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CHEMISTRY
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CHEMISTRY
SOME BASIC CONCEPTS OF CHEMISTRY
Classification of mixtures into homogeneous and heterogeneous
Mixtures having uniform composition and where the components cannot be seen
separately are called homogeneous mixtures.
Eg :  Sugar solution  NaCl solution  Air  Brass etc.
Mixtures not having uniform composition and where the components can be seen
separately are called heterogeneous mixtures.
Eg:  Soil  Mud water  Milk
Laws of Chemical Combinations
1. Law of conservation of mass
Matter can neither be created nor be destroyed.
OR
In a chemical reaction, total mass of the reactants is equal to the total mass of
products.
100 gm of calcium carbonate (CaCO3) on heating gives 56 gm of CaO and 44 gm of
CO2. Here total mass of reactants = 100gm. Total mass of products is also equal to
100 gm.
2. Law of Definite proportion (constant composition)
Same compound always contains the same elements combined in the same fixed
proportion by mass.
Eg : CO2 obtained from different sources have same elements carbon and oxygen
combined in the ratio 12:32
3. Law of multiple proportion
When two elements combine together to produce more than one compound,
different masses of one of the elements which combine with a fixed mass of the
other element bear a simple ratio.
Eg : C combines with O to produce two compounds, CO2 and CO. In CO2 the mass
ratio is 12:32. In CO, the ratio is 12:16. Mass of carbon is fixed. The ratio between
different masses of O is 32:16 or 2:1.
4. Gay Lussac’s law of gaseous volumes
When gases combine to give gaseous products, there exists a simple ratio between
volumes of reactants and products.
Eg : In the reaction between H2 and Cl2 to give HCl, the ratio is 1: 1: 2,
H2 + Cl2  2HCl. N2 + 3H2  2 NH3 Ratio = 1: 3: 2
5. Avogadro’s Law
Equal volumes of all gases under the same conditions of temperature and pressure
contain equal no: of molecules.
Atomic Mass
It is a number which expresses how many times the mass of an atom of an element is
greater than 1/12th mass of C-12 atom.

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Atomic mass of certain elements are given below:

H = 1 O = 16
He = 4 F = 19
Li = 6 Ne = 20
Be = 9 Na = 23
B = 10 Cl = 35.5
C = 12 Ca = 40
N = 14 S = 32
1
th mass of C – 12 atom is called 1 atomic mass unit (amu).
12
1 amu = 1.66  10-24 g = 1/6.022  1023 g
Atomic masses of certain elements are taken as the average of atomic masses of different
isotopes of the element.
Eg : Chlorine exists as 2 isotopes, Cl – 35 and Cl – 37 in the ratio 3:1
35  3  37  1
Atomic mass of chlorine = = 35.5
4
Exact mass of a Hydrogen atom = 1.008 amu = 1.008  1.66  10-24g
Molecular Mass
1
It is a number which shows how many times the mass of a molecule is greater than th
12
mass of C-12 atom.
Molecular mass can be obtained by adding atomic masses of elements.
1. O2 - 2  16 = 32
2. H2 -21 = 2
3. N2 - 2  14 = 28
4. CO2 - 1  12 + 2  16 = 44
5. H2SO4 - 2  1 + 32  1 + 4  16 = 98
6. HNO3 - 1  1 + 1  14 + 16  3 = 63
7. C6H12O6 - 12  6 + 12  1 + 16  6 = 180
Exact mass of a water molecule = 18  1.66  1024g = 18 amu
Exact mass of an O2 molecule = 32 amu = 32  1.66  10-24g
Mole concept
One mole is the amount of a substance containing Avogadro number (NA) of particles.
In the case of a substance existing as atoms, 1 mole contains 6.02  1023 atoms. In the case
of a substance existing as molecules, 1 mole contains 6.02  1023 molecules.
1 mole Na contains 6.02  1023 Na atoms
1 mole O2 contains 6.02  1023 oxygen molecules
1 mole C contains 6.02  1023 C atoms.
1 mole H2O contains 6.02  1023 water molecules.

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Molar mass
Mass of one mole of a substance is called molar mass. For a substance existing as atoms,
molar mass = atomic mass in gms
For a substance existing as molecules, molar mass = molecular mass in gms.
Molar mass of C = 12 g
Molar mass of H2 = 2.016 g
Molar mass of O2 = 32 g
Molar mass of NH3 = 17 g
Molar mass of CO2 = 44 g
Number of moles = Mass in g
Molar mass

LIMITING REAGENT
The reactant which is getting completely consumed in a reaction is called limiting reagent.
When equal no: of moles of N2 and H2 are taken in the reaction,
N2 + 3 H2  2NH3 H2 is the limiting reagent.
When equal masses of N2 and H2, 6gm each is taken, N2 is the limiting reagent. 6g H2
needs 28 g of N2 to react to form 34g of NH3. But only 6g N2 is present. N2 will get
consumed first and it is the limiting reagent.
Methods of Expressing concentration of solutions
b) Mole Fraction
It is the ratio between number of moles of a component to the total number of moles of
different components present in the solution.
For a solution of A and B
nA nB
Mole fraction of A, xA = xB =
n A  nB nA  nB
The sum of mole fractions of different component present in a solution is always equal to
one.
xA + xB = 1 xB = 1 – xA
Molarity
Number of moles of solute present per litre of solution
Number of moles of solute n
Molarity = =
Volume of solution in litres V
or
M = mass/litre (of solute)
molar mass (of solute)
Unit = Moles/litre or M
 Molality (m)
No: of moles of solute present per kg of solvent.
Number of moles of solute(n)
Molality, m =
Mass of solvent in Kg(W)
Unit = mol/kg or mol kg-1 or m

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STRUCTURE OF AN ATOM
Cathode rays (Discovery of electrons)
Cathode rays are produced when a high voltage electric discharge is passed through a gas
at very low pressure. The properties of cathode rays are given below.
 Cathode rays are found to originate from the side of cathode and they move towards
the side of anode.
 They travel along straight lines.
 They consists of material particles.
 They will get deflected when passed through an electric field or magnetic field. The
direction of deflection shows that they consists of negatively charged particles.
 They can produce fluorescence on a screen coated with ZnS.
 The nature of particles in the cathode rays is independent of the nature of the gas
taken in the discharge tube.
The negatively charged particles in cathode rays were named as electrons.
 Anode rays
When the discharge tube experiment is conducted with a perforated cathode some
invisible rays are found to travel from the side of anode towards the side of cathode.
These rays were named as anode rays.
 Properties of Anode rays
 They travel along straight lines.
 Consists of material particles.
 They undergo deflection when passed through an electric field or magnetic field.
 Direction of deflection shows that they consists of positively charged particles.
 The e/m of ratio of particles in anode rays depends on the nature of gas taken inside
the discharge tube.
The particles with lightest e/m ratio was obtained when H2 gas is taken inside the
discharge tube and these particles were named as protons.
Rutherford’s Alpha Particle Scattering Experiment
Rutherford allowed a stream of alpha particles to strike on a thin gold foil and he placed a
screen coated with Zns after the gold foil. From this experiment, he made the following
observations.
 Most of the alpha particles passed through the gold foil without any deflection.
 A few no. of  alpha particles got deflected through small angles.
 A very few (1 in 20000) got bounced back through an angle of 180.
From the above observations, Rutherford made the following conclusions.
 Most of the space in an atom is empty.
 There is a positively charged center in an atom.
 Most of the mass of an atom is concentrated at the positively charged central part
called nucleus.
 The size of the nucleus is very small (10-15m) compared to the size of the atom
(1010m)
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Rutherford’s Model of Atom

