FUNDAMENTAL CONCEPTS IN ORGANIC REACTION MECHANISM

Prepared and compiled by Bharti Kakkar

In organic reactions, the organic molecule undergoing the reaction is

called the substrate which reacts with the other reactant that is called the
attacking reagent to form one or more intermediate/s and finally the
product/s. Generally, the substrate is that molecule which provides carbon
to the new bond but if either the substrate or reagent can supply carbon
to the new bond, then the choice of substrate is arbitrary........The
molecule of our interest is the substrate.
𝑎𝑡𝑡𝑎𝑐𝑘𝑖𝑛𝑔 𝑟𝑒𝑎𝑔𝑒𝑛𝑡
Organic molecule(substrate) [intermediate]
products + by products.

Every reaction involves breaking of some old bonds and formation of

new bonds.

The detailed study of the stepwise description of a reaction ,

electron movement, energetic during bond cleavage and bond formation
and the rates of transformation of reactants into products(kinetics) is
referred to as reaction mechanism.

The knowledge of reaction mechanism helps in understanding of the

reactivity of organic compounds and determining strategies for their
synthesis.

FISSION OF A COVALENT BOND

A covalent bond can be cleaved or broken in two ways: homolytic

fission and heterolytic fission

1. HOMOLYTIC FISSION:
  In homolytic fission, the cleavage of covalent bond between
two atoms takes place in such a way that each bonded atom
retains one electron of the shared pair.
 This is a symmetrical fission and leads to the formation of
neutral apecies which could be atoms or group of atoms
having unpaired electrons. These species are called free
radicals. Free radicals are denoted by putting a dot over the
symbol of atom/group of atoms.
 Thus, in a homolytic cleavage, the movement of a single
electron takes place instead of an electron pair. The single
electron movement is shown by ‘half headed’ or fish hook
arrows.

 A curved or fish hook arrow means that the electron/s

move from the atom at the tail of the arrow to the atom at the
head of the arrow.
2. HETEROLYTIC FISSION:
 In heterolytic cleavage , the bond breaks in such a way
that the shared pair of electrons remains with one of the
fragments.
 Thus, heterolytic fission is unsymmetrical so that one of
the fragments takes both the electrons of the shared pair
leaving none for the other fragment.
  This results in two charged particles. One atom has a
sextet of electrons and therefore has a positive charge. The
other has a valence octet with at least one lone pair and a
negative charge.

xz

 The species with a sextet and a positive charge is called a

carbocation, earlier called as carbonium ion.
 The species that has the carbon atom with the shared pair of
electrons and carrying a negative charge is called carbanion.

REACTION INTERMEDIATES
The species produced during the cleavage of bonds are called reaction
intermediates. The important reaction intermediates are :
1. Free radical-
  A free radical can be defined as an atom or group of atoms having
an unpaired electron and are produced during the homolytic
fission of a bond.
 Free radicls are very reactive as they have a strong tendency to
pair up their unpaired electron with another electron from
wherever available.
 They are very short lived and occur only as reaction
intermediates---never as products.
 Free radicals may be classified as primary, secondary or tertiary
depending upon whether one, two or three carbon atoms are
attached to the carbon carrying the odd electron.

 The order of stability of the free radical is in the order :

Methyl<primary<secondary < tertiary
The order of stability of the free radical can be explained on the basis
of hyperconjugation. Larger the number of alkyl groups attached to
the carbon atom carrying the odd electron, greater is the
delocalisation of the odd electron and hence more stable is the free
radical.
2. CARBOCATION
It is defined as a group of atoms which contain positively charged
carbon atom having only six (sextet) of electrons in its valence shell.
Relative stability of carbocation
  The methyl group has +I inductive effect i.e., it is electron
releasing.
 The alkyl group attached to +vely charged carbon atom tends
to release electrons towards carbon.
 As a result, it decreases the +ve charge on its carbon atom but
itself becomes somewhat positive.
 Due to this, the positive charge on the carbon atom gets
dispersed. This dispersal of charge results in stability.
 So, more the number of alkyl groups, greater will be the
dispersal of charge and therefore more stable will be the
carbocation.
 Tertiary carbocation with three alkyl groups attached to +ve
carbon is most stable and methyl carbocation is least stable
with no alkyl group and thus no dispersal of charge.
 Benzyl and allyl carbocation is also a primary carbocation but it
is highly stable because of resonance.

