GENERAL ORGANIC CHEMISTRY

Total No.of questions in General Organic Chemistry are -

In Chapter Examples.............................................................. 45
Solved Examples ................................................................... 29

Total No. of questions .......................................................... 74

 + I group : The group which donates or gives
1. Electrical effects electron is known as + I group and effect is
The electrical (or electronic) effects are mainly known as + I effect.
divided into following categories :  
1.1 Inductive Effect Alkyl groups, O , CO O are + I groups.
1.2 Resonance (or mesomeric) Effect (a) + I power of different type groups and
1.3 Electromeric Effect anions :
1.4 Hyperconjugation NH– > O – > COO – > ter alkyl > sec. alkyl >
p-alkyl > CH3 > H
1.1 Inductive Effect (Polar nature of covalent bonds)
——————————————————————
The displacement of an electron (shared) pair + I power in decreasing order with reference to H
along the carbon chain due to the presence of an
electron withdrawing or electron releasing groups
in the carbon chain is known as Inductive Effect (b) + I power of same type of alkyl groups :
( –effect). + I power  number of C’s in same type of
+  + alkyl group
 C----C---- C -- G (G : functional group) For example
– –
C ---- C ---- C -- G
But the effect is insignificant beyond third
carbon atom.
 This effect is transmitted through the chain
of  bonds and diminishes. with increasing
Based on I-effect
chain length.
Inductive effect is thus
Ex.1 Inductive effect refers to -
(i) A permanent effect
(A) electron displacement along a carbon
(ii) The electrons never leave their original chain
atomic orbital.
(B) complete transfer of one of the shared
(iii)Operates through  bonds pair of electrons to one of the atoms joined
(iv) Polarisation of electrons is always in by a couble bond
single direction. (C) complete transfer of electron hither to
(v) It is generally observed in saturated unshared
compounds. (D) none of the above
(vi) Its magnitude (i.e., electron withdrawing
or donating power) decreases with Sol. (A) partial displacement of electron takes
increase in distance. place.
On the basis of inductive effect, groups can be of
two types. Ex.2 Which of the following groups has the highest
– I group : The group which withdraws electrons + I effect ?
is known as – I group and its effect is known (A) CH3 – (B) CH3
as – I effect. (C) (CH3)2 CH – (D) (CH3)3 C –
– I power of various group & cation.
Sol. (D) ter. alkyl group have highest + I effect.
 
N F3 > NH3 > NO2 > CN > SO3H > CHO > CO
> COOH > COCl > COOR > Ex.3 Maximum – I effect is exerted by the group-
CONH2 > F > Cl > Br > I > OH > OR > NH2 (A) C6H5 – (B) – OCH3
> C  CH > C6H5 > CH = CH2 > H (C) Cl (D) NO 2
———————————————————— Sol. (D) From series.
– I power of groups in decreasing order with
respect to the reference H
Ex.4 Zero inductive effect is exerted by the group-
1
(A) C6H5 – (B) H (C) CH3 – (D) Cl – I
 I power of the group present on  COOH
Sol. (B)
power of group
APPLICATIONS OF INDUCTIVE EFFECT Consider the following homologous aliphatic acids.
Example 1.
(A) Strength of Carboxylic Acid : Acid strength is
measured by the position of equilibrium of
ionisation in water.
CH3 –– COOH
O O
|| ||  
R – C– O – H R – C – O + H CH3 –– CH2 –– COOH

The further the ionisation go to the right, the CH3 –– CH2 –– CH2 –– COOH
greater the acid strenth. In other words.
CH3 –– CH2 –– CH2 –– CH2 –– COOH
 
 O  + I power of alkyl groups Acid strength in
 ||    are in increasing order decreasing order
 
