ISOMERISM

Compounds having similar molecular formula but having different properties.

ISOMERISM

Structural Isomerism Stereo Isomerism

Geometrical
Chain Positional Tautomerism Functional Metamerism Optical
Isomerism
Isomerism Isomerismn Isomerism
Isomerism (Cis-trans)
STRUCTURAL ISOMERISM
Compounds having same molecular formula but having different structural formula.

a) Chain Isomerism: Compound having same molecular formula but having diferent carbon
chain.
CsH12
i )CH CH2 - CH2 -CH2 -CH Pentane (n- pentane)
i)CH-CH-CH2-CH3 2-methyl butane (lso-pentane)

CH3
ii) CH
CH-C-CH 2,2-dimethyl propane (neo-pentane)

CH
CaH1o
i) CH-CH2 -CH2-CH Butane (n-butane)
ii) CH3-CH- CH3 Isobutane (2-methyl propane)

CH3
b) Postion Isomerism: Compounds having same molecular formula but having different

position of functional group or multiple bond.

CHO
CH3-CH - CH2 -0H Propan -1-ol

CH-CH CH3 Propan-2ol

OH
CaHs
CH-CH- C H = CH2 But-1-ene
CH3-CH= CH CH3 But-2-ene
molecular formula but having different
)Functional Isomerism: Compounds having same
functional groups.
CaH.O
CH-CH-OH Ethanol (Ethyl alcohol)
CH,-0-CH3 Methoxy methane (Dimethyl ether)
Compounds having same molecular formmula but having different alkyl
d Metamerism:
groups on either side of the functional group.
Eg: CH-CH, - 0 - CH - CH, Diethyl ether or Ethoxy ethane (IUPAC)
CH-CH2 -CH2 -0- CH3 Methyl propyl ether or Methoxy propane.
Metamerism mainly occurs in ethers as well as in substituted amines.
Substituted Amines
CaHN
CH-CH- NH - CH - CH, Diethylamine (N- Ethyl ethanamine)
CH-CH CH - NH - CH Methyl propyl amine (N- Methyl propanamine)

2 3 45
C H - C H - C -CH, - CH,
54321
CH CH - CH-C - CH

Pentan 3 - one Pentan 2 one

They are position isomers and not metamers

e)Tautomerism
Some molecules can exist in more than one interconvertable forms.This is known as
tautomerism.For example: keto-enol tautomerism.

CHs C CHs CH:=C -CH3

OH
STEREO IsOMERISM4
Compounds having same molecular formula and structural formula but having different
spacial arrangement.
It is of 2 types: - Geometrical and Optical isomerism.

REACTION MECHANISM
The detailed description of a chemical reaction is called reaction mechanism. The study of
reaction mechanism involves:-
i) Electron displacement effects
ii) Attacking agents
ii) Bond Cleavage
iv) Reaction Intermediates
v) Types of reaction.

ELECTRON DISPLACEMENT EFFECTS

The movement of electrons taking place inside a molecule is called electron displacement
effects. It is of 2 types
i) Permanent Effects: It is always present in the molecule.
ii) Temporary Effects: It takes place in presence of an attacking agent.
The important electron displacement effects are:
i) Inductive effect (1 - effect)
ii) Mesomeric effect (M - effect) Permanent effects
ii) Hyperconjugation effect
iv) Electromeric effect Temporary effect.

2
INDUCTIVEEFFECT(I- effect)
I t is a permanent effect.
. I t involves the movement of sigma electrons, when an atom or a group of atoms
having different electronegativity than the carbon is attached to the carbon chain.
It is of two types:-
a)-I effect :- Here, electron movement takes place from carbon chain to the
functional group.
886 8t lst
-C -C-C--X

Examples of groups showing this effect:

N-N0,> -CN > -c0OH > -F> -Cl > -Br > -I>-0H > -0CH, > -CsH5
b) +I effect:- Here the e"movement takes place from functional group to carbon
chain.
C-C-C-+Y

Examples of group showing this effect:

CH

C-CHs> CH CH>-CH:-CH:>-CH
CH CH
RESONANCE 3 Alkyi group 2 Alkyl group 1 Alkyl group methyl group
A Molecule can be represented by more than one structure, butthe actual structure is
none of them. The actual structure is a intermediate between these different structures.
This phenomenon is known as Resonance
The individual structures are called canonical structures or resonating struetures and
the intermediate is known as Resonance Hybrid.
Eg:- Benzene (CsH6)
Benzene molecule can be represented by the following canonical structures.
H H H

H C-H H-C H-c

C-H
H- - H H-C H
H-C.. - H

H H H

Resonance Hybrid

Canonical Structures

In these canonical structures, there are single bond and double bond between the carbon
atom. The bond length in C-C bond is 154 pm and the bond
length in C C is 134 pm, =

but the actual bond length in benzene is 139 pm. Therefore, the actual structures of
benzene is an intermediate between the canonical structures. This is called resonance
hybrid.