Structure of carbocation

 The carbon atom in carbocation is sp2 hybridised.

 The three sp2 hybridised orbitals form three sigma bonds with
1s orbital of the three hydrogen atoms or other carbon atoms
of alkyl groups.
 The unhybridised p-orbital of carbon remains vacant and is
perpendicular to the molecular plane.
  Thus the shape of carbocation is trigonal planar with a bond
angle of 1200.

3. CARBANION
A carbanion can be defined as a species containing a carbon atom
carrying a negative charge and possessing 8 electrons in its valence
shell.
 These are generated by the heterolytic fission of the covalent
bond involving carbon atom in which the atom linked to carbon
goes without the bonding electrons .

 Carbanions are also highly reactive species.

 Carbanions are also classified as primary 10, secondary 20 and
tertiary 30 depending on whether one, two or three carbon atoms
are attached to the carbon atom bearing negative charge.
 The order of stability of carbanions is reverse of that of
carbocations and free radicals. This can be explained on the basis of
+I inductive effect of the alkyl group. Alkyl groups have electron
releasing tendency and therefore increase the electron density on
the on the negatively charged carbon , thereby making it unstable.
 Larger the number of alkyl groups attached to the negatively
charged carbon, greater will be the electron density on the carbon
atom and lower will be its stability.
 Allyl and benzyl carbanions are stabilised due to resonance.

Structure of carbanion

 The negatively charged carbon atom in carbanion is sp3

hybridised.
 Therefore it has a tetrahedral structure.
 Three of the four sp3 hybridised orbitals form 3 sigma bonds
with hydrogen or carbon atom of the alkyl group. The fourth
sp3hybridised orbital contains the lone pair of electrons.
  The organic freactions which proceed through heterolytic bond
cleavage are called ionic or heteropolar or just polar reactions.
4. CARBENES
The carbenes are reactive neutral species in which the carbon atom has
six electrons in the valence shell out of which two are shared. The
simplest carbene is methyele CH2 .
5. NITRENES
Nitrenes are the nitrogen analogues of carbenes. These are electron
deficient monovalent nitrogen species. In these, N has a sextet of
electrons. The parent compound is nitrene or azine.

These are very reactive species and cannot be isolated.

TYPES OF ATTACKING REAGENTS
Reagents attack the reactive site of the substrate. The reactive site may
be electron deficient portion of the molecule –a positive reaction site or
it could electron rich ---a negative reaction site. The attacking reagents
can be classified into following three types:
i) Free radicals-----already done
ii) Electrophile
iii) Nucleophile
Electrophile is defined as a positively charged or neutral species
which are deficient of electrons and can therefore accept a pair
of electrons.
A reagent that takes away an electron pair is called electrophile.
For eg,
In AlCl3 and BF3, both Al and B have total of six electrons instead
of 8. Therefore they try to complete their octet and act as
electrophiles. According to Lewis concept of acids and bases , they
are called Lewis acids.
All positively charged species cannot act as electrophiles. Only
those positively charged ions that can accept a pair of electrons
act as electrophiles.For e.g., Na+, Ca+2, NH4+ etc cannot act as
electrophiles because all of them have an octet of electrons in
their valence shells and cannot accept electrons.
Nucleophiles is defined as a negatively charged species or neutral
molecules which are electron rich and seek an electron deficient
site. They contain an atom having unshared or lone pair of
electrons and are nucleus (positive charge) loving or nucleus
seeking.
According to Lewis concept of acids and bases, nucleophiles
behave as Lewis bases. For eg,
H-, X-, OH-, R-(carbanion), RCOO-, OR-, SR-, NH2-, (negatively
charged)
NH3, RNH2, R3N, H2O, ROH, ROR etc.

During a polar organic reaction, a nucleophile attacks an

electrophilic center which is a specific atom or part of the
electrophile which is electron deficient. Similarly, the
electrophile attacks a nucleophilhic center which is an electron
rich specific atom or part of the nucleophile.
As a result, the electrophiles get electron pair from the
nucleophiles and the two form a bond. A curved –arrow notation
is used to show the movement of electron from the nucleophile
to the electrophile.