 An atom consists of a central positively charged part called nucleus.
 Most of the mass and the entire positive charge of an atom is concentrated at the
nucleus.
 Negatively charged electrons revolve around the nucleus through circular paths
called orbits.
Atomic number and Mass number
 Atomic number (Z) – No. of protons or no. of electrons in an atom of an element.
 Mass number (A) – Total no. of protons and neutrons
 No. of neutrons = A – Z
Drawbacks of Rutherford Model
 Rutherford model could not explain the stability of an atom. According to Maxwell
when a charged particle like electron is subjected to acceleration, it should emit
energy in the form of radiation continuously and should finally fall into the nucleus.
But this doesn’t happen.
 It doesn’t give an idea about the distribution of electrons around the nucleus.
Photo electric effect
When radiations are allowed to fall on the surface of certain metals electrons are emitted.
This phenomenon is called photo electric effect.
The following observations were made while observing the photo electric effect:
a) The no: of electrons emitted is directly proportional to intensity of the radiation.
b) For each metal, there is a minimum frequency for the incident radiation called
threshold frequency (0) below which there is no emission of electrons.
c) The kinetic energy of electrons emitted  frequency of radiation.
Max Planck’s Quantum Theory
 Radiant energy is emitted from a source not continuously, but discontinuously in the
form of packets of energy called ‘quanta’ (in the case of visible light, quantum is
called photon).
 Energy associated with a quantum  frequency of the radiation.
E  E = h
‘h’ is a constant called Planck’s constant. It’s value is 6.626  10–34 Js
 Energy emitted from a source will be an integral multiple of h.
E = nh n = 1, 2, 3, 4.......
Explanation for photo Electric Effect by Einstein
 When a beam of light strikes on a metal surface, photons present in the radiation will
collide with electrons in metal atoms, transfers their energy into electrons and then
electrons will get ejected.
 Greater the energy carried by the photon Greater will be the kinetic energy of the
electron.
K.E of emitted electrons = h - ho
vo is the frequency of incident radiation.
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vo – threshold frequency.
 As the intensity of light increases, the number of photons striking the metal surface
increases and hence the no: of electrons emitted increases.
Hydrogen spectrum
When an electric discharge is passed through H2 gas, light will get emitted. When this
light is observed through a spectroscope a large number of lines are found. This is called
spectrum of H2. These lines were found as five groups and they were named as Lymann
series, Balmer series, Paschen series, Brackett series and Pfund series. Each line in the
spectrum is produced by radiation having a particular wavelength. Lines in the Lymann
series were made by UV radiation. Lines in the Balmer series were made by visible
radiations and lines in the other 3 series were made by IR radiation.
Rydberg introduced an expression for getting wave numbers of various lines in the
hydrogen spectrum as:
 1 1 
 = R  2  2  cm–1
 n1 n2 
R = Rydberg constant = 109, 677 cm–1
For Lymann series, n1 = 1 n2 = 2, 3, 4, 5.....
For Balmer series, n1 = 2 n2 = 3, 4, 5, 6.....
For Paschen series, n1 = 3 n2 = 4, 5, 6, 7.....
For Brackett series, n1 = 4 n2 = 5, 6, 7, 8.....
For Pfund series, n1 = 5 n2 = 6, 7, 8, 9.....
Boher Model of Atom
1. Atom consists of a central positively charged part called nucleus.
2. Electrons revolve round the nucleus through certain selected circular paths called
orbits. As long as an electron is revolving through a particular orbit, it cannot loose
or gain energy.
3. Only those orbits are permitted for which angular momentum is an integral multiple
of h/2. Angular momentum, mvr = nh/2. n = 1, 2, 3, 4....
4. As the value of ‘n’ increases energy of electron increases.
5. An electron can jump from one orbit to another by absorbing or emitting energy in
the form of radiation. When an electron jumps from a higher energy level, E2 to
lower energy level E1 the frequency of radiation can be obtained from the
E 2  E1
expression, v =
h
Merits of Bohr Model
1. It could explain the stability of an atom. According to Bohr model as long as an
electron is revolving through a particular orbit it cannot gain or loose energy.
Therefore the atom remains stable.
2. Bohr introduced an expression for getting energy of an electron in the ‘nth’ orbit of
hydrogen atoms as.
 1312
En = kJ/molEn
n2

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Defects of Bohr Model

1. It could not explain the fine spectrum of hydrogen.
2. It could not explain the formation of chemical bonds and the shapes of molecules
satisfactorily
3. According to de-Broglie concept and Heisenberg’s uncertainty principle definite
circular paths cannot be assigned for electrons.
de-Broglie concept (Dual Behaviour of Matter)
Louis de-Broglie proposed that small material particles like electrons can posses particle
nature as well as wave nature.
He introduced an expression for getting the wavelength of wave associated with a material
particle as.
h
 = v – velocity, m – mass
mv
h
= (mv = momentum)
p
Heisenberg’s Uncertainty Principle
It is the impossible to determine simultaneously the exact position and momentum or
velocity of a moving subatomic particle like electron.
The principle can be mathematically represented as.
h h
x  p  x  m  v 
4 4
x = Uncertainty in position p = Uncertainty in momentum
v = Uncertainty in velocity m = mass of the particle
h = Planck’s constant
Quantum Numbers
A set of numbers used to denote an orbital or an electron in an atom. They are of 4 types.
1) Principal Quantum number. 2) Azimuthal Quantum number.
3) Magnetic Quantum number. 4) Spin Quantum number.
Principal quantum Number
It is used to denote the energy level to which an orbital or an electron in an atom belongs.
It also gives an idea about size of an orbital. It is represented using ‘n’ and can have
values 1, 2, 3, 4.... These energy levels are also called electron shells They are also
represented using letters K, L, M, N etc.
Azimuthal quantum number
It is used to denote the sublevel to which an orbital or an electron in an atom belongs. It
also gives an idea about the shape of an orbital. It is represented using ‘l’ and can have
values O  n – 1.
For the Ist energy level, n = 1 , l = 0 only ‘s’ sublevel is there
For n = 2 For n = 3 n = 4
l = 0, 1 l = 0, 1, 2 l = 0, 1, 2, 3
s p s p d s p d f

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Magnetic Quantum number

It is used to denote the orientation of an orbital in a particular sublevel. It is represented
using letter ‘m’ and can have values – l  o  +l.
For s sublevel, l = 0 m=0
For P sublevel, l = 1 m = -1, 0, +1
Three P orbitals are there. They are Px, Py and Pz
For d sublevel, l=2 m = -2, -1, 0, 1, 2
Five d orbitals are there. They are dxy, dyz, dxz, dx2-y2, dz2
For f sublevel, l=3 m = -3, -2, -1, 0, 1, 2, 3 seven ‘f’ orbitals.
Spin Quantum number
It is used to denote the spin of an electron in an orbited. It is represented using ‘s’ and can
have values + ½ or - ½ .
SHAPES OF ATOMIC ORBITALS
Shapes of 1s and 2s Orbitals
Shapes of 1s and 2s orbitals are given
below. The region of zero electron density
found within an orbital is called node. 2s
orbital is having 1 node and ns orbital will
be having n – 1 number of nodes.

Shapes of P orbitals
Shapes of P orbitals are given below In a P
orbital there will be a plane of zero electron
density. This is called nodal plane.
For 2Px orbital, nodal plane is y, z plane.

Shapes of ‘d’ orbitals

Electronic Configuration
The distribution of e s in various orbitals of an atom is known as electron configuration. It
can be done on the basis of Aufbau Principle, Pauli’s exclusion principle and Hund’s rule
of maximum multiplicity.

