp2 hybridised carbon with a greater s -character is more

electronegative and can hold the electron pair of C— X bond more tightly than
sp3-hybridised carbon in haloalkane with less s-character

(iii) Instability of phenyl cation:

● In case of haloarene, the phenyl cation formed as a result of self-ionisation will

not be stabilised by resonance and therefore, SN1 mechanism is ruled out.

(iv) Because of the possible repulsion:

● It is less likely for the electron rich nucleophile to approach electron rich
arenes.

⮚ Replacement by hydroxyl group

● Chlorobenzene can be converted into phenol

● The presence of an electron withdrawing group (-NO2) at ortho- and para-positions

increases the reactivity of haloarenes

137

For More Material Join: @JEEAdvanced_2024

 ● No effect on reactivity of haloarenes is observed by the presence of electron
withdrawing groups at meta-position.

● Mechanism of the reaction is as depicted:

⮚ Electrophilic substitution reactions

138

For More Material Join: @JEEAdvanced_2024

● Halogen atoms besides being slightly deactivating are o, p -directing; due to
resonance, the electron density increases more at ortho- and para-positions than at
meta-positions.

(i) Halogenation

(ii) Nitration

(iii) Sulphonation

(iv) Friedel-Crafts reaction

139

For More Material Join: @JEEAdvanced_2024

⮚ Reaction with metals
(i) Wurtz-Fittig reaction
A mixture of an alkyl halide and aryl halide gives an alkyl arene when treated with
sodium in dry ether and is called Wurtz-Fittig reaction.

(ii) Fittig reaction

When two aryl groups are joined together. It is called the Fittig reaction.

Polyhalogen Compounds
Carbon compounds containing more than one halogen atom are usually referred to as
polyhalogen compounds.

● Dichloro-methane (Methylene chloride)

❖ Widely used as a solvent as a paint remover, as a propellant in aerosols.
● Trichloro-methane (Chloroform)
❖ The major use of chloroform today is in the production of the freon refrigerant R-
22.
❖ Slowly oxidised by air in the presence of light to an extremely poisonous gas,
carbonyl chloride, also known as phosgene.

140

For More Material Join: @JEEAdvanced_2024

 ❖ It is therefore stored in closed dark coloured bottles completely filled so that air is
kept out.
● Triiodo-methane (Iodoform)
❖ It was used earlier as an antiseptic but the antiseptic properties are due to the
liberation of free iodine and not due to the iodoform itself.
● Tetrachloro-methane (Carbontetrachloride)
❖ It is also used as feedstock in the synthesis of chlorofluorocarbons.
❖ When carbon tetrachloride is released into the air, it rises to the atmosphere and
depletes the ozone layer.

● Freons
❖ The chlorofluorocarbon compounds of methane and ethane are collectively known
as freons.
❖ It is manufactured from tetrachloromethane by Swarts reaction.
❖ These are usually produced for aerosol propellants, refrigeration and air
conditioning purposes.
❖ In the stratosphere, freon is able to initiate radical chain reactions that can upset the
natural ozone balance.
● p,p’ -Dichlo-rodiphenyl-trichloro-ethane(DDT)
❖ DDT, the first chlorinated organic insecticides.
❖ DDT is not metabolised very rapidly by animals; instead, it is deposited and stored
in the fatty tissues.

141

For More Material Join: @JEEAdvanced_2024

 Alcohols, Phenols and Ethers

 Classification
● On the Basis of Number of Hydroxyl group
Mono, di, or Polyhydric (tri-, tetra-, etc.) compounds

● According to the hybridisation of the carbon atom to which the hydroxyl group is
attached
Compounds Containing sp3 C—OH Bond
(a) Primary, secondary or tertiary alcohols: The –OH group is attached to primary,
secondary and tertiary carbon atoms, respectively.

(b) Allylic Alcohols

The –OH group is attached to an sp3- hybridised carbon atom next to the carbon-
carbon double bond, that is to an allylic carbon.

(c) Benzylic Alcohols: The –OH group is bonded to an sp3 -hybridised carbon atom
next to an aromatic ring.

● Compounds Containing sp2 C—OH Bond

(a) Vinylic Alcohols: Bonded to an sp2 -hybridised carbon atom of carbon-carbon
double bond. CH2 = CH - OH
(b) Aryl Alcohols: Bonded to an sp2 -hybridised carbon atom of an aromatic ring.

142

For More Material Join: @JEEAdvanced_2024

 Ethers: classification
● Simple or symmetrical: If the alkyl or aryl groups attached to the oxygen atom are
the same. C2H5OC2H5.
● Mixed or unsymmetrical: If the alkyl or aryl groups attached to the oxygen atom
are different.
C2H5 OCH3 and C2H5OC6 H5
 Nomenclature:
a) Alcohols:
Common name: The common name of an alcohol is derived from the common name of
the alkyl group and adding the word alcohol to it.
For example, CH3OH is methyl alcohol.
IUPAC naming:
The name of an alcohol is derived from the name of the alkane from which the alcohol is
derived, by substituting ‘e’ of alkane with the suffix ‘ol’.

b) Phenols:
The simplest hydroxy derivative of benzene is phenol. It is its common name and also an
accepted IUPAC name.

143

For More Material Join: @JEEAdvanced_2024

c) Ethers:
Common name: Ethers are derived from the names of alkyl/ aryl groups written as
separate words in alphabetical order and adding the word ‘ether’ at the end.
For example, CH3OC2H5 is ethylmethyl ether.
IUPAC name: Ethers are regarded as hydrocarbon derivatives in which a hydrogen atom
is replaced by an –OR or –OAr group, where R and Ar represent alkyl and aryl groups,
respectively.
For example, CH3OC2H5 is named as 1-methoxy ethane.

144

For More Material Join: @JEEAdvanced_2024

 Structures of Functional Groups

The carbon– oxygen bond length (136 pm) in phenol is slightly less than that in methanol.
This is due to (i) partial double bond character on account of the conjugation of an unshared
electron pair of oxygen with the aromatic ring and (ii) sp2 hybridised state of carbon to
which oxygen is attached.
 Alcohols and Phenols
Preparation of Alcohols:
❖ 1. From Alkene:
(i) By acid catalysed hydration:
➔ In case of unsymmetrical alkenes, the addition reaction takes place in accordance
with Markovnikov’s rule

 Mechanism:
Step 1: Protonation of alkene to form carbocation by electrophilic attack of H3O+
H2O + H+ → H3O+

Step 2: Nucleophilic attack of water on carbocation.

Step 3: Deprotonation to form an alcohol.

(ii) By hydroboration–oxidation:
Diborane (BH3)2 reacts with alkenes to give trialkyl boranes as addition product.
Which is oxidised to alcohol by hydrogen peroxide in the presence of aqueous
sodium hydroxide.
The addition of borane takes place in a way opposite to Markovnikov's rule.

145

For More Material Join: @JEEAdvanced_2024

2. From carbonyl compounds:
(i) By reduction of aldehydes and ketones:
➔ Aldehydes yield primary alcohols whereas ketones give secondary alcohols.
➔ Reducing agents used are by catalytic hydrogenation and by hydride transfer
reducing agents like LiAlH4 and NaBH4.

(ii) By reduction of carboxylic acids and esters:

➔ Carboxylic acids are reduced to primary alcohols by lithium aluminium hydride, a
strong reducing agent.

➔ Commercially, alcohols are prepared by converting acid to the esters followed by

catalytic hydrogenation.

3. From Grignard reagents

➔ Nucleophilic addition of Grignard reagent to the carbonyl group to form an
adduct. Hydrolysis of the adduct yields an alcohol.

146

For More Material Join: @JEEAdvanced_2024

 The reaction of Grignard reagents with methanal produces a primary alcohol, with
other aldehydes, secondary alcohols and with ketones, tertiary alcohols.

 Preparation of Phenols
Phenol, also known as carbolic acid,
1. From haloarenes
Chlorobenzene is fused with NaOH at 623K and 320 atmospheric pressure. Phenol is
obtained by acidification of sodium phenoxide so produced.

2. From benzene sulphonic acid

Benzene first gives benzene sulphonic acid with oleum. Benzene sulphonic acid
converted to sodium phenoxide on heating with molten sodium hydroxide, which on
acidification gives phenol.

3. From diazonium salts

Diazonium salts are hydrolysed to phenols by warming with water or by treating with
dilute acids.

4. From cumene
Cumene (isopropylbenzene) is oxidised in the presence of air to cumene
hydroperoxide. It is converted to phenol and acetone by treating it with dilute acid.

147

For More Material Join: @JEEAdvanced_2024

 Physical Properties
● Boiling Points
❖ In alcohols and phenols increase with increase in the number of carbon atoms
(increase in van der Waals forces).
❖ In alcohols, decrease with increase of branching in the carbon chain.

❖ Boiling points of alcohols and phenols are higher in comparison to other classes of
compounds mainly due to the presence of intermolecular hydrogen bonding.
● Solubility
❖ Solubility is due to their ability to form hydrogen bonds with water molecules
❖ The solubility decreases with increase in size of alkyl/aryl (hydro-phobic) groups.
 Chemical Reactions
● The bond between O–H is broken when alcohols react as nucleophiles.

● The bond between C–O is broken when the protonated alcohol reacts as electrophiles.

(a) Reactions involving cleavage of O–H bond

1. Acidity of alcohols and phenols
(i) Reaction with metals:

phenols react with aqueous sodium hydroxide to form sodium phenoxides

148

For More Material Join: @JEEAdvanced_2024

 alcohols and phenols are Brönsted acids i.e., they can donate a proton to a
stronger base
(ii) Acidity of alcohols:
● The acid strength of alcohols decreases in the following order

● Electron-releasing group (–CH3 , –C2H5) increases electron density on

oxygen tending to decrease the polarity of O-H bond
● Alcohols are weaker acids than water.
(iii) Acidity of phenols:
● Phenols are stronger acids than alcohols and water.
● In alkoxide ion, the negative charge is localised on oxygen while in
phenoxide ion, the charge is delocalised. Which makes phenoxide ion
more stable and favours the ionisation of phenol.