R – C – O [H]
Ka =
[RCOOH] Example 2.
Cl–CH2–COOH Cl2CH–COOH CCl3 – COOH
1 
Acid strength  Ka 
pKa – I power is in increaasing order,
or Acid strength  concentration of acid anion acid strength is in increasing order
or Acid strength  stability of acid anion (B) Acidity of Alcohols : Acidity of alcohol depends
on the stability of alkoxide ion (i.e., conjugate
Thus strength of acid is the function of base of alcohol) which is obtained by the
stability of acid anion. dissociation of alcohols.
The influence of the inductive effect on acidity  
can be summarised as follows : R – O – H R – O + H
Acid strength of alcohol  stability of alkoxide
O
|| ion
(a) EWG – C – O – H Note : As we know that as the distance from
source increases, intensity of effect decrease
O also (distance prefer on power).
||  
EWG  C  O + H Ex. CH2 – OH CH2 – CH2 – OH
Electron withdrawing group (– I gp) stabilises | |
Cl NO 2
group (– I gp) stabilises
acid anion and strengthens the acid I II
or, – I group increases strength of acid and I is more acidic than II even power of NO2
thus : (–I) is more, but in case of Cl distance is
less.
Strength of acid –I power of the group present
on – COOH
(C) Basicity of Amines :
O Basicity is defined as the tendency to donate an
||  electron pair for sharing. The difference in the
(b) EDG  C  O base strength in various amines can be explained
Electron donating groups (i.e, + I gp) destablise on the basis of + - effect.
acid anion and weaken the acid.
The groups producing + effects (alkyl groups)
or, + I group decreases strength of acid and tends to intensity electron density over N in
thus : amines thereby producing a base strengthening
strength of acid  effect.
 Thus, strength of base  + I power of group Sol.
1 (D) Stability of Non-conjugated Cations and
present on – NH2  Kb  Anions : Stability of non-conjugated charge
pKb
species can be compared by the following rules:
Whereas, a group producing - effect [–Cl, –NO2]
tends to decrease electron density over N -atom Rule 1 : Less is the magnitude of charge, more
in amines, thereby producing a base weaking will be stability of charge species.
effect.
Stability of simiar charge species (i.e. stability
Thus, strength of base 
between cations or stability between anions) can
1 be compared by this rule in those cases where:
 Kb
 I power of group present on  NH2
1
The order of basicity is as given below : Thus, stability
magnitude of  ve or  ve ch arg e
Alkyl groups (R—) Relative base strength
(i) CH3 R2NH > RNH2 > R3N > NH3 (i) Charge is present on the same atoms in all
(ii) C2H5 R2NH > RNH2 > NH3 > R3N species, and
(iii) (CH3)2CH RNH2 > NH3 > R2NH > R3N (ii) Hybridisation of atom bearing the charge
(iv) (CH3)3C NH3 > RNH2 > R2 NH > R3N should be same in all species.
Comparing with increasing +  effect, trend is For example :
rather surprising. This is due to the inability of 3°
  
amines to give up their electrons due to presence CH3 – C H2 CH3 – C H – CH3 CH2 = C H
of three bulky alkyl groups over N (steric effect).   
sp 2 sp 2 sp
Acidic and Basic Strength ( ) ( ) ( )

Ex.5 Strongest acid among the following is - Stability of cations I and II can be compared by
(A) CF3COOH (B) CCl3COOH rule -1 because positive charge in (I) and (II) is
(C) CBr3COOH (D) CH3COOH present on same atom (i.e. carbon) and
Sol. (A) F has greater – I effect. 
hybridisation of C is same in both cases.

Ex.6 Basic nature of H3O+, H2O and OH– is in Stability of (I) and (III) cannot be compared by

order - rule-1 because hybridisation of C in (I) and (III)
(A) H3O+ < H2O < OH– is different.
(B) H2O < OH– < H3O –
Rule 2 : For maximum stability : positive
(C) OH– < H2O < H3O +
charge should be present on electropositive atom
(D) OH– = H3O+ = H2O in catrion or negative charge should be present
Sol. (A) Anion are always more basic due to on electrongative atom in anion.
presence of real charge.
This rule can be used in those cases where
hybridisation of atoms bearing charge is different.
Ex.7 Among the following which one is most basic- Thus stability of cations (I) and (III) or (II) and
(A) NH3 (B) CH3NH2 (III) can be compaired by this rule.
(C) CH3CH2NH2 (D) CH2 – NH2 (1) Stability of Alkyl Carbocation :
| Stability of alkyl carbocation 
Cl
Sol. (C) + I group increases the basicity of amine. 1
....(i)
Ex.8 Which one of the following is the weakest magnitude of positive ch arg e
base - Magnitude of positive charge 
(A) (C2H5)3N (B) (C2H5)2NH
(C) C2H5NH2 (D) NH3 1
 I power of group (i.e., alkyl group )
....(ii)
(Ans. A)
From (i) and (ii)
 Stability of alkyl carbocation  +  power of the (3) Stability of Alkyl and Vinyl Carbocation :

group present on C .Thus tertiary alkyl Stability of these two type of species can be
carbocation is more stable than secondary which compared by rule 2.
is more stable than primary carbocations.
CH3 –
   
H – C H2 R – C H2 R– C H –R R – C– R
|
R
 
methyl 1º- 2º-carbocation 3º- Positive charge is present
carbocaton carbocation on less E.N. carbon.
——————————————————————
 CH2 =
(i) Number of + I groups on C is in increasing
order