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Aufbau Principle
Electrons should be filled in various orbitals in the increasing order of their energy.
Energies of various orbitals can be understood from two n + 1 rules, they are given below.
1) Energies of various orbitals increase in the increasing order of n + l values.
1s 2s 2p 3s 3p 3d 4s 4p 4d
n+l 1 2 3 3 4 5 4 5 6
2) If 2 orbitals have the same n + l value, the one having
lower ‘n’ value will be having lower energy.
Order of energy of various orbitals can be obtained
from the following diagram.

Pauli’s Exclusion Principle

No two electrons in an atom can have the same set of values for all the four quantum
numbers. That means only two electrons can be accommodated in an orbital.
Hund’s rule
Filling of electrons in orbitals of a particular sublevel (Eg : 2Px, 2Py and 2Pz) takes place
only after all such orbitals are half filled.
For eg : E.C of Nitrogen (z = 7) is
1s2 2s2 2Px1 2Py1 2Pz1
    
E.C of Certain elements
H - 1s1 N - 1s2, 2s2, 2p3
He - 1s2 O - 1s2, 2s2, 2p4
2 1
Li - 1s 2s F - 1s2, 2s2, 2p5
Be - 1s2, 2s2 Ne - 1s2, 2s2, 2p6
2 2 1
B - 1s , 2s , 2p Na - 1s2, 2s2, 2p6, 3s1
2 2 2
C - 1s , 2s , 2p Cl - 1s2, 2s2, 2p6, 3s2, 3p5
2 2 6 2 6 2 1
Sc - 1s , 2s , 2p , 3s , 3p , 4s , 3d
Cr - 1s2, 2s2, 2p6, 3s2, 3p6, 4s1, 3d5
Cu - 1s2, 2s2, 2p6, 3s2, 3p6, 4s1, 3d10
Exceptional Configuration of Chromium and Copper
The outershell configuration of Cr is 4s1 3d5 and not 4s2 3d4 because in the configuration
4s1 3d5 all ‘d’ orbitals are half filled. It is a symmetrical distribution and hence it is more
stable
The outer shell configuration of Cu is 4s1 3d10 and not 4s2 3d9 because in the configuration
4s1 3d10 all ‘d’ orbitals are completely filled. It is a symmetrical distribution and hence it
is more stable.
***

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CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES

Mendeleev’s Periodic Law
“The physical and chemical properties of elements are a periodic function of their atomic
mass”
Modern Periodic Law
“The physical and chemical properties of elements are a periodic function of their atomic
number”.
Periodic trends in properties
Ionisation Enthalpy
It is the energy required to remove an electron from an isolated gaseous atom. The energy
required to remove the first e from an atom and to convert it into unipositive ion is called
first ionisation Enthalpy.
The energy required to remove an e from a unipositive ion and to convert it into
bipositive ion is called second ionisation Enthalpy.
Second I. E is greater than Ist I. E. This is because it is difficult to remove an e from a
+ve ion than a neutral atom.
From left to right in a period ionisation enthalpy increases. This is because atomic size
decreases, attractive force between nucleus and ē increases.
From top to bottom in a group I. E decreases. This is because atomic size increases,
attractive force between nucleus and ē in the valence shell decreases.
Electron gain Enthalpy
It is the energy change taking place during the addition of an e into a neutral atom and to
convert it into a negatively charged ion. It is represented as eg H.
It can be negative when energy is released and can be positive when energy is absorbed.
Noble gases have positive eg H and all other elements have negative eg H. Group 17
elements have the highest negative eg H. This is because they have the smallest atomic
size and just by gaining one more e they can attain stable noble gas configuration.
From left to right in a period egH becomes more negative. This is because atomic size
decreases. From top to bottom in a group egH becomes less negative. This is because of
increase in atomic size.
egH of F is less negative than that of Cl. This is because in the case of F the additional e
enters into small sized 2 P orbital. Here inter electronic repulsion will be more. But in the
case of Cl the additional e enters into 3P orbital which is larger in size. Here inter
electronic repulsion will be less.
Anomalous Behaviour and diagonal relationship
Properties of the Ist element in a group is found to be different from those of other
elements in the group. This called anomalous behaviour. This is because of the small size,
high ionisation energy, high electronegativity and non- availability of d orbitals in the
valence shell. Properties of the first element in a group is found to be similar to those of
the 2nd element in the next group. This is called diagonal relationship.
Eg : Li  Mg Be  Al B  Si
Reasons for diagonal relationship are:
 Similar size  Similar T. E and I.E.  Similar E. N

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CHEMICAL BONDING AND MOLECULAR STRUCTURE

Polarity of Bonds
When a covalent bond is formed between atoms of 2 different elements, the electron pair
will not be shared equally. It will displace towards the more electro negative atom,
imparting a slight negative charge to the electro negative atom and an equal positive
charge to the other atom. This kind of a covalent bond is called polar covalent bond.
In HCl molecule the polar character can be represented as H +  Cl-
The extent of polarization in a bond is represented using a term called Dipole moment (μ).
μ = qd q = charge developed d = bond length
Dipole moment is expressed in the unit Debye (D)
1D = 3.34  10-30Cm
Dipole moment is a vector quantity with its direction from the positive end to the negative
end. It is represented as ‘ ’.
+ -
H Cl
In a poly atomic molecule, dipole moment depends on the shape of the molecule.
CO2 molecule is having linear shape, where dipole moment vectors
cancel each other and hence net dipole moment is equal to zero.
H2O molecule is having a net dipole moment of 1.85 D. This is
because the molecule is having a bend shape, where dipole moment
vectors will not cancel each other.
Molecules like BeF2, BCl3, CCl4 etc. also have zero net dipole moment.

NH3 molecule having pyramidal shape is having a net dipole moment of 1.47 D. But
similar molecule NF3 is having a net dipole moment of only 0.23 D. This is because in
NH3 the dipole moment vectors of the N-H bond and
the moment due to the lone pair (orbital moment) are
acting in the same direction. But in NF3, they are
acting in opposite directions.
VSEPR Theory to explain shapes of molecules
Sidwick and Powel introduced the VSEPR Theory.
1. Shape of a molecule depends on the number of electron pairs present in the valence
shell of the central atom in the molecule.
2. There will be repulsion between electron pairs and to minimize the repulsion they
try to lay as far apart as possible.
3. The repulsion between electron pairs follows the order:
l.p-l.p > l.p – b.p > b.p – b.p l.p – lone pair b.p – bond pair
Shapes of certain molecules explained on the basis of VSEPR Theory is given below

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 BeF2 molecule
The central atom Be is having 2 bond pairs in the valence shell. To
minimize the repulsion between e pairs BeF2 assumes linear shape
with a bond angle of 180°.
 BCl3 molecule
The central atom B is having 3 bond pairs in the valence shell. To
minimize the repulsion between e pairs BCl3 assumes triangular
planar shape with a bond angle of 120°.
 CH4 molecule
The central atom C is having 4 bond pairs in the valence shell.
Therefore the molecule assumes tetra hedral shape with a bond
angle of 109° 281 (109.5°)

 PCl5 molecule
The central atom P is having 5 bond pairs. Therefore the
molecule assume a triangular bipyramidal shape with bond
angles of 120° and 90°.
[The 3 P Cl bonds directed towards the corners of a triangle are called equatorial bonds
and the P Cl bonds projecting upwards and downwards are called axial bonds. Since the
e pairs in axial bonds face more repulsion, axial bonds are longer than equatorial bonds.
They can easily break to supply Cl atoms. Hence PCl5 is a highly reactive molecule]
SF6 Molecule
The central atom ‘S’ is having 6 bond pairs. Therefore the molecule
assumes an octahedral shape with a bond angle of 90°.
 NH3 Molecule
The central atom ‘N’ is having 3 bond pairs
and one lone pair. Since l.p- b.p repulsion is
greater than b.p-b.p repulsion, the molecule
assumes pyramidal shape with a bond angle of
107.
 H2O Molecule
The central atom ‘O’ is having 2 bond pairs
and 2 lone pairs. Since lone pair- lone pair
repulsion is greater than lone pair – bond pair
repulsion, which is again greater than bond
pair- bond pair repulsion, the molecule
assumes a ‘v’ shape (bent shape) with an bond
angle of 104.5.
Hybridisation
The process of intermixing of atomic orbitals of different shapes and slightly
different energies to give an equal number of identical orbitals is called hybridisation.