● In substituted phenols electron withdrawing groups at ortho and para

positions such as nitro group, enhances the acidic strength.
● In substituted phenols electron releasing groups, such as alkyl groups,
decrease in acid strength.

149

For More Material Join: @JEEAdvanced_2024

2. Esterification
● Alcohols and phenols react with carboxylic acids, acid chlorides and acid
anhydrides to form esters.

● Reaction with acid chloride is carried out in the presence of a base (pyridine)
so as to neutralise HCl.
● The reaction with carboxylic acid and acid anhydride is carried out in the
presence of a small amount of concentrated sulphuric acid. The reaction is
reversible, and therefore, water is removed as soon as it is formed.
● The introduction of acetyl (CH3CO) group in alcohols or phenols is known as
acetylation.

(b) Reactions involving cleavage of carbon – oxygen (C–O) bond in alcohols

The reactions involving cleavage of C–O bonds take place only in alcohols.
Phenols show this type of reaction only with zinc.
1. Reaction with hydrogen halides
ROH + HX → R–X + H2O
Lucas test: Lucas reagent (conc. HCl and ZnCl2)
● Alcohols are soluble in Lucas reagent (conc. HCl and ZnCl2 ) while their
halides are immiscible and produce turbidity in solution.
● Tertiary alcohols, turbidity is produced immediately.
● Primary alcohols do not produce turbidity at room temperature.
2. Reaction with phosphorus trihalides: Alcohols are converted to alkyl
bromides by reaction with phosphorus tribromide.
3R − OH + PX 3 → 3R − X + H 3 PO3 ( X = Cl , Br )

3. Dehydration

150

For More Material Join: @JEEAdvanced_2024

 ● dehydration of alcohols follows the order:
Tertiary > Secondary > Primary

⮚ Mechanism
Step 1: Formation of protonated alcohol.

Step 2: Formation of carbocation is the slowest step and rate determining step

Step 3: Formation of ethene by elimination of a proton.

To drive the equilibrium to the right, ethene is removed as it is formed.

 Oxidation:

These are also known as dehydrogenation reactions as these involve loss of

dihydrogen from an alcohol molecule.
Strong oxidising agents such as acidified potassium permanganate are used for getting
carboxylic acids from alcohols directly.

CrO3 in anhydrous medium is used as the oxidising agent for the isolation of
aldehydes.

151

For More Material Join: @JEEAdvanced_2024

● A better reagent for oxidation of primary alcohols to aldehydes in good yield is
pyridinium chlorochromate (PCC)

● When the vapours of a primary or a secondary alcohol are passed over heated
copper

(c) Reactions of phenols

1. Electrophilic aromatic substitution:
The –OH activates ring towards electrophilic substitution at ortho and para
positions
(i) Nitration

● The ortho and para isomers can be separated by steam distillation.

● o-Nitrophenol is steam volatile due to intramolecular hydrogen bonding while
p -nitrophenol is less volatile due to intermolecular hydrogen bonding which
causes the association of molecules.

152

For More Material Join: @JEEAdvanced_2024

(ii) Halogenation:
(a)

(b) with bromine water, 2,4,6-tribromophenol is formed as white precipitate

2. Kolbe’s reaction

3. Reimer-Tiemann reaction

4. Reaction of phenol with zinc dust

5. Oxidation:

153

For More Material Join: @JEEAdvanced_2024

 In the presence of air, phenols are slowly oxidised to dark coloured mixtures
containing quinones.
⮚ Some Commercially Important Alcohols
1. Methanol
● Also known as ‘wood spirit.
● It is highly poisonous in nature.
● Methanol is used as a solvent in paints, varnishes and chiefly for making
formaldehyde.

2. Ethanol
● Obtained commercially by fermentation.

● Fermentation takes place in anaerobic conditions i.e. in absence of air, because

the oxygen of air oxidises ethanol to ethanoic acid which in turn destroys the taste
of alcoholic drinks.
● The commercial alcohol is made unfit for drinking by mixing in it some copper
sulphate (to give it a colour) and pyridine (a foul smelling liquid). It is known as
denaturation of alcohol.
⮚ Ethers
● Preparation of Ethers
1. By dehydration of alcohols

● The formation of ether is a nucleophilic bimolecular reaction (SN2)

● The method is suitable for the preparation of ethers having primary alkyl groups
only.
● In dehydration of secondary and tertiary alcohols alkenes are easily formed.

154

For More Material Join: @JEEAdvanced_2024

 ● Mechanism

2. Williamson synthesis

● The reaction involves SN2 attack of an alkoxide ion on primary alkyl halide.

● Better results are obtained if the alkyl halide is primary.

● In case of secondary and tertiary alkyl halides, elimination competes over
substitution.
● If tertiary alkyl halide is used, an alkene is the only reaction product.

⮚ Physical Properties
● The large difference in boiling points of alcohols and ethers is due to the presence of
hydrogen bonding in alcohols.
● miscibility of ethers with water resembles those of alcohols of the same molecular
mass

⮚ Chemical Reactions
1. Cleavage of C–O bond in ethers
● The cleavage of C-O bond in ethers takes place under drastic conditions with excess
of hydrogen halides

155

For More Material Join: @JEEAdvanced_2024

 The order of reactivity of hydrogen halides is as follows: HI > HBr > HCl.
Mechanism:
Step 1: protonation of ether molecule

The reaction takes place with HBr or HI because these reagents are sufficiently acidic.
Step 2: primary or secondary alkyl groups are present, it is the lower alkyl group that
forms alkyl iodide (SN2 reaction).

Step 3: When HI is in excess and t at high temperature, ethanol reacts with another
molecule of HI and is converted to ethyl iodide.

● Reaction follows SN1 mechanism when one of the alkyl group is a tertiary group, the
halide formed is a tertiary halide.

● In Anisole, I– ion breaks O–CH3 bond to form CH3I.

● O–CH3 is weaker than the bond O–C6H5 because the carbon of phenyl group is sp2
hybridised and there is a partial double bond character.
2. Electrophilic substitution
The alkoxy group (-OR) is ortho, para directing
(i) Halogenation: Para isomer is obtained in 90% yield.

156

For More Material Join: @JEEAdvanced_2024

(ii) Friedel-Crafts reaction:

(iii) Nitration:

157

For More Material Join: @JEEAdvanced_2024

 Aldehydes and Ketones

Introduction:
Organic compounds containing carbon-oxygen double bonds (>C=O) are called carbonyl
groups.
In aldehydes, the carbonyl group is bonded to a carbon and hydrogen while in the ketones, it is
bonded to two carbon atoms.

They add fragrance and flavour to nature, for example, vanillin (from vanilla beans),
salicylaldehyde (from meadow sweet) and cinnamaldehyde (from cinnamon) have very
pleasant fragrances.

They are used in many food products and pharmaceuticals to add flavours. Some of these
families are manufactured for use as solvents (i.e., acetone) and for preparing materials like
adhesives, paints, resins, perfumes, plastics, fabrics.

⮚ Nomenclature and Structure of Carbonyl Group

Aldehydes and ketones
(a) Common names
● The common names of most aldehydes are derived from the common names of the
corresponding carboxylic acids by replacing the ending –ic of acid with aldehyde
● The location of the substituent indicated by Greek letters α , β, γ , δ , etc.
● The α -carbon being the one directly linked to the aldehyde group.

Some ketones have historical common names, the simplest dimethyl ketone is
called acetone.

158

For More Material Join: @JEEAdvanced_2024

 Alkyl phenyl ketones are usually named by adding the acyl group as prefix to
phenone.

(b) IUPAC names:

● The IUPAC names of open chain aliphatic aldehydes and ketones are derived from
the names of the corresponding alkanes by replacing the ending –e with –al and –
one respectively.
● Common name benzaldehyde is also accepted by IUPAC.
● Other aromatic aldehydes are named as substituted benzaldehydes.

159

For More Material Join: @JEEAdvanced_2024

⮚ Structure of the Carbonyl Group
● The carbonyl carbon atom is sp2-hybridised and forms three sigma (σ) bonds
● The bond angles are approximately 120° as expected of a trigonal coplanar structure

● The carbon-oxygen double bond is polarised due to higher electronegativity of oxygen

relative to carbon. Hence, the carbonyl carbon is an electrophilic (Lewis acid), and
carbonyl oxygen, a nucleophilic (Lewis base) centre.
● Carbonyl compounds have substantial dipole moments and are more polar than ethers.

160

For More Material Join: @JEEAdvanced_2024

⮚ Preparation of Aldehydes and Ketones
1. By oxidation of alcohols: Aldehydes and ketones are generally prepared by oxidation
of primary and secondary alcohols, respectively.
2. By dehydrogenation of alcohols:
● This method is suitable for volatile alcohols and is of industrial application.
● Alcohol vapours are passed over heavy metal catalysts (Ag or Cu). Primary and
secondary alcohols give aldehydes and ketones, respectively.
3. From hydrocarbons:
● By ozonolysis of alkenes: ozonolysis of alkenes followed by reaction with zinc
dust and water gives aldehydes, ketones or a mixture of both depending on the
substitution pattern of the alkene.

● By hydration of alkynes: Addition of water to ethyne in the presence of H2SO4

and HgSO4 gives acetaldehyde. All other alkynes give ketones in this reaction.

⮚ Preparation of Aldehydes
1. From acyl chloride (acid chloride): Rosenmund reduction.

2. From nitriles and esters:

● Stephen reaction: Nitriles are reduced to corresponding imine with stannous
chloride in the presence of hydrochloric acid, which on hydrolysis give
corresponding aldehyde.
+

RCN + SnCl2 + HCl → RCH = NH ⎯⎯⎯

→ RCHO H3 O

● Nitriles are selectively reduced by, (DIBAL-H) to imines followed by hydrolysis

to aldehydes.