DIFFERENCE BETWEEN ELECTROPHILE AND NUCLEOPHILE

 ELECTROPHILES NUCLEOPHILES
1. These are deficient in These are rich in electrons
electrons
2. They accept a pair of They donate a pair of
electrons from the substrate electrons to the substrate.
3. They behave as Lewis acids They behave as Lewis bases
4. They have atleast one empty They have atleast one lone
orbital due to which they pair of electrons which can be
accept electrons from the easily donated to the
substrate molecule. substrate molecule.
5. They are either neutral or They are neutral or negatively
positively charged chemical charges chemical species.
species.

ELECTRON DISPLACEMENTS IN COVALENT BONDS AND THEIR

EFFECTS

Organic compounds mainly contain covalent bonds. The electron pairs in

these covalent bonds may undergo displacements

i) either on their own

ii) under the influence of some other atom or group of atoms
iii) in the presence of an attacking reagent.
These effects could be temporary or permanent. The electron
displacements due to the influence of an atom or a substituent group
cause permanent polarisation of the bond such as Inductive effect ,
Hyperconjugation and Resonance effect. The electron displacements that
occur under the influence of the attacking reagent and go back to the
original electronic condition when the attacking reagent is removed cause
temporary effect such as electromeric effect.
1. Inductive effect:
This is a permane
nt effect which arises when a covalent bond is formed between atoms
of different electronegativity. The shared electron pair will shift
towards the atom with greater electronegativity resulting in induced
polarity of the covalent bond. It can be defined as:
The process of displacement of  electrons along the saturated carbon
chain due to the presence of a polar covalent bond at one end of the
chain is called inductive effect and is denoted as I effect.
For e.g., in chloropropane, CH3CH2CH2Cl,

Chlorine being more electronegative than carbon, the C—Cl bond

becomes polar as the electron pair between C and Cl shifts more
towards Cl atom. As a result, Cl atom acquires a partial negative
charge(δ-) and C acquires a partial positive charge (δ+). This
displacement of shared electron pair is not limited to C—Cl bond but is
transmitted to other C atoms along the chain. This happens because C1
which has developed partial positive charge draws some electron
density towards it from the adjacent C2 atom. Consequently some
positive charge, though relatively smaller, develops on C2 also .
However, charge on C2 is less than that on C1.
 This effect is passed on to the subsequent bonds also but the effect
decreases rapidly as we move away from the atoms involved in the
initial polar bond and becomes negligible from the fourth atom
onwards.
Types of Inductive effects
There are two types of inductive effects designated as –I or +I effect
depending upon whether the substituent atom or group is electron
withdrawing or electron donating.
For comparing the relative effects, hydrogen is taken as standard and
the substituent atoms or groups are classified into two categories:
i) electron withdrawing or attracting atoms or groups of atoms are
referred to as having –I effect. For e.g.,--NO2>--CN>--
COOH>COOR>F>Cl>Br>I>--OH.OCH2>--C6H5>H
ii) electron donating or repelling atoms or groups are referred to as
having +I effect. For e.g.,(CH3)3C-- > (CH3)2 CH-- > CH3CH2 -- >
CH3—
the more substituted the alkyl group, more is the +I effect
C-- Cl -I effect
C-----CH3 +I effect
Inductive effect helps in understanding organic reactions such as
methyl chloride is readily attacked by any negatively charged species
such as OH-, because the carbon of methyl chloride acquires a positive
charge due to shift of electrons towards chlorine.

2. Electromeric effect:
The phenomenon of movement of electrons from one atom to another
in a multiple bond at the demand of the attacking reagent is called
electromeric effect and is denoted as E effect.
It is a temporary effect which takes place between two atoms joined by
a double or triple bond. It involves instantaneous transfer of shared pair
of electrons of the multiple bond to one of the linked atoms at the
requirement of the attacking reagent. However, when the attacking
reagent is removed, the molecule acquires its original electronic
condition. Thus, the electromeric shift of electrons occurs only at the
moment of reaction.
For e.g., aldehydes and ketones contain the carbonyl group >C=O.
When a nucleophile- a negatively charged reagent seeking a positive
site approaches the molecule, it causes instant shift of electron pair of
carbonyl group to oxygen which is more electronegative than carbon.
As a result, carbon acquires positive charge and oxygen negative
charge. This results in the cleavage and losing of one bond in the
presence of the attacking reagent, making one valency of carbon free
where the attacking reagent gets attached.