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Types of hybridisation
 sp hybridisation
Here one s and one p orbital take part in hybridisation to
produce two sp hybrid orbitals with 50% s character and
50% p character.
The 2 hybrid orbitals will get arranged in space in opposite directions imparting a linear
shape to the molecule formed. (One hybrid orbital will be having a big lobe and a small
lobe )
Formation of BeF2 Molecule
E.C of Be is 1s2 2s2. During the formation of BeF2 molecule, the configuration of Be
becomes 1s2 2s1 2px1 half filled 2s and 2px orbitals undergoes sp hybridisation to produce
two hybrid orbitals. These hybrid orbitals then overlap with half filled 2pz orbitals of two
fluorine atoms to produce BeF2 molecule with linear shape and bond angle of 180.

sp2 hybridisation
One s and two p orbitals undergo hybridisation to produce
3sp2 hybrid orbitals directed towards the corners of a triangle.
(33.5% s character and 66.6% p character)

BCl3 Molecule
E.C of B  1s2 2s2 2px1
During the formation of BCl3 molecule the configuration
becomes 1s2 2s1 2px1 2py1. Half filled 2s and 2p orbitals undergo
sp2 hybridisation produce three hybrid orbitals. These hybrid
orbitals then overlap with 3pz orbitals of 3 chlorine atoms to
produce BCl3 molecule with triangular planar shape with a bond
angle of 120.
sp3 hybridisation
One s and three p orbitals undergo hybridisation to produce
4 hybrid orbitals directed towards the corners of
a tetrahedron (25% s character, 75% p character).
Formation of CH4 molecule
E.C of C is 1s2 2s2 2px1 2py1 during the formation
of CH4 molecule, the configuration becomes 1s2
2s1 2px1 2py1 2pz1 half filled one s and three p
orbitals undergo sp3 hybridisation to produce 4
hybrid orbitals.

These hybrid orbitals then overlap with s orbitals of 4 hydrogen atoms to produce CH4
molecule with tetra headral shape and with bond angle of 109.5.

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NH3 molecule
E.C of N is 1s2 2s2 2px1 2py1 2pz1 filled 2s orbital and half filled 2p orbitals under go sp3
hybridisation to produce 4 hybrid orbitals. One of the hybrid orbitals will be carrying the
lone pair and the remaining hybrid orbitals overlap with half filled 1s
orbitals of hydrogen atoms to produce NH3
molecule. Due to the presence of a lone pair
this molecule will be having pyramidal shape
with a bond angle of 107.
H2O molecule
E.C. of O is 1s2 2s2 2px2 2py1 2pz1 filled 2s and 2px and half filled 2py
and 2pz undergo sp3 hybridisation to produce 4 hybrid orbitals. Two
hybrid orbitals carry lone pairs and the remaining hybrid orbitals
overlap with 1s orbitals of hydrogen atoms to produce H2O molecule.
Due to the presence of 2 lone pairs the molecule will be having bent
shape with a bond angle of 104.5.
C2H6 (Ethane)
During the formation of C2H6, carbon assumes the configuration 1s2 2s1 2px1 2py1 2pz1 .
Half filled 2s and 2p orbitals under go sp3 hybridisation. A hybrid orbital on the Ist carbon
overlaps with a hybrid orbital on the 2nd carbon to produce C  C  bond. The remaining
hybrid orbitals overlap with half filled 1s orbitals of hydrogen atoms to produce C2H6
molecule.

C2H4 (Ethene, Ethylene)

During the formation of C2H4, carbon assumes the configuration 1s2 2s1 2px1 2py1 2pz1.
Half filled 2s and 2px and 2py orbitals undergo sp2 hybridisation produce 3 hybrid orbitals
on each carbon. A hybrid orbitals on the Ist carbon overlaps with a hybrid orbitals on the
2nd carbon to produce C C  bond. The remaining hybrid orbitals overlap with 1s orbital
of hydrogen atom. The unhybridised 2pz orbitals on each carbon overlap side wise to
form C C  bond.

C2H2 (Ethyne, Acetylene)

During the formation of C2H2 molecule, C assumes the configuration 1s2 2s1 2px1 2py1
2pz1. Half filled 2s and 2px orbitals undergo sp hybridisation to produce 2 hybrid orbitals
on each carbon. A hybrid orbital on the Ist carbon overlaps with a hybrid orbital on the 2nd
carbon to produce C C  bond.
The remaining hybrid orbitals overlap with 1s orbital of
hydrogen atom. The unhybridised 2py and 2pz orbitals
on each carbon overlap sidewise to form C C  bond.
Note : C C (single bond length) – 154 pm

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C = C (double bond length) – 134 pm

C  C (triple bond length) – 128 pm
 PCl5
During the formation of PCl5(P, Z =15) the P assumes a configuration of 1s2 2s2 2p6 3s1
3px1 3py1 3pz1 3dz21. Half filled 3s and 3p and 3d orbitals undergo sp3d
hybridisation to produce 5 hybrid orbitals. These
hybrid orbitals then overlap with half filled 3pz
orbitals of Cl atoms to produce PCl5 molecule with
trigonal bipyramidal shape with bond angles 120
and 90.
 SF6
E.C of S = 1s2 2s2 2p6 3s2 3px2 3py1 3pz1 . During the formation of SF6 molecule the s
assumes a configuration of 1s2 2s2 2p6 3s1 3px1 3py1 3pz1 3dz21 3dx2-y21.
Half filled 3s, 3p and 3d orbitals undergo sp3d2
hybridisation to produce 6 hybrid orbitals. These
hybrid orbitals then overlap with the half filled 2pz
orbitals of F atoms to produce SF6 molecule with
octahedral shape and a bond angle of 90.
Molecular orbital theory (MOT)
Energy level diagram
Various molecular orbitals can be arranged in the order of their energy as given below.

Various MO’s can be arranged in the order of their energies as;

1s < *1s < 2s < *2s <  2pz < 2px =  2py < *2px = *2py < * 2pz
In the case of certain molecules (Li2, C2, N2) the order of energies of MO’s is
1s < *1s < 2s < *2s <  2px =  2py <  2pz < *2px = *2py < * 2pz
Bond order
It is half of the difference between Nb and Na

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Nb  Na
Bond order =
2
The following information’s are obtained from bond order
 If bond order is positive, the molecule will be stable. If it is zero or negative, the
molecule will be unstable.
 Bond order = number of bonds  Bond order  stability
1
 Bond order  bond dissociation energy  Bond order 
bond length
 N2 Molecule
 Number of e s = 14

 E.C   1s2 *1s2 2s2 *2s2 2px2 2py2 2pz2

 Magnetic behaviour diamagnetic
10  4
 Bond order =
2
6
= =3
2
 Number of bonds =3
 Stable molecule, Bond order is positive

 O2 molecule
 Number of e s = 16

 E.C   1s2 *1s2 2s2 *2s2 2pz2 2px2 2py2 *2px1 *2py1
 Magnetic behaviour  paramagnetic

10  6
 Bond order =
2
4
=2 =
2
 Number of bonds = 2
 Stable molecule Bond order is positive
 F2 molecule
 Number of e s = 18

 E.C   1s2 *1s2 2s2 *2s2 2pz2 2px2 2py2 *2px2 *2py2
 Magnetic behaviour  diamagnetic
10  8 2
 Bond order = = =1
2 2
 Number of bonds = 1
 The molecule is stable because the bond order is positive
Hydrogen bonding
When hydrogen is bonded to atoms of highly electronegative elements (F, O & N).
Hydrogen atom may carry slight positive charge and the electro negative atom may be

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carrying slight negative charge. Then there is a chance for a weak attractive forcebetween
positively charged H of 1 molecule and negatively charged atom of another molecule.
This attractive force is called hydrogen bonding.
Formation of hydrogen bonds in H2O, HF and NH3 can be represented as shown below.