3
Resonance Energy: Resonance hybrid has less energy than any of the canonical structures.
The difference in energy between the resonance hybrid and most stable canonical structure is

called resonance energy.

Resonance Structures of Nitro Methane( NO2

0:
CHs-N CH- CH N
0
Resonance Hybrid

Canonical Structures

Resonance Structures of Acetate lon |CH3-cOO]

0:

CH C CHs- C = CHs-C.()
*o
Resonance Hybrid

Canonical Structures

Stability of different resonance structures

Among different resonance structures, the most stable structure is
i) One which has more number of covalent bonds.
ii) All the atom with octet of electrons.
ii) Less separation of opposite charges.
iv) Negative charge on more electro-negative atom.

MESOMERIC EFFECT(M-effect or Resonance effect)

It is a permanent effect.
It is defined as the polarity produced in a molecule by the interaction of two n bonds or
between a n bond and a lone pair.
It operates only in a conjugated system alternate single and double bonds)
Therefore, this effect is also called conjugative effect.
As a result of mesomeric effect, a no. of resonance structures are possible. It is of 2
types, +M effectand-M effect.
+Meffect |+R effectl
Here, electron movement takes place from functional group to carbon chain.
.The group showing +M effect are-OH,-OR, -NH:.-Cl etc.

+Meffect in Aniline.
NH2

4
+M effectin Phenol
'OH OH OH :OH
r:OH

+M effect in Chlorobenzene
:Cl:
:C C

- Meffect -R effectl
Here electron displacement takes place from carbon chain to functional group. Groups
showing-M effect are -NO2,-COOH,-CHO, -CN etc
- Meffect in Nitrobenzene
.

(+)

HYPERCONJUGATION (She- Nattan eflect/Ne bend Aesonance

I t is a permanent effect.
Here C-H sigma bond becomes C=C rbond.
Hyperconjugation is the delocalisation of sigma electrons of a C-H bond :o adjacent
atom of unsaturated system. (C-C) or to an atom with empty P-orbitals.
.It is present in (i) carbocation (i) alkene (ii) alkyl benzene.
As a result of hyperconjugation a no. of resonance structures are possible. In these
resonance structures there is no bond between C and H. Therefore, hypercorjugation is
also known as no-bond resonance.

Hyper conjugation in Ethyl Carbocation[CH3-CHZ]

H H H

H-CCH: >H-C=CH:+>H C=CH: H-C=CH:

H H
114 Juo st
Orbital diagramshowinghyperconjugation inethylearbocation
(
- C

By using hyper conjugation we can explain the stability of carbocations.

CH
CHCH-CH<CH -CH <CH -C
Methy
carbocabon 1 Carbocadon CH
2 Carbocabon
CH
3 Carbocation

Greater the number of alkyl groups attached to the positively charged carbon greater the
hyper conjugation and greater the stability. [Stability of carb0-cation can also be explained by
+I effect).

Hyper conjugation in Alkene

Eg: Propene
CH3-CH = CH2

H H H

H-CCHcGHH-C =CH-C:H c=CH-CHH-C=CH-CH

H H

Orbital diagram showinghyper conjugation in Propene

H

H-C -CH-CH
ELECTROMERICEFFECT
I t is a temporary effect.
I t is the shifting ofne" to one ofthe atoms in the presence of an attacking agent. It is
of 2 types
i) +E effect ii) - E effect

+E effect
Here the attacking agent gets attached to the atom to which the electrons are shiftecl.

- E effect
Here the attacking agent gets attached to the atom from which the electrons are removed.

CN -C
CN
6
BONDCLEAVAGE
A covalent bond can break in two different ways:
(i) Homolytic cleavage (i) Heterolytic cleavage

Homolytic Cleavage
Inhomolytic cleavage, each bonded atom gets one c from the shared pair of e.

Cl-Cl Cl+Cl
Here, the products are free radicles. Homolytic cleavage is represented by fish hook
arrow.[I
.Homolytic cleavage is favoured by
i) non-polar nature of bond.
ii) high temperature and presence of radiation.
Heterolytie cleavage
In heterolytic cleavage both the shared electrons are taken away by one of th: atoms.
H

H-C- l>H-c+
H
Here, the products formed are positive and negative ions. It is favoured by:-
i) Polar nature of bond.
ii) Presence of polar solvent.