161

For More Material Join: @JEEAdvanced_2024

 ● Esters are also reduced to aldehydes with DIBAL-H

3. From hydrocarbons
I. By oxidation of methylbenzene
❖ Strong oxidising agents oxidise toluene and its derivatives to benzoic acids.
❖ To stop the oxidation at the aldehyde stage suitable reagents are used that
convert the methyl group to an intermediate that is difficult to oxidise further.
a) Use of chromyl chloride (CrO2Cl2):Etard reaction

b) Use of chromic oxide (CrO3)

II. By side chain chlorination followed by hydrolysis

This is a commercial method of manufacture of benzaldehyde

III. By Gatterman – Koch reaction

⮚ Preparation of Ketones
1. From acyl chlorides:

162

For More Material Join: @JEEAdvanced_2024

 2. From nitriles:

3. From benzene or substituted benzenes: Friedel-Crafts acylation reaction:

⮚ Physical Properties
● Methanal is a gas at room temperature. Ethanal is a volatile liquid.
● Boiling points of aldehydes and ketones are higher than hydrocarbons and ethers &
lower than those of alcohols of similar molecular masses.
● Methanal, ethanal and propanone are miscible with water in all proportions because
they form hydrogen bonds with water.

● All aldehydes and ketones are fairly soluble in organic solvents like benzene, ether,
methanol, chloroform.
● The lower aldehydes have sharp pungent odours. As the size of the molecule
increases, the odour becomes less pungent and more fragrant.

⮚ Chemical Reactions
1. Nucleophilic addition reactions
(i) Mechanism of nucleophilic addition reaction.
● A nucleophile attacks the electrophilic carbon atom of the polar carbonyl
group.
● The hybridisation of carbon changes from sp2 to sp3 in this process, and a
tetrahedral alkoxide intermediate is produced.
● This intermediate captures a proton from the reaction medium to give the
electrically neutral product.
● The net result is addition of Nu– and H+ across the carbon oxygen double
bond.

163

For More Material Join: @JEEAdvanced_2024

(ii) Reactivity
● Aldehydes are generally more reactive than ketones in nucleophilic addition
reactions due to steric and electronic reasons.
(iii)Some important examples of nucleophilic addition and nucleophilic addition-
elimination reactions:
(a) Addition of hydrogen cyanide (HCN): This reaction is catalysed by a base
to generate strong nucleophile cyanide ion (CN- ).

(b) Addition of sodium hydrogensulphite:

● The position of the equilibrium lies largely to the right hand side for most
aldehydes and to the left for most ketones due to steric reasons.
● The hydrogen sulphite addition compound is water soluble and can be
converted back to the original carbonyl compound by treating it with dilute
mineral acid or alkali.
● These are useful for separation and purification of aldehydes.
(c) Addition of Grignard reagents:

(d) Addition of alcohols:

Ketones react with ethylene glycol to form cyclic products known as ethylene
glycol ketals

164

For More Material Join: @JEEAdvanced_2024

 ● Acetals and ketals are hydrolysed with aqueous mineral acids to yield
corresponding aldehydes and ketones respectively.
(e) Addition of ammonia and its derivatives :
● The reaction is reversible and catalysed by acid.
● The equilibrium favours the product formation due to rapid dehydration of
the intermediate to form >C=N-Z

2. Reduction:
(i) Reduction to alcohols: Reduced to primary and secondary alcohols respectively
by NaBH4 or LiAlH4 as well as by catalytic hydrogenation.
(ii) Reduction to hydrocarbons:
❖ Clemmensen Reduction

❖ Wolff-Kishner reduction:

165

For More Material Join: @JEEAdvanced_2024

3. Oxidation:
Aldehydes are easily oxidised to carboxylic acids on treatment with common oxidising
agents.

Ketones are generally oxidised under vigorous conditions, i.e., strong oxidising agents
and at elevated temperatures.
Their oxidation involves carbon-carbon bond cleavage to afford a mixture of carboxylic
acids having lesser number of carbon atoms than the parent ketone.

The mild oxidising agents given below are used to distinguish aldehydes from
ketones.
(i) Tollens’ test:
● Ammoniacal silver nitrate solution (Tollens’ reagent)
● A bright silver mirror is produced due to the formation of silver metal.

(ii) Fehling’s test

● Fehling solution A is aqueous copper sulphate and Fehling solution B is
alkaline sodium potassium tartrate (Rochelle salt).
● Aromatic aldehydes do not respond to this test.

(iii) Oxidation of methyl ketones by haloform reaction:

● Aldehydes & ketones having at least one methyl group linked to the carbonyl
carbon atom are oxidised by sodium hypohalite to sodium salts of
corresponding carboxylic acids having one carbon atom less than that of
carbonyl compound.
● This oxidation does not affect a carbon-carbon double bond.
● Iodoform reaction with sodium hypoiodite is also used for detection of
CH3CO group or CH3CH(OH) group.

166

For More Material Join: @JEEAdvanced_2024

4. Reactions due to α-hydrogen
Acidity of α-hydrogens of aldehydes and ketones:
It is due to the strong electron withdrawing effect of the carbonyl group and resonance
stabilisation of the conjugate base.

(i) Aldol condensation:

Aldehydes and ketones having at least one α-hydrogen undergo a reaction in the
presence of dilute alkali as catalyst to form β-hydroxy aldehydes (aldol) or β-hydroxy
ketones (ketol), respectively. This is known as the Aldol reaction.

The aldol and ketol readily lose water to give α ,β-unsaturated carbonyl compounds
which is called Aldol condensation .
(ii) Cross aldol condensation
● Carried out between two different aldehydes and / or ketones,
● If both of them contain α -hydrogen atoms, it gives a mixture of four products.

167

For More Material Join: @JEEAdvanced_2024

5. Other reactions:
(i) Cannizzaro reaction:
● Aldehydes which do not have an α -hydrogen atom, undergo self-oxidation and
reduction (disproportionation) reaction on treatment with concentrated alkali.
● One molecule of the aldehyde is reduced to alcohol while another is oxidised
to carboxylic acid salt.

(ii) Electrophilic substitution reaction: Carbonyl group acts as a deactivating and

meta-directing group.

(iii)Uses of Aldehydes and Ketones

● Formaldehyde is well known as formalin (40%) solution used to preserve
biological specimens and to prepare bakelite.
● Benzaldehyde is used in perfumery and in dye industries.
● Many aldehydes and ketones, e.g., butyraldehyde, vanillin, acetophenone,
camphor, etc. are well known for their odours and flavours.

168

For More Material Join: @JEEAdvanced_2024

 Amines

Amines can be considered as derivatives of ammonia.

⮚ Structure of Amines: The geometry of amines is pyramidal and sp3 hybridization.The

fourth orbital of nitrogen in all amines contains an unshared pair of electrons. Due to the
presence of an unshared pair of electrons, the angle C–N–E, (where E is C or H) is less than
109.5°; for instance, it is 108o in case of trimethylamine.

⮚ Classification:
Amines are classified as primary (1o), secondary (2o) and tertiary (3o) depending upon the
number of hydrogen atoms replaced by alkyl or aryl groups in ammonia molecules.

⮚ Nomenclature:
In common name system, an aliphatic amine is named by prefixing alkyl group to amine,
i.e., alkylamine as one word (e.g., methylamine) IUPAC system, amines are named as
alkanamines.

169

For More Material Join: @JEEAdvanced_2024

 C6H5NH2 in the common system, it is known as aniline.
It is also an accepted IUPAC name. While naming arylamines according to the IUPAC
system, the suffix ‘e’ of arene is replaced by ‘amine’.
Thus, in the IUPAC system, C6H5 NH2 is named as benzenamine.

⮚ Preparation of Amines
1. Reduction of nitro compounds:

Reduction with iron scrap and hydrochloric acid is preferred because FeCl2 formed
gets hydrolysed to release hydrochloric acid during the reaction.
2. Ammonolysis of alkyl halides: Process of cleavage of the C–X bond by ammonia
molecule is known as ammonolysis.

170

For More Material Join: @JEEAdvanced_2024

 Ammonolysis has the disadvantage of yielding a mixture of primary, secondary and
tertiary amines and also a quaternary ammonium salt.
The free amine can be obtained from the ammonium salt by treatment with a strong
base

The order of reactivity of halides with amines is RI > RBr >RCl.

3. Reduction of nitriles:
Reduction with lithium aluminium hydride (LiAlH4) or catalytic hydrogenation
produces primary amines.
This reaction is used for ascent of amine series, i.e., for preparation of amines
containing one carbon atom more than the starting amine.

4. Reduction of amides

5. Gabriel phthalimide synthesis

● Used for the preparation of primary amines.
● Aromatic primary amines cannot be prepared by this method.

6. Hoffmann bromamide degradation reaction:

● Preparation of primary amines
● The amine so formed contains one carbon less than that present in the amide.

171

For More Material Join: @JEEAdvanced_2024

 O
||
R − C − NH 2 + Br2 + 4 NaOH → R − NH 2 + Na2 CO3 + 2 NaBr + 2 H 2 O
⮚ Physical Properties
● Aniline and other arylamines are usually colourless but get coloured on storage due to
atmospheric oxidation.
● Lower aliphatic amines are soluble in water because they can form hydrogen bonds
with water molecules.
● Amines are soluble in organic solvents like alcohol, ether and benzene
● The order of boiling points of isomeric amines is as follows:
Primary > Secondary > Tertiary
● Intermolecular hydrogen bonding in primary amines

● Comparison of Boiling Points of Amines, Alcohols and Alkanes of Similar Molecular

Masses

⮚ Chemical Reactions: Amines behave as nucleophiles due to the presence of an unshared

electron pair.
1. Basic character of amines
● Amines, being basic in nature, react with acids to form salts.

● Amine salts on treatment with a base like NaOH, regenerate the parent amine.