The electromeric effect can be of following two types:

i) Electron donating or +E effect: When the electrons of the -bond
are transferred to the atom to which to which the attacking
reagent finally gets attached is called positive or +E effect. For
e.g., the addition of H+ to alkenes:

ii) Electron withdrawing or –E effect: When the electrons of the -

bond are transferred to the atom other than the one to which
the reagent gets finally attached, the effect is called –E(negative
electromeric) effect. For e.g., addition of CN- to the carbonyl
group.

Thus, it can be concluded that electromeric effect is said to be +E

effect when the displacement of electrons is towards the atom
or group and –E effect when the displacement of electrons is
away from the atom or group on which the attacking reagent is
added.
DIFFERENCES BETWEEN INDUCTIVE AND ELECTROMERIC EFFECT
INDUCTIVE EFFECT ELECTROMERIC EFFECT
1. It is a permanent effect 1. It is a temporary effect
which involves slight which involves complete
drifting of shared - transfer -electrons to one
electrons towards more of the bonded atoms.
electronegative atom.
 2. It operates only in 2. It operates in unsaturated
saturated compounds compounds which contain
which contain at least one atleast one multiple bond
polar bond. which may be polar or
nonpolar.
3. It does not need any 3. It operates only in the
outside reagent for its presence of an outside
operation. reagent.
4. It involves a partial 4. It involves complete
separation of charges transfer of electrons from
without formation of ions. the reagent to substrate
and vice versa. As a result
of this effect, ions are
formed.

3. Resonance or Mesomeric effect

There are many molecules whose behaviour cannot be explained by
single Lewis structure.
Resonance is a phenomenon wherein a molecule has to assigned two
or more structures , none of which alone can describe all the
properties of that compound ,then the actual structure is
intermediate of all the proposed structures and is called as the
resonance hybrid of these structures. Some examples are :

i) ii)
 i) Benzene may be represented by a cyclic structure having
alternate C-C single and C=C double bonds. According to
this structure two different bond lengths of carbon-carbon
bonds should be expected—154pm for C—C single bond
134pm for C=C double bond. However, as determined
experimentally, benzene has a uniform carbon -- carbon
bond length of 139pm which is intermediate between that
of single and double bond. Hence, the structure of benzene
cannot be adequetly represented by a single structure.
ii) Similarly, nitomethane also has two types of NO bonds but
experimentally obtained value is in between N-O and N=O.
Therefore, the actual structure of nitrobenzene is regarded
as a resonance hybrid of two structures.
Some features of resonance:
i) The resonance structures which are also called canonical
structures or contributing structures are hypothetical and
individually do not represent any real molecule.
ii) The various canonical structures contribute to the actual
structure in proportion to their stability.
iii) The energy of the actual structure or resonance hybrid is lower
than that of any of the contributing structures.
iv) The difference in energy between the actual structure and the
most stable of the resonating structures is called resonance
energy or resonance stabilisation energy.
v) More the number of contributing , more is the resonance energy
, hence greater the stability.
RULES FOR WRITING RESONANCE STRUCTURES
i) The resonance structures must have the same number of nuclei
and the same number of unpaired electrons.
ii) Structures which are indistinguishable are of equal energy and
hence equally towards resonance hybrid. For e.g.,
 Allylic carbocation-

iii) Structures with more number of covalent bonds contribute

more towards the resonance hybrid. For e.g., 1,3-butadiene
may be represented by the following structures:

Structure I makes more contribution towards resonance hybrid

because it has two  bonds (11 covalent bonds) than structures
2 and 3 which have only one  bond (10 covalent bonds).
iv) The structures with negative charge on more electronegative
atom and positive charge on less electronegative atom are of
lower energy and hence contribute more towards the
resonance hybrid.
v) Structures which involve separation of positive and negative
charges are of higher energy and contribute less towards the

resonance hybrid.
vi) Structures having like charges on adjacent atoms are highly
unstable and hence contribute less towards resonance hybrid.
Dispersal of charge always favours the resonance hybrid.
vii) Resonance hybrid in which each atom has complete octet of
electrons are more stable and contribute more to resonance
hybrid.
RESONANCE EFFECT
Resonance effect is defined as the polarity produced in the
molecule by the interaction of two - bonds or between a -
bond and a lone pair of electrons present on an adjacent atom.
This effect is transmitted through the chain. It plays a very
important role in case of conjugated systems (having alternate
 and  bonds). Due to this effect electrons can flow from one
part of the system to the other.
There are two types of resonance or mesomeric effect
designated as R or M effect
i) Positive Resonance effect or +R effect
 If a substituent associated with a conjugated
system has a tendency to donate electrons to the
double bond , the effect is called positive resonance
effect or +R effect.
 In this effect the transfer of electrons is away from
the substituent of the conjugated system.
 This electron displacement makes certain positions
in the molecule of high electron densities. E.g.,
Groups such as –OH, -- OR , -- NH2, --NHR, -- NR2, -- Cl, --Br, --I , --
NHCOR etc show +R effect.
ii) Negative Resonance effect or –R effect
 If a substituent associated with a conjugated system
has a tendency to withdraw electrons from a double
bond towards itself, the effect is called negative
resonance effect or – R effect.
 In this effect the transfer of electrons is towards the
substituent of the conjugated system.
 This electron displacement makes certain positions
in the molecule of low electron densities. E.g., figure
above-nitobenzene
Groups such as >C=O, --CHO, --CN, --NO2, --COOR, etc show –R effect.

DIFFERENCE BETWEN INDUCTIVE EFFECT AND RESONANCE EFFECT

Inductive effect Resonance effect
1. This effect involves It involves displacement of -
displacement of  electrons electrons or lone pair electrons
2. It operates in saturated It operates only in unsaturated
compounds conjugated systems
3. It moves up to three C It moves all along the length of
atoms in the chain and then the conjugated system
becomes negligible
4. This effect causes slight This effect results in complete
drift of -electrons towards transfer of electrons and hence
the more electronegative proper +ve and –ve charges are
 atom and hence only partial developed.
charges are developed

4. HYPERCONJUGATION
 It is also known as Baker and Nathan effect after the name of the
scientist who developed the concept of hyperconjugation.
 Hyperconjugation is a general stabilising interaction which
involves delocalisation of  electrons of C—H bond of an alkyl
group directly attached to an unsaturated system such as double
bond or a benzene ring.
 In such a situation, the  electrons of the H—C bond interact or
enter into partial conjugation with the unsaturated system.
Thus, hyperconjugation can be defined as the interaction
between the electrons of  systems (= and  bonds) and the
adjacent  bonds (single bonds ) of the substituent groups in
organic compounds.
Hyperconjugation is the stabilising interaction that results from
the interaction of the electrons in a σ-bond (usually C-H or C-C)
with an adjacent empty or partially filled p-orbital or a π-orbital to
give an extended molecular orbital that increases the stability of
the system. In many ways hyperconjugation effect is similar to
resonance effect. Since there is no bond between the -carbon
atom and one of the hydrogen atoms, hyperconjugation is also
called no-bond resonance. The carbon atom next to the C=C is
called  carbon and the hydrogen bonded to it is called -
hydrogen.
According to this concept, if an alkyl group carrying at least one
hydrogen atom is attached to an unsaturated carbon atom, it
releases electrons of carbon-hydrogen single bond towards the
multible bond (= or ). For e.g., ethyl cation:
In ethyl cation, the positively charged carbon atom has an empty
p-orbital. One of the C—H bonds of the methyl group can align in
the plane of this empty p-orbital and the electrons constituting
the C—H bond in plane with this p-orbital can then be
delocalised into the empty p-orbital as shown in the figure
above. This type of overlap stabilises the ethyl carbocation
because electron density from the adjacent -bond helps in
dispersing the positive charge.