REACTION INTERMEDIATES
These are species formed during the course of a chemical reaction. They ar
temporary in nature.
They are lost before the reaction is complete.
They are of 4 types.
i) Carbocation ii) Carbanion ii) Free radicles iv) Carbenes.
Carbocation
These are species in which carbon atom has a positive charge.
They are formed as a result of heterolytic cleavage.
H H

CH- l>CH- +C

Different types of carbocation are:

i) Primary carbocation (1°) ii) Secondary Carbocation (2°)
ii) Tertiary carbocation (3°) iv) Methyl carbocation.

Stability of different carbocations are in the order: CH

CH CH-
(19
CH: CH-CH<CH:-C
Methyl
CHs CHs

The Stability of carbocation is explained on the basis of hyper conjugation and + I effect.
Structure of carbocation
The positively charged carbon in carbocation is sp' hybridised. Therefore it has a
triagonal planar shape.

Carbanions
These are species in which carbon atom has negative charge.
They are formed as a result of heterolytic cleavage. H

CHs C-Z >Cly -C: Z

Different types of carbanions are:-
i) Methyl ii) Primary ii) Secondary iv) Tertiary

Stability of carbanions are in the order:

CHs
CH CH H: > CHs-H >CH»-¢:
Mehy (19
CH CH
(3)

The Stability is explained on the basis of +I effect of alkyl groups.

Structure of Carbanions
The negatively charged carbon in carbanions is sp' hybridised.
Therefore, it has a pyramidal shape.Somecarbanions are also
stabilised by resonance. Eg. Allylic and Benzyliccarbanions.

AllicCarbanions
CH = CH- H: CH:-CH = CH2

Free Radicals
These are reaction intermediates in which H
an atom has an unpaired electron. If the A
unpaired electron is present in a carbon
atom, they are called alkyl free radicals.
CHs-C CH-C X
H
They are formed as a result of homolytic
Free radicals
cleavage.
There are different types of free radicals:- Methyl, Primary, Secondary, Tertiary.
Their stability is in the order:-
CH
CH< CHs -CH:<CH-CH CHs-¢ <

Methyt 1
CH CHs
(2) (3)
 and+ I effect.
Stability is explained by Hyper conjugation
Structure
The exact hybridisation of carbon having an
unpaired eis not exactly predictable.
An alkyl free radicle is either pyramidal or
sp- Tnagonal planar Sp' Pyrunidal
planar as shown below:

ATTACKINGAGENTS the
The organic reaction usually proceeds by the attack of certain active species or

reactant molecules. These are called attacking agents.

It is of 3 types:
i) Nucleophiles i) Electrophiles ii) Free radicals

Nucleophiles
They are negatively charged or neutral species which are capables are donating a pair
of electron to some other molecules.
.They attack e deficient centres.
.They can act as Lewis base.
Examples of charged nucleophiles: CF, Br, OH, CN", R-CO0.

Examples of neutral nucleophiles: NHg, H0:, R- OH, . . .

Electrophiles
These are neutral or positively charged species which are capable of accepting a pair
of e from some other molecules.
They attack e rich centres.

.They can act as Lewisacids.

Examples of charged electrophiles: H', NO:, NO',...

TYPES OF REACTIONN
An organic reaction can be classified into 4 types:
i) Substitution reaction ii) Addition reaction
ii) Elimination reaction iv) Rearrangement reaction

Substitution Reaction The

Here, an atom or a group of atoms in a molecule is substituted by another.
be nucleophilic, electrophilic or a free radical type. Therefore,
substituting species may
substitution reaction may be classified into:-
ii) Free radical Substitution
i) Nucleophilic Substitution ii) Electrophilic Substitution

Nucleophilic Substitution
Here, aweaker nucleophile is replaced by a stronger nucleophile.
Eg:- Hydrolysis of an alkyl halide with an aqueous base.
CH3 CH2 -Cl + Na0H CH3-CH2 -0H + NaCl
OH.
In this reaction, the weaker nucleophile C is replaced by stronger nucleophile

Electrophilic Substitution ele cthophile.

This type reaction
Here, a weaker electrophile is replaced by a stronger nucleophile. or

occurs mainly in aromatic systems.

9
Eg: Benzene is an e" rich system and it is attacked by electrophile to give the subst ituted
product.

+E + H
Nitration of Benzene is a typical electrophilic substitution reaction:
NO:

H:SO4
+HNO3 +H:0

Here NO2' Nitrobenzene

acts as electrophile.
Nitrating mixture - HNO; + H2SO4

H2SO4
O-NOH NO: + H:0+H:SO

Free radical Substitution

Here, one free radicle is replaced by another free radical. These reactions are initiated
by sunlight, oxygen. peroxides, other free radicals etc.
Eg: Halogenation of an alkane in presence of sunlight.