Consequences of hydrogen bonding

 H2O, the hydride of group 16 element O exist as a liquid. Where as hydrides of
remaining elements in group 16 like, S, Se etc exist as gases.
 Ice floats over water. This is because the extent of hydrogen bonding is more in ice
and there is a cage like structure with lot of vacant space between molecules. When
ice gets converted into liquid water, some of these hydrogen bonds may break, water
molecules may come close and hence density of liquid water will be greater than
that of ice (water exhibits maximum density at 4C)
THERMODYNAMICS

System & Surroundings

Any part of the universe subjected to experimental study is called system and the rest of
the universe is called surroundings.
Systems can be classified into open, closed and isolated.
A system which can exchange matter as well as energy with surroundings is called open
system.
Eg : Hot water placed in an open vessel.
A system which can exchange only energy and not matter is called closed system.
Eg : Hot water placed in a closed vessel.
A system which cannot exchange energy as well as matter is called isolated system.
Eg : Hot water placed in a thermoflask.
Thermodynamic Properties
The properties of a system like T, P, V etc are called thermodynamic properties or
thermodynamic functions.
These properties are classified into state functions and path functions. Properties which
depend only on the initial and final state of systems are called state functions.
Eg : V, P, T, Internal energy etc.
Properties which depend on the path through which a process take place are called path
functions.
Eg: Heat and work
Ist Law of Thermodynamics
“Energy can neither be created nor be destroyed”
The first law can be mathematically represented as:
u = q + w q – heat w – work
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Extensive and Intensive Properties

Properties which depend on the amount of substance present are called extensive
properties.
Eg: mass, volume, Internal energy, enthalpy etc.
Properties which do not depend on the amount of substance are called intensive
properties.
Eg: Pressure, Temperature, Density, Surface tension etc.
Hess’s Law
If a reaction take place in a number of steps, over all enthalpy
change can be taken as equal to the sum of enthalpy changes for
individual steps. H1 = H2 + H3
Application
Hess’s law can be used to calculate enthalpy change of a reaction which cannot
be determined experimentally.
Spontaneity of a reaction
A process which can take place without the help of an external agency is called
spontaneous process.
A process accompanied by decrease in energy can became spontaneous.
Entropy (S)
It is the degree of disorder or randomness in a system.
A process accompanied by increase in entropy can become spontaneous. The change in
entropy, S in a process can be positive or negative.
S positive
Solid  liquid
Liquid  gas
Solid  gas
Dissolution of a solid in a liquid
C(s) + O2(g)  CO2 (g)
NH4Cl(s)  NH3(g) + HCl(g)
S negative
Liquid  solid
Gas  liquid
Gas  solid
NH3(g) + HCl(g)  NH4Cl(s)
2SO2(g) + O2(g)  2SO3(g)
[Number of molecules decreases]
q rev
Change in entropy, S = qrev – heat exchanged in a process
T
taking place reversibly.
T – temperature.
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Second Law of Thermodynamics

Entropy of the universe increases in the course of every spontaneous process.
For a spontaneous process, S universe should be positive.
S universe = S system + S surroundings
Gibb’s Energy (G) and Spontaneity
Gibb’s energy is an energy term related to enthalpy and entropy as: G = H – TS
For a process at constant T, G = H – TS

A process can become spontaneous when G is negative.

[This is the criteria for a process to become spontaneous].
It G is positive, the reaction will be non-spontaneous. If G = O, the process will be at
equilibrium.
Following are the conditions under which G become negative.
1) H = –ve, S = +ve
[Exothermic process accompanied by increase in entropy. Eg : Burning of fuels]
2) H = –ve, S = –ve
[Exothermic process accompanied by decrease in entropy] and when H > TS.
Such a process can become spontaneous at low Temperature.
Eg: Freezing of water – condensation of water, vapour etc.
3) H = +ve, S = +ve and when H < TS
[Endothermic process accompanied by increase in entropy]
Such a process can become spontaneous at high temperature
Eg : Melting of ice, Evaporation of liquid etc.

EQUILIBRIUM
Equilibrium constant
For the reversible reaction, aA + bB º cC + dD

Equilibrium constant, Kc =
CC Dd
Aa Bb
[ ] – molar concentration (moles/litre)

If the reaction is not at equilibrium, Qc =

CC Dd
Aa Bb
At equilibrium, Qc = Kc
If Qc < Kc, The reaction will proceeds in the forward direction.
If Qc > Kc, The reaction will proceeds in the backward direction.
N2 + 3H2 º 2NH3

Kc =
NH 3 2
N 2  H 2 3

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If the reaction involves solid substances, their concentrations need not be given in the
expression for Kc.
For the reaction, CaCO3(s)  CaO(s) + CO2(g)
Kc = [CO2]
Equilibrium Constant in terms of Partial Pressure
In the case of a reaction involving gaseous substances, partial pressure can be used instead
of molar concentration. Then the equilibrium constant is represented as Kp. for the
reaction.
N2(g) + 3H2(g) º 2NH3(g)
P 
NH 3
2

KP =
PN 2 (PH 2 ) 3

For the reaction, CaCO3(s) º CaO(s) + CO2(g)

Kp = PCO2
KP and Kc are related as: KP = Kc(RT)n
n = number of moles of gaseous products - number of moles of gaseous reactants.
Factors Affecting Equilibrium
 Le-Chatelier’s Principle
If a process at equilibrium is subjected to change in pressure, temperature or concentration
the system adjusts itself to cancel the effect of the change.
Effect of change in concentration (C)
If the concentration of reactants is increased, the rate of the forward reaction increases,
more reactants will get converted into products.
If the concentration of reactants is decreased, rate of backward reaction increases, product
will get converted into reactants.
If the concentration of products in increased, the rate of the backward reaction increases,
more products will get converted into reactants.
If the concentration of the product decreases, the forward reaction will increase. Then
more reactants will be converted into products.
Effect of change in pressure (P)
Pressure is having influence only in the case of a reaction having gaseous reactants.
(Pressure will not be having influence in the case of a reaction where no. of moles of
gaseous reactants is equal to no. of moles of gaseous products).
If we increase the pressure, the rate of the reaction accompanied by the decrease in no. of
moles increases.
In the reaction.
N2(g) + 3H2(g) º 2NH3(g)
On increasing the pressure, rate of forward reaction increases, more NH3 will get
produced. In Haber process for the manufacture of NH3, a pressure of around 300 atm is
used to increase the yield of NH3.