172

For More Material Join: @JEEAdvanced_2024

● Amine salts are soluble in water but insoluble in organic solvents like ether. This
reaction is the basis for the separation of amines from the non-basic organic
compounds insoluble in water.
● Amines behave as Lewis base.
❖ Kb values as explained below

● Larger the value of Kb or smaller the value of pKb, stronger is the base.
❖ Table: Kb Values of Amines in Aqueous Phase

● Structure-basicity relationship of amines: Basic character of an amine depends

upon the ease of formation of the cation by accepting a proton from the acid. The
more stable the cation is relative to the amine, the more basic is the amine.
a) Alkyl amines versus ammonia:
❖ Aliphatic amines are stronger bases than ammonia due to +I effect of alkyl
groups

173

For More Material Join: @JEEAdvanced_2024

● Gaseous phase
❖ The order of basicity of amines: tertiary amine > secondary amine>
primary amine > NH3
● Aqueous phase
❖ Substituted ammonium cations get stabilised not only by +I effect of the alkyl
group but also by solvation with water molecules.
❖ The greater the size of the ion, lesser will be the solvation and the less stabilised
is the ion.
❖ Decreasing order of extent of H-bonding in water and order of stability of ions
by solvation

❖ Considering the Inductive effect, solvation effect and steric hindrance of the
alkyl group decides the order of basic strength in aqueous solution.

b) Arylamines versus ammonia

❖ In arylamines unshared electron pair on nitrogen atoms is in conjugation with
the benzene ring and thus making it less available for protonation.
❖ Hence, the proton acceptability or the basic nature of aniline or other aromatic
amines would be less than that of ammonia

174

For More Material Join: @JEEAdvanced_2024

 ❖ In case of substituted aniline,electron releasing groups like –OCH3, –CH3
increase basic strength whereas electron withdrawing groups like –NO2 , –
SO3,–COOH, –X decrease it.
2. Alkylation: Amines undergo alkylation on reaction with alkyl halides.
3. Acylation:
● Carried out in the presence of a base stronger than the amine, like pyridine, which
removes HCl so formed and shifts the equilibrium to the right hand side.

● Amines react with benzoyl chloride (C6H5COCl). & the reaction known as
benzoylation
CH 3 NH 2 + C6 H 5 COCl → CH 3 NHCOC6 H 5 + HCl
Methanamine Benzoyl chloride N-Methylbenzamide

4. Carbylamine reaction
● Known as carbylamine reaction or isocyanide test and is used as a test for Aliphatic
and aromatic primary amines.
● In this reaction isocyanides or carbylamines which are foul smelling substances.
● Secondary and tertiary amines do not show this reaction.

5. Reaction with nitrous acid:

a) Primary aliphatic amines react to form aliphatic diazonium salts which, being
unstable, liberate nitrogen gas quantitatively and alcohols.

175

For More Material Join: @JEEAdvanced_2024

 b) Aromatic amines react at low temperatures (273-278 K) to form diazonium
salts.

Secondary and tertiary amines react with nitrous acid in a different manner.
6. Reaction with arylsulphonyl chloride:
● Benzenesulphonyl chloride (C6H5SO2Cl), Hinsberg’s reagent
● Used for the distinction of primary, secondary and tertiary amines and also for the
separation of a mixture of amines.
● These days benzenesulphonyl chloride is replaced by p -toluenesulphonyl chloride
a) Primary amine:

The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the

presence of a strong electron withdrawing sulphonyl group. Hence, it is soluble in
alkali.
b) Secondary amine:

No hydrogen atom attached to nitrogen atom and hence insoluble in alkali.

c) Tertiary amines do not react with benzenesulphonyl chloride.
7. Electrophilic substitution: -NH2 group is ortho and para directing and a powerful
activating group.
a) Bromination: With bromine water give a white precipitate of 2,4,6-
tribromoaniline.

● Monosubstituted aniline derivatives are formed by protecting the -NH2 group

by acetylation with acetic anhydride, followed by hydrolysis.

176

For More Material Join: @JEEAdvanced_2024

 ● The lone pair of electrons on nitrogen of acetanilide interacts with oxygen
atom due to resonance as shown below:

b) Nitration:
● Strongly acidic medium, aniline is protonated to form the anilinium ion which
is meta directing.

● By protecting the –NH2 group by acetylation, p-nitro derivatives obtained as

the major product.

c) Sulphonation:

Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) due
to salt formation with aluminium chloride.

177

For More Material Join: @JEEAdvanced_2024

⮚ Diazonium Salts
● General formula –RN2+X–
N2+ group is called the diazonium group. R is aryl group and –X ion may be Cl–, Br–,
HSO4–, BF4–.
● Primary aliphatic amines form highly unstable alkyldiazonium salts. Primary aromatic
amines form arenediazonium salts which are stable for a short time in solution at low
temperatures.
● The stability of arenediazonium ion is explained on the basis of resonance.

❖ Method of Preparation of Diazonium Salts

● The conversion of primary aromatic amines into diazonium salts is known as
diazotization.
● Due to its instability, the diazonium salt is not generally stored and is used
immediately after its preparation.

❖ Physical Properties
● Readily soluble in water and is stable in cold but reacts with water when warmed.
● It decomposes easily in the dry state.
● Benzenediazonium fluoroborate is water insoluble and stable at room temperature.
❖ Chemical Reactions:
a) Reactions involving displacement of nitrogen
Diazonium group being a very good leaving group, is substituted by other groups
1. Replacement by halide or cyanide ion:
Sandmeyer reaction

Gatterman reaction

2. Replacement by iodide
Iodine is not easily introduced into the benzene ring directly, but, when the
diazonium salt solution is treated with potassium iodide, iodobenzene is formed

178

For More Material Join: @JEEAdvanced_2024

3. Replacement by fluoride ion:

4. Replacement by H:

5. Replacement by hydroxyl group:

6. Replacement by –NO2 group:

b) Reactions involving retention of the diazo group.

❖ Coupling reactions
● Reaction having both the aromatic rings joined through the –N=N– bond is
known as coupling reaction
● The azo products obtained with an extended conjugate system are often
coloured and are used as dyes.

❖ Importance of Diazonium Salts in Synthesis of Aromatic Compounds

The replacement of diazo group by other groups is helpful in preparing those
substituted aromatic compounds which cannot be prepared by direct substitution
like Aryl fluorides and iodides & cyanobenzene.

179

For More Material Join: @JEEAdvanced_2024

 Biomolecules

⮚ Carbohydrates
● Optically active polyhydroxy aldehydes or ketones or the compounds which produce
such units on hydrolysis.
● General formula: Cx(H2O)y
● Hydrates of Carbon. Eg: C6H12O6 fits in C6(H2O)6
● Not all molecules fitting to the formula are carbohydrates Eg: CH3COOH is not a
carbohydrate.
● Examples: Sugar, glucose, starch etc

⮚ Classification of carbohydrates
Based on reducing nature:
● Reducing sugar: Reduce Fehling’s solution and Tollens’ reagent.
● Nonreducing sugar: Do not reduce Fehling’s solution and Tollens’ reagent

⮚ Based on sweetness:
● Sugars: Carbohydrates which are sweet to taste. Eg: Sucrose
● Non sugars: Carbohydrates which are not sweet to taste. Eg: Starch

⮚ Based on behaviour on hydrolysis:

● Monosaccharides:
❖ Simplest form and cannot be further hydrolysed.Eg: Glucose, fructose, ribose etc.
❖ Aldose: Has aldehyde group, Ketose: Has ketone group
❖ Naming of compounds:

● Oligosaccharides:
❖ Yield two to ten monosaccharide units on hydrolysis.
❖ Disaccharides, trisaccharides, tetrasaccharides produce 2, 3, 4 units on hydrolysis.
❖ Eg: Sucrose (disaccharide) on hydrolysis produces glucose and fructose, Maltose
produces 2 glucose molecules.
● Polysaccharides:
❖ Yield a large number of monosaccharide units on hydrolysis.
❖ Eg: Starch, cellulose, glycogen, etc.

180
For More Material Join: @JEEAdvanced_2024
⮚ Monosaccharides
1. Glucose
● Aldohexose. Formula: C6H12O6.
● Structure:

● Preparation:
❖ From sucrose:

C12 H 22 O11 + H 2 O+ H 2 O ⎯⎯→
H
C6 H12 O6 + C6 H12 O6
Sucrose Glucose Fructose

❖ From starch:
( C6 H10 O5 )n + nH 2 O ⎯⎯⎯⎯⎯

H
393 K , 2 −3 atm
→ nC6 H12 O6
Starch or Cellulose Glucose

● Chemical reactions:

● Configuration of glucose
NOTE: D and d are both different. D represents the configuration i.e -OH on the
right. +/d represents that the molecule is dextrorotatory

181
For More Material Join: @JEEAdvanced_2024
● Cyclic structures of glucose
❖ 2 crystalline forms of glucose: α and β form which differ only in the configuration
of the hydroxyl group at C1, called anomeric carbon.
❖ α-form (m.p. 419 K): By crystallisation of conc. glucose at 303 K.
❖ β-form (m.p. 423 K): By crystallisation of hot and saturated glucose at 371 K.
❖ Glucose forms a six-membered hemiacetal ring in which –OH at C-5 is involved in
ring formation.

❖ α, β forms exist in equilibrium with the open chain form whose specific rotation is
+52.50.
❖ Due to absence of free -CHO in cyclic form:
▪ Doesn't give Schiff’s test (with NaHSO3 it does not form hydrogensulphite).
▪ Pentaacetate of glucose does not react with hydroxylamine
❖ Cyclic structures: Called ‘pyranose’ due to its analogy with pyran

182
For More Material Join: @JEEAdvanced_2024
 2. Fructose
● Ketohexose (keto group on carbon-2). Formula: C6H12O6.
● Structure:

● Cyclic form of fructose: Called furanose due to its analogy with furan

Note: Both glucose and fructose give tollen’s test and fehling’s test.