Cl
CH-ChCH-cI CHs-CHCICH:C
Di Cn, CHCI,C ccCl
Methane -HCI Mono -HCI ChioroformHC Carboa
Chloromethane Choromethane tetrac hlonide

The reaction takes place in three steps:-

Initiation

Propogation
H- i H1- HC

CH +I- CHs-ClCl
Termination
CI-CC:
CHs+ClCHs -C1
CHs+CH CH:-CH
Addition Reaction
These are reactions which involve combination of2 molecules to form a single molecule.
These reaction are given by molecules containing multiple bonds.
Ni
Eg: CH = CH + H2 CH-CH CH. = CH + HBr CH, -CH
Ethene Ethane
Ethene Ethyl Bromide
Br

10
Addition reactions may be:-
i) Nucleophilic addition ii) Electrophilic addition ii) Free radical addition

i) Nucleophilic Addition The

of the
Here, a nucleophile initiates the reaction, the n e" are then shifted
to one atom.

reaction is then completed by the addition of an electrophile.

+Nu

Nu Nu E

Eg: Base catalysed addition of HCN to Acetone

H-CN Base H' +CN
CHs CHs
CHs
= 0 +CN- CH-Ç-0- CHs-C-OH
Electtophie CN
Nucleophikc CN
CH3 Acetone

ii) Electrophilic Addition

Here, the reaction is initiated by an electrophile.
Then, n eof the multiple bond get
shifted to one of the atom. The reaction
is then completed by a nucleophile.
Eg: Addition of hydrogen halide to an
alkene.
CH2= CH2 +HCl CH-CH2 -Cl
Mechanism
H Base H+Cl

CH=CH +H CH-CHs + CH-CH

Cl
Ethyd chloride
Another example:-
CH CH = CH2 + HCl CH, - CH CH3

Propene CL
2-chloropropane

Markonikov' S rule
When a hydrogen halide is added to an unsymmetrical alkene, the -ve part of the
addendum adds to the carbon containing less no: of hydrogen atoms.

Mechanism
H-CI H+Cl
CH)-CH- CH
(2 carbocation)More stable
CH-CH=CH:+H
CH3-CH:-CH:
(1 carbocation) less stable
 The secondary carbocation is more
stable. Therefore, it is mainly formed. CHs-CH-CHs+CI CH-CH-CHs
Then it is attacked by Cl. (2 carbocaion) CI
(2 chlorcpropane)
iii)Free Radical Addition
The addition reaction which involve the initial attack by a free radical is called free
radical addition reaction.
Eg: Addition of HBr to an alkene
C H - C H = CH2 + HBr Benzoyl peroxide
CH-CH:-CH:
in presence of a peroxide.
(Benzoyl peroxide) Br

Anti -Markonikov's rule [peroxide effect or kharasch effect]

When HBr is added to an unsymmetrical alkene in the presence of peroxide the -ve part
of the addendum adds to the carbon
containing more no: of H atoms. This is not applicable
for HCl and HI.
Mechanismn
Initiation
R-0d-R R-0+R-
R-0+ HBr R- OH +Br

Propogation
(2 free radical) more stable
CHs-CH-CH:
CH -Br Br

CH-CH-H:
Br
(1° free radical) less stable

CH-CH CH:+ Á-B CHs-CH:-CH2+Br

Br Br
Termination
Br +Br Br2

Elimination Reaction
Here, two atoms or group of atoms are eliminated from a molecule to give the product.
Eliminations are classified as

i) g-Elimination Here, two atoms or groups are removed from the same carbon atorn. Here,
an electron deficient molecule is formed.
R R R

R-C1HR-¢ CI C
H R
Carben

12
i) B-ELIMINATION
Here, two atoms or groups are eliminated KOH
from adjacent positions CH:-CH-C1 CH=CH: + HCI
Ethene
Eg: Elimination reaction of an alkyl halide H
using alcoholic KOH. Ethyl chloride

ii) -ELIMINATION
Here, atoms or groups are removed from a position and Y position.
Eg: CH
Zn dust CH:
+ZnBr2
CH: CH: CH2- CH2
Br Br

1,3-Dibromopropane Cycopropane

Rearrangement Reaction.
This reaction involve the rearrangement of atoms within a molecule under suitable
conditions to form the product.
Eg
NHCNO-- HN-C -NH2
A
Ammonnm O
cyanate

Urea

13