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In the reaction, N2(g) + O2(g)  2NO(g)

Pressure is not having any influence.
Effect of Temperature (T)
If we increase the temperature the rate of Endothermic reaction increases. [If in a
particular reaction, H negative, then forward reaction is exothermic and then backward
reaction will be endothermic. If H positive in a particular reaction, forward reaction is
endothermic and backward reaction is exothermic.]
In the reaction: N2 + 3H2 º 2NH3  H = -92.8 kJ/mol
Forward reaction - exothermic Backward reaction – endothermic
On increasing the temperature, the rate of Backward reaction increases. NH3 will
decompose. Therefore very high temperature is not suitable. But at very low temperature
there will be no reaction. Therefore an optimum temperature of 723 K is utilized in the
manufacture of NH3.
Effect of catalyst
In a reversible reaction, catalyst increases rates of Forward reaction and Backward
reaction to the same extent. Thus it helps in attaining the state of equilibrium quickly.
After attaining equilibrium, catalyst will not be having any influence. Iron is used as
catalyst in Haber process for the manufacture of NH3 V2O5 or platinum (Pt) is used as
catalysts in the contact process for the manufacture of H2SO4.
Acids & Bases
 Arrhenius Concept
Acid is a substance capable of supplying H+ ions in solution.
Base is a substance capable of supplying OH ions in solution.
Acids - HCl, HNO3, H2SO4,
Bases - NaOH, KOH etc...
 Lowry – Bronsted Concept
Acid is a substance which can donate H+ ion (Proton)
Base is a substance which can accept H+ ion (Proton)
HCl + H2O º H3O+ + Cl
Acid Base Acid Base

NH3 + H2O º NH4+ + OH

Base Acid Acid Base

An acid on donating a proton (H+) gets converted into a base, which is called conjugate
base. Base on accepting a proton gets converted into an acid, which is called conjugate
acid. An acid-base pair which differ in a proton is called conjugate acid –base pair.
Eg:- HCl – Cl NH3 – NH4+ H2O  OH H2O – H3O+
A substance which can donate as well as accept a proton is called ampoteric
substance.
Eg:- HSO4 HCO3 H2O.
Conjugate base of a weak acid will be strong and vice-versa. The same is applicable in the
case of a base and its conjugate acid. HCl is a strong acid its conjugate base Cl is weak
CH3COOH is a weak acid its conjugate base CH3COO is strong.
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Lewis concept
Acid is a substance capable of accepting a pair of e s.
Base is a substance capable of donating a pair of e s.
Eg: In the reaction between BF3 and NH3 to give an addition compound, BF3 acts as
Lewis acid and NH3 acts as Lewis base.
BF3 + NH3  H3N  BF3
Electron deficient molecules and positive ions behave as Lewis acids.
Eg:- BF3, BCl3, AlCl3, FeCl3, Mg2+, Ag+, H+
Electron rich molecules (central atom having
lone pair) and negative ions behave as Lewis
bases.
Eg:- NH3, H2O, OH, Cl , Br.
NH3 + H+  NH4+
Basic Acid

Structure of NH4+
Ionic Product of Water
The product of molar concentrations of Hydronium ion (H3O+) and Hydroxyl ion (OH) in
water or in any aqueous solution is called ionic product of water.
Ionic Product, Kw = [H3O+] [OH]
At 298 K, the value of ionic product is found to be 10-14 mol2L-2. It is a constant at a
particular temperature but its value increases with increase in temperature.
. Kw  temperature

pH Scale
pH is the negative logarithm of H3O+ ion concentration in any solution.
pH = log[H3O+]
For a neutral solution, [H3O+] = 107
Then,
pH = log 10 7 = (7  log 10)
= (7  1) = 7 (since log 10 =1)
For an acidic solution, [H3O+] > 10-7
Then, pH will be less than 7.
For a basic solution, pH > 7
Common ion effect
The suppression of degree of dissociation of a weak electrolyte on the addition of a strong
electrolyte having a common ion is called common ion effect.
Eg: degree of dissociation of NH4OH may suppressed on the addition of NH4Cl.
NH4OH º NH4+ + OH
NH4Cl  NH4+ + Cl

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CH3COOH º CH3COO + H+
CH3COONa  CH3COO + Na+
Buffer solution
Solutions which can resist changes in pH on the addition of small amounts of
acid/base are called buffer solutions.
Solutions of a mixture of weak acid and its salt with strong base can act as buffer.
Eg:- CH3COOH + CH3COONa
H2CO3 + NaHCO3
A solution of a mixture of weak base and its satt with a strong acid can also act as a
buffer.
Eg:- NH4OH + NH4Cl
Solubility Product
It is the product of molar concentrations of ions in the saturated solution of a
sparingly soluble salt in water.
Eg:- BaSO4(q) º Ba2+(aq) + SO42(aq)
2
Solubility product, Ksp = [Ba 2  ] [SO 4 ]

PbCl2(s) º Pb2+(aq) + 2 Cl (aq)

Ksp = [Pb2+] [Cl-]2

REDOX REACTIONS
Oxidation Number
It is the charge that can be assigned to an atom of an element in a compound if the
compound is assumed to be ionic.
Rules for assigning oxidation Number
1) Alkali metals (Li, Na, K...) always exhibit +1
2) Alkaline earth metals (Be, Mg, Ca.....) exhibit +2
3) Halogens (F, Cl, Br....) usually exhibit 1. F always exhibit 1 but other halogens
can also exhibit positive oxidation states.
4) Hydrogen usually exhibits +1. But in ionic hydrides (Hydrides with Alkali metals
and Alkaline earth metals), it exhibit 1. (Examples for ionic hydrides – NaH, KH,
CaH2 etc)
5) Oxygen usually exhibit 2. But in peroxides (Na2O2, H2O2, BaO2 etc) it is 1 and in
OF2, it is +2.
6) Oxidation number of a free element is zero.
7) Sum of oxidation numbers of various elements in a neutral molecule is equal to zero.
But in a charged species (NH4+, SO42, CO32, NO3...) sum of oxidation number =
Charge of the species.
Eg: NaCl Na  +1, Cl  1
MgO Mg  2+, O  2

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H2O2 H  +1, O  1
CaH2 Ca  2+, H  1
Oxidation & Reduction in terms of oxidation Number
During oxidation, oxidation number of an element increases.
During reduction, oxidation number of an element decreases.

ORGANIC CHEMISTRY SOME BASIC

PRINCIPLES AND TECHNIQUES

Nomenclature of Organic compounds

In the IUPAC system name of an organic compound consists of the following.
2 prefix + 1 prefix + root word + 1 suffix + 2 suffix
Root word indicates the number of carbon atoms in a compound.
No. of carbon atoms 1 2 3 4 5 6 7 8 9 10
Root word Meth Eth Prop But Pent Hex Hept Oct Non Dec
1 suffix is used to show whether the compound is saturated or unsaturated. If the
compound is saturated the 1 suffix used is ‘– ane’. If the compound is unsaturated with
double bond the 1 suffix used is ‘–ene’ and if the compound is unsaturated with triple
bond the 1 suffix used is ‘–yne’.
2 suffix is used to indicate the presence of functional group if any in the compound. 2
suffix used in the case of certain functional groups are given below.
Functional group – OH – CHO > CO – COOH
2 suffix used – ol – al – one – oic acid
1 prefix is used when the compound is cyclic. The 1 prefix used is ‘cyclo’.
2 prefix is used to show the presence of substituents like – X (halo), –NO2 (nitro) etc.
Naming of branched chain alkanes
Naming of a branched chain alkane involves the following steps.
 Select the longest possible carbon chain.
 Number the carbon atoms so that the carbon carrying the branch gets the lowest
possible number.
 Root world and suffix are given according to the number of carbon atoms in the
longest chain selected.
 The position and name of the branch is given as prefix.
 If there is more than one branch of the same kind the prefixes di, tri, tetra etc are
used.
 If there two or more different branches their names are given in the alphabetical
order.
 Names of alkyl groups are
– CH3 – methyl
CH3 – CH2 – – ethyl
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CH3 – CH2 – CH2– – n-propyl