⮚ Disaccharides:
● Two monosaccharides join together by an oxide linkage called glycosidic linkage,
formed by the loss of a water molecule
● If the reducing groups of monosaccharides i.e., aldehydic or ketonic groups are free
then reducing sugars else they would be non-reducing.
1. Sucrose:
● Monosaccharides: α-D-glucose & β-D-fructose
● Glycosidic linkage: C1 of α-D-glucose and C2 of β-D-fructose
● Reducing nature: Non reducing

183
For More Material Join: @JEEAdvanced_2024
 ● Is dextrorotatory, but on hydrolysis gives a laevorotatory mixture. Also called
invert sugar due to this reason
● Structure:

2. Maltose:
● Monosaccharides: 2 α-D-glucose
● Glycosidic linkage: C1 of glucose (I) and C4 of glucose (II)
● Reducing nature: Reducing (Free aldehyde at C1 of glucose (II))
● Structure:

3. Lactose (Milk sugar):

● Monosaccharides: β-D-galactose and β-D-glucose.
● Glycosidic linkage: C1 of galactose and C4 of glucose (II)
● Reducing nature: Reducing (Free aldehyde at C1 of glucose)
● Structure:

184
For More Material Join: @JEEAdvanced_2024
⮚ Polysaccharides
1. Starch:
● Monosaccharides: α-glucose
● 2 components: Amylose and Amylopectin
● Amylose (15 -20 %): Water soluble, long unbranched chain with C1– C4
glycosidic linkage of α-D-(+)-glucose units.

● Amylopectin (80- 85% ): Water insoluble, long branched chain formed by C1–C4
glycosidic linkage and branching is formed by C1–C6 glycosidic linkage.

2. Cellulose:
● Predominant constituent of cell wall of plant cells.
● Monosaccharide: β-D-glucose units by glycosidic linkage between C1 & C4 of
glucose units.

185
For More Material Join: @JEEAdvanced_2024
 3. Glycogen:
● Carbohydrates are stored in the animal body as glycogen.
● Called animal starch as it is similar to amylopectin but more highly branched.
● Present in liver,muscles, brain, in yeast and fungi.
● Glycogen is broken into glucose when the body needs glucose.
⮚ Proteins:
● Polymers of α-amino acids connected by peptide linkage
● Majorly found in milk, cheese, pulses, peanuts, fish, meat, etc.
⮚ Amino acids:
● Contain amino (–NH2 ) and carboxyl (–COOH) groups.
● Based on relative position of -NH2 and -COOH they are classified as α, β, γ, δ etc
● General structure: α-amino acid

● Colourless, crystalline solids, Water-soluble, high melting solids

● Behave like salts due to presence of both acidic and basic groups.
● Total 22 amino acids are naturally represented and the list is given below

186
For More Material Join: @JEEAdvanced_2024
 N – Neutral
A – Acidic
B – Basic

● Classification of amino acids:

❖ Essential amino acids: Cannot be synthesized by body and need to be obtained
from diet.
Nonessential amino acids: Synthesized by body
❖ Acidic, Basic and Neutral amino acids based on they overall charge present on
them
● Zwitterion:
❖ In aqueous solution the -COOH group loses proton and -NH2 accepts proton.
❖ Neutral but has both negative and positive charges i.e dipolar ion.
❖ Amphoteric and reacts with both acid and base

● Optical activity: Except glycine, all are optically active

● D and L configuration: ‘L’ represents -NH2 on left and ‘D’ represents -NH2 on right.
Naturally occurring amino acids usually have L configuration.
⮚ Structure of proteins:
● Amino acids join together by amide linkage also called as peptide linkage

187
For More Material Join: @JEEAdvanced_2024
 ● All the amino acids join together to form polypeptides. Long polypeptide chains of
Mol.mass > 10,000u is called a protein
● Classification of proteins: Based on molecular shapes into 2 types

Fibrous proteins Globular proteins

Polypeptide chains run parallel and are held Polypeptides coil around to give a
together by hydrogen and disulphide bonds spherical shape
forming fibrous structures.

Insoluble in water Soluble in water

Eg: keratin (In hair, wool, silk) and myosin Eg: Insulin, albumin
(in muscles)

● Structure of protein is divided into 4 levels: Primary, secondary, tertiary and quaternary
(1) Primary structure: Specific sequence of amino acids in a polypeptide chain is said
to be the primary structure of protein. Any change in it will create a different protein.

(2) Secondary structure: It refers to the shape in which a long polypeptide chain can
exist. Due to H-bonding, the polypeptide chain can fold into two shapes: α-helix and β-
pleated sheet structure.
α-helix: Polypeptide chain is twisted into a right-handed screw (helix) due to H-
bonding between the –NH group of each amino acid with -C=O of the adjacent amino
acid.
β-pleated sheet: Polypeptide chains are stretched out and then laid side by side, which
are held together by intermolecular hydrogen bonds.

(3) Tertiary structure: 2° structure on further folding gives tertiary structure. Folding
gives rise to 2 shapes - fibrous and globular. Forces present here are hydrogen bonds,
disulphide linkages, van der Waals and electrostatic forces of attraction

(4) Quaternary structure: Two or more polypeptide chains referred to as subunits are
spatially arranged with respect to each other to form quaternary structure.

⮚ Denaturation of proteins:
● Each protein has its own unique 3D structure called native protein.
● Denaturation: If this native protein is subjected to change in pH or temperature or any
physical change then the hydrogen bonds are disturbed causing the protein to unfold
and it loses its biological activity. 2°, 3° structures are destroyed but 1° remains intact

188
For More Material Join: @JEEAdvanced_2024
 Eg: The coagulation of egg white on boiling, curdling of milk due to the formation of
lactic acid by the bacteria present in milk.

⮚ Enzymes:
● Biocatalysts which catalyse various biochemical reactions like digestion of food etc
● Usually, enzymes are globular proteins
● Named after the compound or class of compounds upon which they work. Eg: Maltase
enzyme catalyses hydrolysis of maltose.
● Named after reactions also. Eg: Enzyme’s catalysis oxidation of one substrate and
reduction of other are called oxidoreductase enzymes.
● Mechanism of action: They bind to the specific substrate similar to lock and key and
convert it into product. They reduce the magnitude of activation energy.

⮚ Vitamins:
● “Vitamin” = vital + amine (Earlier identified compounds had amino groups).
● Organic compounds required in small amounts in diet to perform specific biological
functions for normal maintenance of optimum growth.
● Deficiency causes specific diseases => essential food factors for the human body.
● Generally synthesized by plants. In humans, bacteria present in gut synthesizes few
vitamins
● Different vitamins include: A, B, C, D, K. Vitamin B has subgroups B1, B2 , B6 , B12,
etc.
● Classification: Based on water soluble or fat soluble
❖ Fat soluble vitamins: Vitamin A,D,E,K are fat soluble. They are stored in liver
and adipose tissue.
❖ Water soluble vitamins: Group B and C vitamins are water soluble. Must to be
supplied in diet and are not stored in body but are excreted in urine (except B12)
Important vitamins
Vitamin Sources Deficiency diseases
(i) Vitamin-A (Retinol or Milk, cod liver oil, Night blindness,
eye vitamin) butter, carrots, green xerophthalmia (i.e.
leaves, tomatoes, eggs, hardening of cornea of
etc. eye) and xerosis.
(ii) Vitamin – B Thiamine Pulses, nuts, green Beriberi (a disease of
or Aneurin vegetables, and polished the nervous system) and
rice. Yeast and egg loss of appetite.
yolk.
(iii) Vitamin – B2 or Milk, meat, green Inflammation of tongue
Riboflavin or vegetables and yeast, or dark red tongue
Lactoflavin (glossitis), and cheilosis
(cracking or fissuring
the lips and corners of
the mouth)
(IV) Vitamin – B6 or Rice, bran, yeast, meat, Specific dermatitis
Pyridoxine or fish, egg, yolk, maize, called acrodynia,
Adermine spinach and lettuce. pellagra (shrivelled

189
For More Material Join: @JEEAdvanced_2024
 skin) anaemia and
convulsions.
(V) Vitamin – B12 or Milk, liver, kidney, and Inflammation of tongue,
Cyanocobalamin eggs. mouth etc. and
pernicious anaemia.
(VI) Vitamin – C or L- Citrous fruits, amla, Scurvy and brittleness
Ascorbic (oranges, lemons), of bones, swelling and
sprouted pulses, bleeding of gums and
germinated. loosening of teeth.
(VII) Vitamin D or Fish liver oil, cod liver Rickets (softening and
Ergocalciferol (or oil, milk and eggs. bending of bones) in
antirachitic vitamin of children, controls Ca
sunshine vitamin) and P metabolism.
(VIII) Vitamin-E or Eggs, milk, fish wheat Sterility (loss of sexual
tocopherols (α, β and γ) germ, oil, cotton seed power and reproduction)
or Antisterility oil etc.
(IX) Vitamin – H (Biotin) Yeast, liver, Kidney and Dermatitis, loss of hair
milk. and paralysis.
(X) Vitamin-K or Cabbage, alfalfa, Haemorrhage and
phylloquinone or spinach and carrot tops, lengthens time of blood
Antihemorrhagic clotting.
vitamin

⮚ Nucleic Acids:
● Long chain polymers of nucleotides also called as polynucleotides
● Hereditary components present in the cell, called chromosomes, are made of nucleic
acids.
● 2 types: Deoxyribonucleic acid (DNA) and Ribonucleic acid (RNA)
● Hydrolysis of DNA or RNA yields pentose sugar, phosphoric acid and nitrogen
containing heterocyclic compounds (called bases).
● DNA: Made of β-D-2-deoxyribose units, RNA: Made of β-D-ribose units.

● DNA contains four bases: adenine (A), guanine (G),cytosine (C) and thymine (T)
RNA contains four bases: adenine (A), guanine (G),cytosine (C) and uracil (U).

190
For More Material Join: @JEEAdvanced_2024
 ● Structure of a nucleotide:

● Structure of a nucleic acid:

Nucleotides join together by phosphodiester linkage between 5’ and 3’ atoms of the
pentose sugar to form nucleic acid chains.