It may be noted that although free proton has been shown in the
above structures, it is still bound quite firmly to the -cloud and
hence is not free to move.
As hyperconjugation occurs through the H-atoms present on the
carbon atom next to the double bond(-hydrogen), therefore,
more the number of -hydrogen atoms in the molecule, more
are the number of hyperconjugative structures. Thus,
hyperconjugative effect is expected to be more due to methy
CH3—group than due to ethyl C2H5—group because the ethyl
group has only 2 H atoms on the -carbon whereas methy group
has 3 H atoms on -carbon. Similarly hyperconjugation effect
will be less in isopropyl group (CH3)2CH—with only one H atom
on -carbon and there will be no hyperconjugation effect if tert-
butyl (CH3)3C—group is attached to the -carbon of the
unsaturated system as there is no H atom on it.
Thus, the order of hyperconjugation effect among alkyl radicles
decreases as follows:

As hyperconjugation helps in dispersing the positive charge in

carbocations thereby stabilising them, greater the number of
alkyl groups attached to the positively charged carbon atom,
greater is the hyperconjugation interaction and more stable will
be the cation. Consequently, the relative stability of the
carbocations is in the reverse order as compared to alkyl radicles
as follows:

4
 Hyperconjugation can happen in alkenes also. For e.g., propene

In propene, the electron pair of C—H bond () bond is involved

in conjugation with the -electron pair of the double bond.
Therefore, hyperconjugation involves delocalisation of -
electrons of H—C bond through overlapping of p-orbitals of
double bond.
APPLICATIONS OF HYPERCONJUGATION
The concept of hyperconjugation is very useful in explaining the
stabilities of some organic molecules.
i) Shortening of C—C single bonds adjacent to multiple(= or
) bonds.
ii) Relative stability of methylated alkenes. Larger the number
of methyl groups linked to the C=C, more is the number of
hyperconjugative C—H bonds and greater is the stability
of the alkene. More the hyperconjugation, larger is the
delocalisation of the -electrons.....more the stability (less
reactivity) of the alkene.
TYPES OF ORGANIC REACTIONS
Organic reactions can be broadly organised in two ways:
i) Kinds of reactions and
ii) Mechanism of reaction-how they occur
Some basic types of organic reactions are:
1. Substitution reactions-the reactions in which an atom or group of
atoms in a molecule is replaced or substituted by different atoms
or groups of atoms. Eg-1,
CH3Br + NAOHCH3OH + NaBr
In this reaction, a nucleophile (OH-) substitutes the bromide in the
substrate and hence this reaction is also called nucleophilic
substitution reaction.
Eg-2,

Nitration of benzene is an example of electrophilic substitution

where nitronium ion NO2+ acts as an electrophile.
Eg-3,

Halogenations of alkanes is an example of free radical substitution,

in which free radical Cl attacks the methane molecule.
2. Addition reactions
The organic reactions in which two molecules react to form a single
product having all the atoms of the combining units are called
addition reactions. For eg,
 Like substitution reactions, the addition reactions can also occur by
free radical , electrophilc or nucleophilic mechanisms.
3. Elimination reactions
The reactions in which two or more atoms or groups of the molecule
are removed are called elimination reactions.

In the elimination reactions, the two atoms or groups of atoms may

be removed from the same or adjacent atoms of the molecule.
Depending upon the relative positions of the atoms or groups
eliminated, these reactions are classified as  (alpha),  (beta) or γ
(gamma) elimination reactions.
i) -Elimination- the loss of two atoms or groups occurs from the
same atom(called as -positions) of the substrate. This type of
elimination results into electron deficient reactive
intermediates, which further react to form stable products. For
 e.g., formation of carbine is an example of -elimination
reaction.

ii) -Elimination- the loss of two atoms or groups occurs from the
adjacent positions (,) of the substance.

iii) Γ-Elimination- the loss of two atoms or groups occurs from one
and next to adjacent carbon atoms i.e.,  and γ positions. This
elimination results in the formation of a three membered ring.

4. Rearrangement reactions
These reactions involve the migration of atoms or group of atoms to
another position within the molecule under suitable conditions.
5. Condensation reactions
In these reactions , two different or same organic reactants
combine with or without the elimination of a simple molecule to
give a product.