1 – CH
CH3 – CH – iso propyl
3

1 2 3 4 5
CH3 – CH2 – CH – CH2 – CH3
|
CH3
3 – Methyl pentane

CH3 CH3
1 |2 3 4 3 |2 1
CH3  C CH3 CH3  CH  C CH3
| | |
CH3 CH3 CH3
2, 2, - Dimethyl propane 2, 2, 3 – Trimethyl butane

CH3  CH2  CH  CH2  CH CH3

| |
CH2  CH3 CH3
4 – Ethyl – 2- methyl hexane

Nomenclature of alkenes
 Select the longest possible carbon chain containing the double bond.
 Number the carbon atoms so that carbon carrying the double bond gets the lowest
possible number.
 Give root word and suffix (ene )
 If there is any branch its name and position is given as prefix
CH2 = CH2 CH3 – CH = CH2
Ethene Propene

CH3 – CH2 – CH = CH2 CH3 – CH = CH – CH3

1 – Butene OR But -1-ene 2 – Butene OR But-2-ene

Nomenclature of Alkynes
CH ≡ CH CH3 – C ≡ CH CH3 – CH2 – C ≡ CH
Ethyne Propyne 1 – Butyne OR But -1-yne

CH3 – C ≡ C – CH3
2 – Butyne OR But-2-yne

Nomenclature of organic compounds having functional groups.

 Select the longest – possible chain containing the functional group.
 Number the carbon atoms so that carbon carrying the functional group gets the
lowest possible number.
 Give root word and 1 suffix
 Add 2 suffix after replacing the ending – e of 1 suffix.
 Give the name and position of branch if any as prefix.
CH3OH CH3CH2OH CH3CH2CH2OH
Methanol Ethanol 1 – Propanol OR Propan-1-ol

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CH3 – CH – CH3 CH3 – CH2 – CH2 – CH – CH2 – CH3

| |
OH CH2 – OH
2 – Propanol OR Propan-2-ol 2 – Ethyl – 1 – pentanol OR 2-Ethylpentan-1-ol

CH3 – CH2 – CH = CH – CH2OH

Pent – 2 – ene – 1 – ol

HCHO CH3CHO CH3CH2CH2CHO

Methanal Ethanal Butanal

CH3 – CH = CH – CH2 – CHO

Pent – 3 – enal

CH3COCH3 CH3CH2COCH2CH3
Propanone Pentan – 3 – one

HCOOH CH3COOH
Methanoic acid Ethanoic acid

CH3CH2CH2COOH CH2 = CH – CH2 – COOH

Butanoic acid But – 3 – enoic acid

Isomerism
The phenomenon of existence of two or more compounds possessing the same molecular
formula but different properties is known as isomerism. Isomerism can be classified into
the following.
Isomerism

Structural isomerism Stereoisomerism

Chain Position Functional Metamerism

Isomerism Isomerism Isomerism
Geometrical Optical
Isomerism Isomerism
Chain Isomerism
Chain isomers are those in which there is a difference in the nature of carbon chain.
n-pentane, isopentane and neopentane are chain isomers with the same formula C5H12
CH3 CH3
| |
CH3 CH2 CH2 CH2 CH3 CH3 – CH – CH2 – CH3 CH3 – C – CH3
n – pentane Isopentane (2 – methyl butane)
|
CH3
Neopentane (2, 2 – Dimethylpropane)

Position Isomers
Position isomers are those in which there is a difference in the position of a functional
group.
OH
|
CH3CH2CH2OH CH3 – CH – CH3
Propan – 1 – ol Propan – 2 – ol

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Functional Isomerism
Functional isomers are those in which there is a difference in the nature of the functional
group.
CH3 CH2 OH CH3 O CH3
Ethanol Dimethyl ether

(C2H6O) (C2H6O)

O
||
CH3 – C – CH3 CH3 CH2 CHO
Propanone Propanal

(C3H6O) (C3H6O)

Stereoisomerism
Stereo isomers are those in which there is a difference in the spatial arrangement of atoms
or groups. It is classified into geometrical isomerism and optical isomerism. In
geometrical isomerism there is a difference in the spatial arrangement of groups about a
carbon – carbon double bond.

Cis – 2 – butene Trans – 2 – butene

Nucleophiles and electrophiles

Negatively charged species and electron rich molecules (molecules having lone pairs on
central atom) seeking a positive centre are called nucleophiles.
 

Eg : -  OH,  NH2 , CN, H2O , NH3 etc.
Positively charged species and electron deficient molecules (central atom having less than
eight electrons in the valence shell) seeking a negative centre in a molecule are called
electrophiles.
+ + +
Eg : -  NO2, Cl , H , BCl3 , AlCl3 etc.
Qualitative Analysis of Organic Compounds
1. Detection of Carbon and Hydrogen
A sample of compound is heated with copper (II) oxide. C in the compound gets
converted into CO2 and H into H2O. Formation of CO2 is tested with lime water
(lime water turns milky) and H2O with anhydrous CuSO4 (anhydrous CuSO4 turns
blue)
2. Detection of Nitrogen, Sulphur, halogens and Phosphorus (Lassaigne’s Test)
A sample of organic compound is fused with sodium metal in small glass tube and
the red hot tube is suddenly plunged into water taken in a beaker. The tube breaks
and the contents get dissolved in water the solution thus obtained is called sodium
fusion extract or Lawaigne’s extract. Nitrogen in the compound gets converted into
NaCN, Sulphur as Na2S halogens as sodium halides and phosphorus as sodium
phosphate.

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a) Test for Nitrogen

Sodium fusion extract is heated with iron (II) sulphate and then it is treated with
conc. H2SO4 and then formation of a blue colour (Prussion blue) indicates the
presence of nitrogen. (Sodium cyanide in the sodium fusion extract reacts with iron
(II) sulphate to form sodium hexacyanoferrate (II). Concentrated H2SO4 oxidizes a
part of iron (II) sulphate into iron (III), sulphate which reacts with sodium
hexacyanoferrate to produce iron (III), hexacyanoferrate (II) (ferriferro cyanide)
which is prussion blue in colour.)
6 NaCN + FeSO4 → Na4[Fe(CN)6] + Na2SO4
3Na4[Fe(CN)6] + 2Fe(SO4)3 → Fe4[Fe(CN)6]3 + 6Na2SO4
b) Test for sulphur
The sodium fusion extract containing sodium sulphide is acidified with acetic acid
and lead acetate is added. A black precipitate of lead sulphide indicates the presence
of sulphur.
c) Test for Halogens
Sodium fusion extract containing sodium halides is acidified with nitric acid and
then treated with silver nitrate. A white precipitate (AgCl) soluble in ammonium
hydroxide shows the presence of chlorine, pale yellow precipitate (AgBr) partially
soluble in ammonium hydroxide shows the presence of bromine and yellow
precipitate (AgI) insoluble in ammonium hydroxide shows the presence of iodine.
HYDRO CARBONS
Alkanes
 Methods of Preparation
1. From unsaturated hydrocarbons (Hydrogenation)
When an alkene or alkyne is treated with H2 in presence of Pt, Pd or Ni alkane will
be obtained.
CH2 = CH2 + H2 
Pd
CH3 – CH3
Ethene
(ethylene)

CH3 – C ≡ CH + 2H2 

Ni
CH3 CH2 CH3
Propyne Propane

2. From alkyl halides

i) By reduction
When an alkyl halide is treated with zinc and dilute hydrochloric acid alkane will be
obtained.
CH3 CH2Cl + H2   CH3 CH3 + HCl
Zn / HCl