⮚ Structure of DNA:
● Double stranded, helix structure (Proposed byWatson and crick)
● 2 nucleic acid chains are wound about each other and held together by hydrogen
bonds between pairs of bases.
● Both strands are complementary. Adenine (A) forms hydrogen bonds with Thymine
(T) and Cytosine (C) forms hydrogen bonds with Guanine (G)

191
For More Material Join: @JEEAdvanced_2024
⮚ Structure of RNA:
● Single stranded.
● 3 types: messenger RNA (m-RNA), ribosomal RNA (r-RNA) and transfer RNA (t-
RNA). All are used for different functions within cell

⮚ Biological function of RNA and DNA:

● Reserve of genetic information and basis of heredity.
● DNA maintains the identity of different species over millions of years
● DNA is capable of self duplication and identical DNA is transferred to daughter cells.
● RNA is used to synthesize proteins in the cell but the message for synthesis is present
in DNA
⮚ DNA fingerprinting:
● Sequence of bases on DNA is unique for a person and the information regarding this
is called DNA fingerprinting.
● Used in forensics for identification of criminals, determination of paternity of an
individual, identification of dead bodies in any accident by comparing with parental
DNA and to identify racial groups to rewrite biological evolution

⮚ HORMONES:
● Intracellular messengers
● Produced by endocrine glands and poured directly into bloodstream
● They can be
❖ Steroids - Eg: Estrogens and androgens
❖ Polypeptides - Eg: Insulin and endorphins
❖ Amino Acid derivatives - Eg: epinephrine and norepinephrine

⮚ Biological activities of few hormones:

● Insulin is released when the blood glucose levels are high and it reduces the levels.
Glucagon tends to increase blood glucose level. Both of them regulate the amount of
glucose in blood.
● Growth and sex hormones: Important for growth and development
● Epinephrine and norepinephrine: Mediate responses to external stimuli.
● Thyroxine: An iodinated derivative of amino acid tyrosine, is important in maintenance
of bones, brain development etc. Low levels cause hypothyroidism. characterised by
lethargicness and obesity. High levels cause hyperthyroidism.

192
For More Material Join: @JEEAdvanced_2024
 Note: Low level iodine diet leads to hypothyroidism and enlargement of thyroid gland.
Patients with such medical conditions are advised to take iodised salt.
● Adrenal cortex hormones (Steroid hormone):
❖ Glucocorticoids: Control the carbohydrate metabolism, modulate inflammatory
reactions, and are involved in reactions to stress.
❖ Mineralocorticoids: Control the level of excretion of water and salt by the kidney
❖ Addison’s disease: Due to improper functioning of adrenal cortex. Causes
hypoglycemia, weakness and increased susceptibility to stress. Should be treated
with glucocorticoids and mineralocorticoids.
● Hormones by gonads (Steroid hormone):
❖ For the development of secondary sex characters.
❖ Testosterone: Main male sex hormone and is responsible for development of
secondary male characteristics (deep voice, facial hair etc)
❖ Estradiol: Main female sex hormone and is responsible for development of
secondary female characteristics and in the control of menstrual cycle.
❖ Progesterone: responsible for preparing the uterus for implantation of fertilised egg.

193
For More Material Join: @JEEAdvanced_2024
 Polymers

The term polymer is defined as very large molecules having high molecular mass.
Referred to as macromolecules, which are formed by joining of repeating structural units on a
large scale. The repeating structural units are derived from some simple and reactive molecules
known as monomers and are linked to each other by covalent bonds. This process of formation
of polymers from respective monomers is called polymerisation.

➢ Classification of polymer
Classification based on source
1. Natural Polymer- Found in plants and animals. e.g., proteins, cellulose, starch, some
resins.
2. Semi-synthetic polymers- Cellulose derivatives as cellulose acetate (rayon) and
cellulose nitrate
3. Man Made / Synthetic polymers - used in daily life as well as in industry. Examples -
plastic (polythene), synthetic fibres (nylon 6,6) and synthetic rubbers (Buna - S)

➢ Classification based on structure of the polymers

1. Linear polymers- Consist of long and straight chains. e.g. - high density polythene,
polyvinyl chloride, etc. These are represented as:

2. Branched chain polymers- Contain linear chains having some branches, e.g., low
density polythene. These are depicted as follows

3. Cross linked or Network polymers- Formed from bi-functional and trifunctional

monomers and contain strong covalent bonds between various linear polymer chains,
e.g. bakelite, melamine, etc. These polymers are depicted as follows:

➢ Classification Based on Mode of Polymerisation

1. Addition polymers -
❖ Formed by the repeated addition of monomer molecules possessing double or
triple bonds, e.g., polythene from ethene and polypropene from propene.
❖ Homopolymers - Formed by polymerisation of a single monomeric species. e.g.,
polythene.

194
For More Material Join: @JEEAdvanced_2024
 ❖ Copolymers - Formed using two different monomers are termed as, e.g., Buna-S,
Buna-N

2. Condensation polymers -
❖ Formed by repeated condensation reactions between two different bi-functional or
tri-functional monomeric units.
❖ In these polymerisation reactions, the elimination of small molecules such as
water, alcohol, hydrogen chloride, etc. take place. E.g. terylene (dacron), nylon 6,
6, nylon 6, etc. For example, nylon 6, 6 is formed by the condensation of
hexamethylenediamine with adipic acid.

➢ Classification Based on Molecular Forces

Polymer applications in different fields depend on their unique mechanical properties like
tensile strength, elasticity, toughness, etc. These mechanical properties are governed by
intermolecular forces, e.g., van der Waals forces and hydrogen bonds, present in the
polymer.
1. Elastomers - Rubber like solids with elastic properties. Held together by the weakest
intermolecular forces. These weak binding forces permit the polymer to be
stretched.examples are buna-S, buna-N, neoprene, etc.

2. Fibres - Thread forming solids which possess high tensile strength and high modulus.
These strong forces like H Bonding lead to close packing of chains and thus impart
crystalline nature. The examples are polyamides (nylon 6, 6), polyesters (terylene),
etc.

3. Thermoplastic polymers - Linear or slightly branched long chain molecules capable of

repeatedly softening on heating and hardening on cooling. These polymers possess
intermolecular forces of attraction intermediate between elastomers and fibres. e.g.
polythene, polystyrene, polyvinyls, etc.

195
For More Material Join: @JEEAdvanced_2024
 4. Thermosetting polymers - Cross linked or heavily branched molecules, which on
heating undergo extensive cross linking in moulds and again become infusible. cannot
be reused. e.g bakelite, urea-formaldehyde resins, etc.

➢ Classification Based on Growth Polymerisation

Addition and condensation polymers are also known as chain growth polymers and step
growth polymers depending on the type of polymerisation mechanism they undergo
during their formation.

➢ Types of Polymerisation Reactions

Addition Polymerisation or Chain Growth Polymerisation -
The monomers used to add together on a large scale to form a polymer are unsaturated
compounds, e.g., alkenes, alkadienes and their derivatives. This mode of polymerisation
leading to an increase in chain length or chain growth can take place through the formation
of either free radicals or ionic species.
➢ Free radical mechanism
● Polymerised in the presence of a free radical generating initiator (catalyst) like benzoyl
peroxide, acetyl peroxide, tert-butyl peroxide, etc. For example, the polymerisation of
ethene to polythene consists of heating or exposing to light a mixture of ethene with a
small amount of benzoyl peroxide initiator.
● The process starts with the addition of phenyl free radical formed by the peroxide to
the ethene double bond thus generating a new and larger free radical. This step is called
chain initiation step. As this radical reacts with another molecule of ethene, another
bigger sized radical is formed.
● The repetition of this sequence with new and bigger radicals carries the reaction forward
and the step is termed as chain propagation step.
● Ultimately, at some stage the product radical thus formed reacts with another radical to
form the polymerised product. This step is called the chain terminating step. The
sequence of steps may be depicted as follows:

196
For More Material Join: @JEEAdvanced_2024
 Chain termination:

➢ Preparation of some important addition polymers

a) Polythene
i) Low density polythene:
▪ Obtained by the polymerisation of ethene under high pressure of 1000 to 2000
atmospheres at a temperature of 350 K to 570 K in the presence of traces of
dioxygen or a peroxide initiator (catalyst).
▪ Low density polythene (LDP) obtained through the free radical addition and H-
atom abstraction has a highly branched structure.
▪ Chemically inert and tough but flexible and a poor conductor of electricity.
ii) High density polythene:
▪ Formed when addition polymerisation of ethene takes place in a hydrocarbon
solvent in the presence of a catalyst such as triethyl aluminium and titanium
tetrachloride (Ziegler-Natta catalyst) at a temperature of 333 K to 343 K and
under a pressure of 6-7 atmospheres.
▪ Consists of linear molecules and has a high density due to close packing.
▪ Chemically inert and more tough and hard. It is used for manufacturing buckets,
dustbins, bottles, pipes, etc.
b) Polytetrafluoroethene (Teflon)
▪ Manufactured by heating tetrafluoroethene with a free radical or persulphate
catalyst at high pressures.
▪ Chemically inert and resistant to attack by corrosive reagents.

c) Polyacrylonitrile
▪ The addition polymerisation of acrylonitrile in presence of a peroxide catalyst
leads to the formation.
▪ Used as a substitute for wool in making commercial fibres as orlon or acrilan.

➢ Condensation Polymerisation or Step Growth polymerisation

● Involves a repetitive condensation reaction between two bi-functional monomers.
● Reactions may result in the loss of some simple molecules such as water, alcohol, etc.,
and lead to the formation of high molecular mass condensation polymers.
● Product of each step is again bi-functional species and the sequence of condensation
goes on.

197
For More Material Join: @JEEAdvanced_2024
 ● Since each step produces a distinct functionalized species and is independent of each
other, this process is also called step growth polymerisation.
● The formation of terylene or dacron by the interaction of ethylene glycol and
terephthalic acid is an example

➢ Polyamides
● Polymers possessing amide linkages are important examples of synthetic fibres and
are termed as nylons.
● Method of preparation consists of the condensation polymerisation of diamines with
dicarboxylic acids and also of amino acids and their lactams.

❖ Nylon 6,6:
● Prepared by the condensation polymerisation of hexamethylenediamine with adipic
acid under high pressure and at high temperature.
● Used in making sheets, bristles for brushes and in the textile industry.

❖ Nylon 6:
● Obtained by heating caprolactum with water at a high temperature.
● Used for the manufacture of tyre cords, fabrics and ropes.