6. Isomerisation reactions
These reactions involve the interconversion of isomers wherein the
molecular formulae and carbon skeletons of reactants and
products always remains the same.
PURIFICATION OF ORGANIC COMPOUNDS
Organic compounds , whether extracted from natural sources or
prepared in laboratory, are generally impure and need to be
purified. The various methods used for their purification are based
on the nature of the compound and the impurity present in it.
Some common techniques of purification are:
1. Filtration
The process of filtration is used to separate an insoluble solid
component of the mixture from the soluble component in a given
solvent. The mixture is dissolved in a suitable solvent in which
one component dissolves. The filtrate containing the soluble
component is collected separately.
e.g., a mixture containing naphthalene and urea can be separated
by using water as a solvent. Naphthalene is obtained as the
residue while urea which is soluble in water is obtained as the
filtrate. It is obtained fro mthe filtrate by evaporating water.
2. Recrystallisation
This method is based on the difference in the solubility of an
organic compound and the impurity present in it in a suitable
solvent.
 The impure compound is dissolved in a solvent in which it is
sparingly soluble at room temperature but appreciably
soluble at higher temperature.
 The solution is concentrated to get a nearly saturated
solution.
  On cooling the solution, pure compound crystallises out and
is removed by filtration.
 The filtrate , called mother liquor contains impurities and
traces of the compound.
 Impurities which impart colour to the solution can be
removed by adsorption on activated charcoal.
 Repeated crystallisation is necessary for the purification of
compounds containing impurities of comparable solubilities.
3. Sublimation
This process is used for the separation of sublimable volatile
compounds from non sublimable impurities. The process is used
for the purification of camphor, naphthalene, anthracene,
benzoic acid etc cont3aining non volatile impurities.
4. Distillation
This method is used for the purification of liquids which boil
without decomposition and contain non volatile impurities.
Simple distillation can be used to
i) Separate volatile liquids from non-volatile impurities
ii) Separate liquids having sufficient difference in their boiling
points. The liquids having different boiling points vapourize
at different temperatures.
 The mixture is heated in a distillation flask.
 On boiling, the vapours of lower boiling component are
formed first. These vapours are condensed by using a
condenser and the liquid-distillate is collected in a separate
flask(receiver).
 The vapours of the higher boiling component form later
and the liquid is collected separately in a similar way.
 The distillate contains pure liquid while the impurities are
left behind in the distillation flask.
Distillation method can be used to separate a mixture of

i) Chloroform (bp-334K) and aniline(bp 457K)

ii) Ether(bp 308K) and toluene(bp-384 K)
iii) Benzene (bp-353K) and aniline(457K)

Fractional distillation

If the difference in the boiling points of two liquids is not much, the
vapours of such liquids are formed within the same temperature
range and get condensed simultaneously. Simple distillation
technique cannot be used to separate such mixtures.

Fractional distillation is used to separate a mixture of two or more

miscible liquids which have boiling points close to each other. In this
technique, vapours of the liquid mixture are passed through a
fractionating column before condensation. A fractionating column is
a long tube provided with obstructions or packed with glass beads or
porcelain rings to the passage of vapours moving upwards and liquid
moving downwards.

Role of fractionating column:

 The fractionating column provides a larger surface area for

heat exchanges and obstructs the ascending vapours and
descending liquid.
 When the flask is heated, the vapours of the more volatile
liquid(low boiling component)begin to rise up in the
fractionating column.