Chloro ethane

ii) By Wurtz reaction

When an alkyl halide is treated with sodium metal in ether medium an alkane will be
obtained. (Here alkane obtained will be having double the number of carbon atoms
than in the alkyl halide)
2CH3 Br + 2Na ether
  CH3 – CH3 + 2NaBr
Bronometane Ethane

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2CH3 CH2Cl + 2Na ether

  CH3 CH2 CH2 CH3 + 2NaCl
Chloro ethane Butane

3) From Carboxylic acids

i) By soda lime decarboxylation
When sodium salt of a carboxylic acid is heated with soda lime (a mixture of
NaOH and CaO) an alkane will be obtained (Here the alkane obtained will be having
one carbon atom less than that in the starting carboxylic acid)
CH3 COO Na + NaOH CaO 
 CH4 + Na2CO3
sodium salt of ethanoic acid  methane

CH3CH2COONa + NaOH CaO 

 CH3 CH3 + Na2CO3
sodium salt of propanoic acid  Ethane

ii) Kolbe’s electrolytic method

An aqueous solution of sodium or potassium salt of a carboxylic acid on
electrolysis gives alkane containing even number of carbon atoms.
2CH3 COONa + 2H2O electrolys
  is
 CH3  CH3 + 2CO2 + 2NaOH + H2
Chemical Properties
1. Isomerisation
When a straight chain alkane is heated in the presence of anhydrous AlCl3 and HCl gas
isomerisation take place leading to the formation of branched chain alkanes
CH3 (CH2)4CH3   CH3 – CH – (CH2)2 – CH3
AlCl3 / HCl

n – Hexane  |
CH3
2 – Methylpentane

2. Aromatization
When a straight chain alkane is heated under high pressure in the presence in the
pressence of a catalyst like V2O5 it gets converted into an aromatic hydrocarbon.
CH3 (CH2)4CH3 V

2O5

773 K/20 atm

benzene

CH3 (CH2)5 CH3 V


2O5

773 K/20 atm

Toluene

3. Pyrolysis
When a higher alkane is heated in the presence of a catalyst decomposition of higher
alkanes into lower alkanes take place. This is called pyrolysis.
Eg: C6 H14 773
  K
 C4H8 +C2H6
Hexane butene ethane

Pyrolysis is utilized for converting higher alkanes in lubricant oil or diesel oil into lower
alkanes of petrol.
Conformations
The instantaneous spatial arrangements possible for an alkane due to the free rotation of
atoms or groups about a carbon – carbon single bond.

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Conformations of ethane can be represented using either sawhorse projections or Newman

projections.
Sawhorse Projections

Ecclipsed Staggered

Newman Projections

Ecclipsed Staggered

Alkenes
Methods of Preparation
From alkyl halide
When an alkyl halide is subjected to dehydrohalogenation by treating with alcoholic KOH
an alkene will be obtained.
CH3CH2Cl Alc
KOH
 CH2 = CH2 + HCl
Chloro ethane Ethene

Cl
|
CH3 CH2 – CH – CH3 Alc
KOH
 CH3 – CH = CH – CH3 + HCl
2 – Chlorobutane 2 – Butene

(When an alkyl halide is subjected to dehydro halogenation the more substituted alkene
will be obtained as per saytzeff rule) when 2 – chlorobutane is subjected to dehydro
halogenation 2 – butene is the major product and not 1 – butene.
Chemical Properties
1. Addition of hydrogen halide
Hydrogen halides add up to alkenes to form alkyl halides. The order of reactivity of
hydrogen halides is HI > HBr > HCl
CH2 = CH2 + HBr → CH3 CH2Br
Addition of hydrogen halide into an unsymmetrical alkene take place according to
Markonikov rule. This rule states that when an unsymmetrical reagent is added to an
unsymmetrical alkene positive part of the reagent goes to the carbon having more number
of hydrogen atoms.
Br

CH3 – CH = CH2 + HBr → CH3 – CH – CH3
Propene 2 – Bromopropane

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Anti Markovnikov addition or Peroxide effect or Kharasch effect

In the presence of a peroxide like benzoyl peroxide addition of HBr to an unsymmetrical
alkene take place contrary to Markovnikov rule.
CH3 – CH = CH2 + HBr    CH3 – CH2 – CH2Br
( C6 H 5COO ) 2

Propene 1- Bromopropane

2. Ozonolysis
When an alkene is treated with ozone an ozonide will be obtained which on treating with
water in presence of zinc an aldehyde or ketone will be obtained.
 Zn
CH2 = CH2 + O3 → H2 O
 2 HCHO
Ethene Methanol

2 O  Zn
CH3 – CH = CH2 + O3 → CH3  H  CH3 CHO + HCHO
Propene Ethanal Methanal

 Zn
CH3 – CH = CH – CH3 + O3 → CH3   CH3 H2O
 2CH3 CHO
2 – Butene Ethanal

CH3 O
 ||
H OZn
CH3 – C =CH–CH3 + O3 →CH3  CH3  CH3–C –CH3+ CH3CHO
2

2 – Methyl – but – 2 – ene Propanene Ethanal

Alkynes
Alkynes are unsaturated hydrocarbons having carbon - carbon triple bond.
Preparation
1. From calcium carbide
Ethyne can be prepared by the hydrolysis of calcium carbide.
CaC2 + 2H2O → Ca(OH)2 + C2H2
Properties
1) Acidic character of alkyne
1 – Alkynes like ethyne show acidic nature. The – C – H bond in ethyne is polar because
here hydrogen is attached to an sp hybridised carbon. As sp hybrid orbital will be having
50% s – character. sp hybridised carbon will be having higher electro negativity. It will
attract the shared pair of electron in the – C – H bond towards its side making the – C – H
bond polar which can thus break to supply H+ ion. Because of acidic nature 1 – alkynes
like ethyne react with sodium metal or sodamide to produce sodium salts.
HC  CH + Na → HC  CNa + ½ H2
Sodium ethynide

CH3 – C  CH + Na → CH3 – C  CNa + ½ H2

Sodium Propynide

Alkanes, alkenes and alkynes follow the following trend in their acidic behaviour.
HC  CH > CH2 = CH2 > CH3 – CH3

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2) Addition of water
When alkyne is subjected to hydration by treating with dilute sulphuric acid in the
presence of mercuric sulphate either an aldehyde or ketone will be the product.
HC  CH + H2O dil
H  CH2 = CH – OH rearranges
SO 2
  CH3CHO
4

Ethyne HgSO4 Ethanal

O
||
CH3 – C  CH + H2O HgSO  CH3 –C – CH3
dil H SO 2 4
4
Propyne Propanone

3) Polymerisation
When ethyne gas is passed through red hot iron tube at 873 K three molecules of ethyne
combine to give benzene.
3HC  CH red
hotiron
tube

973K
Preparation of Benzene
1. From ethyne
When ethyne is passed through a hot iron tube at a temperature of 873 K gives benzene.

3 CH  CH hotirontub
 e
ethyne 873 K

benzene

2. From aromatic acids

Sodium salt of benzoic acid on
heating with sodalime gives
benzene.
Sodium benzoate benzene

3. From phenol
When phenol is heated with
zinc dust benzene is obtained.

 Chemical properties
(i) Friedel – Crafts alkylation reaction
When benzene is treated with an alkyl halide in the presence of anhydrous aluminium
chloride, alkyl benzene is formed.

(ii) Friedel – Craft acylation

When benzene is treated with an acid chloride or
acid anhydride in the presence of anhydrous
AlCl3 acyl benzene (aromatic ketone is formed.

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