➢ Polyesters
● Polycondensation products of dicarboxylic acids and diols. e.g. Dacron or
terylene is Manufactured by heating a mixture of ethylene glycol and terephthalic acid
at 420 to 460 K in the presence of zinc acetate antimony trioxide catalyst.
❖ Phenol - formaldehyde polymer (Bakelite and related polymers)
● Oldest synthetic polymers.
● Obtained by the condensation reaction of phenol with formaldehyde in the presence of
either an acid or a base catalyst.

198
For More Material Join: @JEEAdvanced_2024
● Reaction starts with the initial formation of o-and/or p-hydroxymethyl phenol
derivatives, which further react with phenol to form compounds having rings joined to
each other through –CH2 groups. The initial product could be a linear product – Novolac
which is used in paints

● Novolac on heating with formaldehyde undergoes cross linking to form an infusible

solid mass called bakelite.
● Used for making combs, phonograph records, electrical switches and handles of various
utensils.

❖ Melamine
● Formed by the condensation polymerisation of melamine and formaldehyde.
● Used in the manufacture of unbreakable crockery.

199
For More Material Join: @JEEAdvanced_2024
➢ Copolymerization

● Polymerisation reaction in which a mixture of more than one monomeric species is

allowed to polymerise and form a copolymer.
● Can be made not only by chain growth polymerisation but by step growth
polymerisation also. It contains multiple units of each monomer used in the same
polymeric chain.
● Example - a mixture of 1, 3 – butadiene and styrene can form a copolymer.
● Used for the manufacture of auto tyres, floor tiles, footwear components, cable
insulation, etc.

➢ Rubber
❖ Natural rubber
● Natural polymer and possesses elastic properties. Also termed as elastomer.
● Manufactured from rubber latex which is a colloidal dispersion of rubber in water.
● Obtained from the bark of rubber tree and is found in India, Srilanka, Indonesia,
Malaysia.
● Natural rubber may be considered as a linear polymer of isoprene (2-methyl-1, 3-
butadiene) and is also called as cis - 1, 4 - polyisoprene.

● cis-polyisoprene molecule consists of various chains held together by weak van der
Waals interactions and has a coiled structure. Thus, it can be stretched like a spring and
exhibits elastic properties.
❖ Vulcanisation of rubber:
● Natural rubber becomes soft at high temperature (>335 K) and brittle at low
temperatures (<283 K) and shows high water absorption capacity. It is soluble in non-
polar solvents and is non-resistant to attack by oxidising agents. To improve upon these
physical properties, a process of vulcanisation is carried out.
● Process consists of heating a mixture of raw rubber with sulphur and an appropriate
additive at a temperature range between 373 K to 415 K. On vulcanisation, sulphur
forms cross links at the reactive sites of double bonds and thus the rubber gets stiffened.
In the manufacture of tyre rubber, 5% of sulphur is used as a crosslinking agent.

200
For More Material Join: @JEEAdvanced_2024
 ❖ Vulcanised structures -:

❖ Synthetic rubbers
● Any vulcanised rubber-like polymer, which is capable of getting stretched to twice its
length.
● Returns to its original shape and size as soon as the external stretching force is released.
● Thus, synthetic rubbers are either homopolymers of 1, 3 - butadiene derivatives or
copolymers of 1, 3 - butadiene or its derivatives with another unsaturated monomer.

➢ Preparation of Synthetic Rubbers

i) Neoprene - formed by the free radical polymerisation of chloroprene.

ii) Buna – N
● Obtained by the copolymerisation of 1, 3 – butadiene and acrylonitrile
● Resistant to the action of petrol, lubricating oil and organic solvents. It is used in making
oil seals, tank lining, etc.

➢ Molecular Mass of Polymers

Polymer properties are closely related to their molecular mass, size and structure. The
growth of the polymer chain during their synthesis is dependent upon the availability of the
monomers in the reaction mixture. Thus, the polymer sample contains chains of varying
lengths and hence its molecular mass is always expressed as an average. The molecular
mass of polymers can be determined by chemical and physical methods.

➢ Biodegradable Polymers
Contains functional groups similar to the functional groups present in biopolymers.
Aliphatic polyesters are one of the important classes of biodegradable polymers. examples
-
1. Poly β-hydroxybutyrate – co-β-hydroxy valerate (PHBV)

201
For More Material Join: @JEEAdvanced_2024
 ● Obtained by the copolymerisation of 3-hydroxybutanoic acid and 3 - hydroxypentanoic
acid.
● Used in speciality packaging, orthopaedic devices and in controlled release of drugs.
● Undergoes bacterial degradation in the environment

➢ Nylon 2–nylon 6
● An alternating polyamide copolymer of glycine (H2N–CH2–COOH) and amino caproic
acid [H2N (CH2)5COOH] and is biodegradable.

➢ Polymers of Commercial Importance

202
For More Material Join: @JEEAdvanced_2024
 Chemistry in Everyday Life

⮚ Chemistry in drugs:
● Drug: Low molecular weight chemicals used for diagnosis, prevention, treatment and
cure.
● Drugs interact with macromolecular targets to produce biological response
● Medicine: Drugs used for therapeutic purposes. If chemicals are used for therapeutic
purposes, it is called chemotherapy
● If higher doses are taken than prescribed, they are dangerous.

⮚ Classification of drugs:

Based on pharmacological Eg: Analgesics - Painkillers, Antiseptic - Kill or arrest

effect growth of microbes.

Based on drug action on Eg: Antihistamines -Inhibit histamine which causes

particular biochemical process inflammation in body

Based on chemical structure Eg: sulphonamides

Note: Similar structures features → similar

pharmacological activity.

Based on molecular targets Drug targets can be Carbohydrates, proteins, nucleic acids
or lipids

Note: Drugs with common structural features may have same mechanism of action on
targets
⮚ Drug target interaction:
● Two types of protein targets
1. Enzymes: Biological catalysts
2. Receptors: Communication system of cells

1. Enzymes as drug targets:

● Enzymatic action:
❖ Enzymes consist of active sites at which the substrate binds and forms enzyme
substrate complexes.
❖ Substrate binds due to interactions such as ionic bonding, hydrogen bonding, van
der Waals interaction or dipole-dipole interaction
❖ It provides functional groups which attack substrates and convert them to products.
❖ E + S ⇋ ES complex → E + products.

203
For More Material Join: @JEEAdvanced_2024
● Drug, enzyme interaction:
❖ Drugs act by inhibiting the enzymes, thereby preventing product formation.
❖ Inhibition can be of two types:
▪ Competitive inhibition: Drug binds at the active site instead of substrate and
thus inhibiting product formation

▪ Non-competitive inhibition: Drug binds to enzymes at a region called

allosteric site. This changes the structure of the active site and thereby prevents
binding of substrate.
❖ If the bond b/w drug and enzyme is a strong covalent bond then it cannot be broken
easily and thus the enzyme-drug complex would finally be degraded by the body.

2. Receptors as drug targets:

● Receptors are the proteins embedded in the cell membranes and are important
communication systems.
● Similar to enzymes, they also have active sites which are projected on the outer
region of the cell.
● In body messages from neurons to muscles are transferred by chemicals called
chemical messengers.
● Receptors bind only to specific messenger molecules because their binding sites
have different shape, structure and amino acid composition.
❖ Action of receptors:
● Receptor binds specifically to chemical messengers.
● Due to binding of messenger molecules, the shape of the receptor changes
which result in transfer of message into cells.
● Due to change in the shape of the receptor, chemical messengers detach from
the receptor and then the receptor regains its shape.

204
For More Material Join: @JEEAdvanced_2024
 ❖ Based on drug’s interaction with receptor:
● Agonist: Mimics the action of a natural messenger. Used when there is
deficiency of natural messengers
● Antagonist: Opposes the action of a natural messenger, blocking the
transmission of messages into cells.
⮚ Therapeutic action of different class of drugs:
1. Antacids:
● Used when the stomach overproduces acid causing irritation and pain which may
lead to ulcers in extreme conditions
● Chronology:
❖ Till 1970:
▪ Treatment: Antacids such as sodium hydrogencarbonate or a mixture of
aluminium and magnesium hydroxide used.
▪ Disadvantages: All control only symptoms but not the cause. Excess of sodium
hydrogencarbonate causes an alkaline stomach, triggering production of excess
acid. Metal hydroxides are better as they do not increase pH above neutrality.
Also in advanced stages of ulcers, surgical removal of the affected part is the
only treatment.
❖ After 1970:
▪ Treatment: Cimetidine (Tagamet) drug
▪ Drug action: Histamine is a chemical which stimulates secretion of pepsin and
HCl in the stomach. By targeting histamine i.e preventing histamine to bind to
its receptors, acid production would be reduced.
❖ Currently:
▪ Treatment: Ranitidine (Zantac) drug
● Structures of examples:

2. Antihistamines:
● Histamine: Potent vasodilator, contracts smooth muscles in bronchi, gut and relaxes
other muscles such as walls of blood vessels. Also responsible for nasal congestion
during common cold and allergic response to pollen
● Antihistamine drugs: Brompheniramine (Dimetapp) and terfenadine (Seldane).
They compete with histamine and bind to its receptor sites inhibiting its action.