 Due to obstructions in the fractionating column, some of the

vapours condense and fall back in the column. At the same
time, some of the condensing liquid in the fractionating column
gets heat from the ascending vapours and revaporises.
 As a result, the vapours become richer in low boiling
component. They rise up and are condensed in the condenser
and collected separately.
 The vapours of the less volatile or high boiling liquid also rise in
the column but due to many obstructions they get condensed
in the column and flow back to the distillation flask.
 After a series of successive distillations, the remaining liquid in
the distillation flask gets richer in higher boiling component.
 Each successive condensation and vapourisation is called
theoretical plate. Commercially, columns with hundreds of
plates are available.
 A mixture of acetone(p-330K) and methyl alcohol(bp-338K) can
be separated by this method as their boiling points are very
close.
 A technological application of fractional distillation is to
separate different fractions of crude oil in petroleum industry.
Distillation under reduced pressure
 Vacuum distillation method is used to purify liquids that have
very high boiling points or/and those which decompose at or
before their boiling points.
 Such liquids are made to boil at a temperature lower than their
boiling point by reducing the pressure on their surface.
 A liquid boils at a temperature at which its vapour pressure
equals the external pressure. When this external pressure is
reduced with the help of a water pump or vacuum pump, its bp
also gets lowered and its vapours can form at a lower
temperature without any risk of decomposition.
 This method is employed for the separation of glycerol and
spent-lye(NaOH) in the soap industry.
Steam distillation
This technique can be applied for the purification of liquids which
are:
i) Volatile in steam but are nor miscible in water.
ii) Possess sufficiently high vapour pressure at the bp of water-
1000C.
iii) Contain non-volatile impurities.
 In this method, steam from a steam generator is continuously
bubbled through impure organic liquid heated in a flask.
The heat of the steam is enough to heat the liquid but the
steam itself gets condensed.
 After sometime the sum of the vapour pressures of the organic
liquid and water(formed due to condensation of steam) –p1 and
p2 respectively, become equal to the atmospheric pressure.
P=p1 + p2
Since p1 is lower than p, the organic liquid vaporises at lower
temperature than its boiling point.
At this point, mixture of the organic liquid and water starts
boiling at a temperature lower than its boiling point, gets distills
over and collects in the receiver.
The components of this mixture are then separated by simple
methods.
Thus in steam distillation, water and organic substance
vapourise together so that the total vapour pressure equals the
atmospheric pressure earlier than when the organic substance
would have been pure.
 This method is used for the separation of a mixture of o-
nitrophenol and p-nitrophenol. O-nitrophenol being more
volatile condenses earlier with water vapours and is collected
separately in the receiver leaving behind p-nitrophenol with a
higher boiling point in the distillation flask.
It can also be used for the purification of an impure sample of
aniline.

5. Differential extraction
 This method is used to separate a given organic compound
present in aqueous solution by shaking it with a suitable
organic solvent in which the compound is more soluble than
water.
 The basic requirement of the organic solvent is that it should
be immiscible with water so that the organic and water
layers can be easily separated by a separating funnel.
 The organic solvent is later removed by distillation or by
evaporation to get back the compound.
 If the organic compound is less soluble in the organic
solvent, a very large quantity of the solvent would be
required to extract even a small quantity of the compound.
 The technique of continuous extraction is employed in such
cases where the same solvent is repeatedly used for the
extraction of the compound.
6. Chromatography

This method is used for

i) Separation of mixtures into their components
ii) Purification of compounds
iii) Testing the purity of compounds
 The word chromatography has been taken from two greek
words chroma meaning colour and graphy for writing because
this method was first used for separation of coloured
substances (pigments) found in plants.
 Principle – the technique of chromatography is based on the
difference in the rates at which the components of a mixture
move through a porous medium (called stationary phase)
under the influence of some solvent –liquid or gas (called
moving phase).
 The stationary phase is either a solid or a liquid and has large
surface area.
 The moving or mobile phase is a liquid or gas which is allowed
to move slowly over the stationary phase.
 Based on the principle involved , chromatography can be of
following two types:
1. Adsorption Chromatography
It is based on the fact that different compounds are adsorbed on
an adsorbent to different degrees. Commonly used adsorbents are
silica gel and alumina. Thus, adsorption chromatography works on
the principle of differential adsorption.
i) Column chromatography
ii) Thin layer chromatography
2. Partition chromatography-is based on the differences in
the tendencies of to distribute or partition between two
phases.
The eluent or eluant is the "carrier" portion of the mobile phase. It moves
the analytes through the chromatograph. In liquid chromatography, the
eluent is the liquid solvent; in gas chromatography, it is the carrier gas.

Ninhydrin is a synthetic crystalline compound which forms deeply coloured

products with primary amines and is used in analytical tests for amino
acids.