205
For More Material Join: @JEEAdvanced_2024
 ● Note: Antacids and antiallergic drugs both target histamine molecules, but work on
different receptors
● Structures of examples:

.
3. Neurologically active drugs:
Function by affecting the message transfer mechanism from nerve to receptor.
I. Tranquilisers:
● Treatment of stress and mild or severe mental disorders.
● Essential component of sleeping pills.
● Antidepressant drugs:
❖ Noradrenaline, a neurotransmitter, is responsible for mood changes. If levels
are very low, it causes depression. In such cases antidepressants are given
which inhibit enzymes which degrade noradrenaline thereby increasing the
span of noradrenaline. Eg: Iproniazid and phenelzine are antidepressants.
● Other examples of tranquilisers:
❖ Chlordiazepoxide and meprobamate - For relieving tension
❖ Equanil - depression and hypertension
❖ Derivatives of barbituric acid such as Veronal, amytal, nembutal, luminal and
seconal - Hypnotic i.e. sleep producing agents.
❖ Valium
❖ Serotonin
● Structures of examples:

206
For More Material Join: @JEEAdvanced_2024
 II. Analgesics:
● Reduces pain without impairment of consciousness, mental confusion,
incoordination or paralysis or other disturbances of the nervous system.
● Two types:
i. Non-narcotic (non-addictive):
● Eg: Paracetamol and Aspirin
Aspirin - Painkiller, relieves skeletal pain such as due to arthritis,
antipyretic (reduces fever), prevention of heart attacks as it prevents
platelet coagulation. Aspirin acts by inhibiting prostaglandins which
cause inflammation and pain in tissue.
ii. Narcotic (Addictive):
● Used for relief of postoperative pain, cardiac pain and pains of terminal
cancer and during childbirth
● Administered in medicinal doses relieves pain and produces sleep. In
large amounts causes coma, convulsions, stupor and ultimately death.
● Eg: Opiates (Obtained from opium poppy) such as morphine, heroin,
codeine etc.
● Structure of examples:

4. Antimicrobials:
● Destroys or inhibits pathogenic action of microbes such as bacteria (antibacterial
drugs), fungi (antifungal drugs), viruses (antiviral drugs), or other parasites
(antiparasitic drugs).
● Different types include antibiotics, antiseptics, disinfectants.
1. Antibiotics:
● Past definition: Chemical substances produced by microorganisms that inhibit the
growth or even destroy microorganisms.

207
For More Material Join: @JEEAdvanced_2024
● Current definition: Substance produced wholly or partly by chemical synthesis,
which in low concentrations inhibits the growth or destroys microorganisms by
intervening in their metabolic processes.
● Examples:
❖ Arsphenamine (salvarsan): Arsenic based compound used for treatment of
syphilis. Its toxicity is much higher on spirochete (causes syphilis) than humans
❖ Azo Dyes: Have structural similarities with salvarsan. (-As=As- in salvarsan is
similar to -N=N- in azo dyes).
❖ Prontosil (Resembles salvaran): In the body it is converted into sulphanilamide
(actual active compound).
❖ Sulphapyridine: Analogue of sulphonamide
❖ Penicillin - Alexander Fleming isolated it from Penicillium fungus which has
antibacterial properties.
● Two types:
❖ Bactericidal: Kills microbes. Eg: Penicillin, Aminoglycosides, Ofloxacin
❖ Bacteriostatic: Inhibits microbes. Eg: Erythromycin, Tetracycline,
Chloramphenicol.
● Classification based on spectrum of action:
❖ Broad range spectrum:
▪ Kill or inhibit a wide range of gram negative and gram-positive bacteria.
▪ Eg: Ampicillin and Amoxicillin (synthetically modified penicillins)
❖ Narrow range spectrum:
▪ Kill or inhibit a narrow range of gram negative or gram-positive bacteria.
▪ Examples:
● Penicillin. (Manufactured by Hindustan antibiotics, Pimpri in India)
Note: It's important to test for sensitivity (allergy) to penicillin before
administering.
● Chloramphenicol: Rapidly absorbed from the gastrointestinal tract and hence can
be given orally in case of typhoid, dysentery, acute fever, certain form of urinary
infections, meningitis and pneumonia.
● Vancomycin and ofloxacin
❖ Limited spectrum:
▪ Effective against a single organism or disease.
▪ Example: dysidazirine - Toxic to few strains of cancer
● Structures of examples:

208
For More Material Join: @JEEAdvanced_2024
2. Antiseptics:
● Applied to living tissues like wounds, cuts, ulcers or diseased skin surfaces.
● Should Not be ingested like antibiotics
● Examples:
❖ Dettol: Mixture of chloroxylenol and terpineol
❖ Bithionol or biothional: Added to soaps.
❖ Iodine: 2-3% mixture is called tincture of iodine. Used to sterilize skin
before surgical procedures.
❖ Iodoform: For wounds.
❖ Boric acid: Weak antiseptic for eyes.
❖ Others include furacine, soframycin etc
● Structures of examples:

3. Disinfectants:
● Applied to inanimate objects like floors, drainage systems, instruments etc.
● Examples: Chlorine (0.2-04 ppm), SO2 in very low concentration
● Note: Phenol - 0.2% act as antiseptic, 1% act as disinfectant.

209
For More Material Join: @JEEAdvanced_2024
 5. Antifertility drugs:
● For population control and family planning
● Birth control pills contain a mixture of synthetic estrogen and progesterone
derivatives. Eg: Norethindrone (synthetic progesterone), Ethynylestradiol
/novestrol (estrogen derivative used with progesterone derivative.
● progesterone suppresses ovulation. Synthetic progesterone derivatives are more
potent than progesterone
● Structures of examples:

⮚ Chemistry in food:
● Added for: Preservation, enhancing appeal, adding nutritional value.
● Main Categories:
(i) Food colours
(ii) Flavours and sweeteners
(iii) Fat emulsifiers and stabilising agents
(iv) Flour improvers - antistaling agents and bleaches
(v) Antioxidants
(vi) Preservatives
(vii) Nutritional supplements such as minerals, vitamins and amino acids.
⮚ Artificial sweetening agents:
● Importance: Natural sweeteners are high in calories so artificial sweeteners are used as
substituents.
● Few examples:
Compound Sweetness Points Structure

saccharin 550 Use: For diabetic persons

Points:
1. Also called Ortho-
sulphobenzimide
2. Excreted from the body in
urine unchanged.
3. Harmless and inert.

Aspartame 100 Use: In cold foods and soft

drinks as it is unstable at high
temperatures.

Points:
1. Methyl ester of dipeptide

210
For More Material Join: @JEEAdvanced_2024
 formed from aspartic acid and
phenylalanine

Alitame 2000 Points:

1. High potency sweetener
2. Stable than aspartame but
tough to control sweetness.

Sucralose 600 Points:

1. Trichloro derivative of
sucrose
2. Appearance and taste as sugar
3. No calories
4. Stable at cooking temperature

⮚ Food preservatives:
● Prevent spoilage of food due to microbial growth.
● Common eg: table salt, sugar, vegetable oils, sodium benzoate (C6H5COONa), salts of
sorbic acid & propanoic acid.

⮚ Chemistry in Cleansing agents:

● Substances to remove stains, dirt etc.
● Two types of detergents used as cleansing agents: (1) Soaps, (2) Synthetic detergents
● Helps in removal of fats which bind other materials to the fabric or skin
Soaps
● Sodium or potassium salts of long chain fatty acids are soluble in water and are used
for cleaning purpose
Eg: stearic, oleic and palmitic acids
● Preparation:
1. Heating fat (i.e. Glyceryl ester of fatty acid) with NaOH form sodium salt and the
process is called saponification.

2. Esters of fatty acids are hydrolysed and the soap obtained remains in colloidal form.
It is precipitated from the solution by adding NaCl. The solution left after removing
the soap contains glycerol, which can be recovered by fractional distillation.
3. To prepare potassium salt use KOH instead of NaOH.

211
For More Material Join: @JEEAdvanced_2024
 ● Potassium soaps are softer to skin than sodium soaps.
● Types of soaps:
Different types of soaps can be made by using different raw materials
● Toilet soap: Better grade of fats and oils used. Excess alkali is removed. Colour
and perfumes are added for aesthetic purpose
● Soaps floating in water: Made by beating tiny air bubbles before their hardening
● Transparent soaps: Made by dissolving the soap in ethanol and then evaporating
the excess solvent.
● Medicated soaps: By adding medicinal substances.
● Shaving soaps: Contain glycerol for rapid drying. Rosin gum is added to form
rosinate which lathers well.
● Laundry soaps: Contain fillers like sodium rosinate, sodium silicate, borax and
sodium carbonate.
● Soap chips: Made by running a thin sheet of melted soap onto a cool cylinder and
scraping off the soaps in small broken pieces.
● Soap granules: Dried miniature soap bubbles.
● Soap powder and scouring soap: Contains some soap, a scouring agent (abrasive)
such as powdered pumice or finely divided sand, and builders like sodium
carbonate and trisodium phosphate. Builders make the soaps act more rapidly.

● Soaps in Hard water:

● Hard water has Ca, Mg salts. These react with sodium salt in soap and form Ca and
Mg soaps. The insoluble Ca, Mg soaps separate out as scum and are useless with
no cleansing activity.

● Precipitates of these soaps adhere onto the fibre of the cloth as gummy mass.
● Hair becomes dull, dyes do not absorb evenly on cloth due to this sticky precipitate.

⮚ Synthetic detergents:
● Have all properties of soap but do not contain any soap.
● Can give foam with hard water unlike soaps. Some of them give foam even with ice
cold water also.
● Classification: Anionic, cationic, non ionic
(1) Anionic detergents:
⮚ Sodium salts of sulphonated long chain alcohols or hydrocarbons.
⮚ Anionic part is involved in cleansing activity.
⮚ Eg: Sodium salts of alkylbenzenesulfonates
⮚ Preparation: Treating long chain alcohols with conc.H2SO4 and neutralised with
alkali to form anionic detergents. Similarly alkyl benzene sulphonates are
obtained by neutralising alkyl benzene sulphonic acids with alkali.

212
For More Material Join: @JEEAdvanced_2024
 ⮚ Used in household work and in toothpaste

(2) Cationic detergents:

⮚ Quaternary ammonium salts of amines with acetates, chlorides or bromides as
anions.
⮚ Eg: Cetyltrimethylammonium bromide

⮚ Used in hair conditioners. Have germicidal properties and are expensive.

(3) Non ionic detergents:
⮚ No ions
⮚ Preparation: Stearic acid with polyethylene glycol.

⮚ Cleansing action is the same as soap, removes grease and oil by micelle
formation.
⮚ Used in liquid dish washing.
● Problems with detergents:
⮚ Water pollutant: Cannot be degraded by bacteria due to highly branched
hydrocarbons and are accumulated. They persist even after sewage treatment
and reach rivers, ponds etc causing foaming and thereby polluting water bodies.
These days branching is controlled and kept to a minimum. Unbranched chains
are biodegradable.

213
For More Material Join: @JEEAdvanced_2024