(ii) + I power on C is in increasing order

(iii) Magnitude of positive charge is in decreasing
Positive charge is present on
order
(iv) Stability is in increasing order electropositive carbon
Hence alkyl carbocation is always more stable
than vinyl carbocation.
Note : Stability of free redical varies in same order
as carbocation. Note :
(A) Order of electronegativity of different type of
(2) Stability of Alkyl Carbanion
hybridised orbital is sp > sp2 > sp3
Stability of alkyl carbanion 
(B) Less E.N. carbon consist of +ve charge is
1 more stable.
magnitude of negative ch arg e
....(i) (4) Stability of Alkyl, Vinyl and Acetylenic
Carbanions : Stability of these three species
Magnitude of negative charge  + I power of the can be compared by rule 2.
group (i.e., alkyl group)....(ii)
Stability of alkyl carbanion  (I)CH3 –
1

 I power of the alkyl group present on C
For examples : 
Negative charge is present on
electropositive carbon

(II) CH2 = CH
2
sp -hybrid carbon
It is electronegative carbon
( % s-character is 33.33)
 

(i) Number of alkyl groups on C is in increasing Negative charge is present on electronegative
order. carbon (less electronegative)

(ii) + I power on C is in increasing order

(iii) Negative charge on C is in increasing order
(iv) Stability is in decreasing order
 Ex.13 Most stable carbocation is -
(III)
 
(A) CH3 – CH 2 (B) CH 2 CHCl2

 
(C) CH 2 CH2Cl (D) CH 2 – CH2NO 2

 (Ans, A)
Negativ e charge is present on more Sol.
electronegative carbon 1.2 Resonance (or Mesomeric Effect)
Hence, acetylenic carbanion is more stable than When a molecule or ion can be represented by
vinylic carbanion which is more stable than two or more structures which have the same
alkyl-carbanion. arrangement of atomic nuclei but differ in
Note : distribution of electrons, the phenomenon is called
More E.N. carbon consist –ve charge is more as Resonance. The various structures are called
stable. contributing or resonating structures. None of
these structures truly represents all the properties
Stability of that molecule or ion. The actual structure is a
resonance hybrid of sev eral contributing
structures.
Ex.9 Which of the following ions is most stable : In the molecule if resonance is present then
 
(A) CH3CH2 C H2 (B) CH3 C HCH2CH3 mesomeric effect may be present or may not be
present. Resonance generally occurs when there
  is a conjugation of -bonds (alternate double -
(C) (CH3)3 C (D) (CH3)3 C . C H2 single - double bond arrangement) known as
Sol. (C) ter. carbocation is more stable. (Rule 1) conjugated system.
Conjugate positions of the molecule :
Ex.10 The most stable carbanion is -
Alternate positions of the molecule having  bond,
(A) methyl carbanion
positive charge, negative charge, odd electron or
(B) primary carbanion lone pari of electrons are known as conjugative
(C) seccondary carbanion ion positions.
(D) tertiary carbanion
CH3– CH2 – CH = CH – CH = CH – CH = CH2
Sol. (A) + I group decreases the stability of 1 3 5
carbonion. 1, 3, 5 are alternate positions having  bonds.
Hence these positons are known as conjugate
Ex.11 Which of the following statements is wrong ?
positions.
(A) a tertiary free radical is more stable than

a secondary free radical
CH 2 = CH – CH = CH – C H – CH3
(B)a secondary free radical is more stable 1
3 5

than a primary free radical 1, 3 and 5 are conjugate positons.

(C)a tertiary carbonium ion is more stable  
than a secondary carbonium ion CH 2 = CH – CH = CH – CH = CH – N H 2
1 3 5 7
(D)a primary carbonium ion is more stable Conjugate positions
than a secondary carbonium ion Note : Compound having at least two conjugate
Sol. (D) (due to + I effect) positions is known as conjugated compound.

Ex.12 The species CH3 C HCH3 is less stable Type of Conjugates
than- (1) ,  conjugation : If all conjugate positions have
  bonds, then conjugation is known as , 
(A) (CH3)3 C+ (B) CH3CH2 C H2 conjugation

(C) CH3 C H2 (D) CH3+ CH 2 = CH – CH = CH2
1 3

Sol. (A) (more + I group) CH3 – CH2 – CH = CH – CH = CH – CH = CH2

1 3 5
 Thus conjugated electrons are delocalised
electrons and conjugated compounds are
delocalised compounds.
2. Conjugated compounds can be represented
by two or more than two possible structures
due to the delocalisation of conjugated
All of the above compounds have ,  conjugation.
electrons. These possible structures are
(2) Positive charge,  conjugation : In this case known as resonating structures.
all conjugate positions have  bonds and only Thus
one conjugate positon has positive charge. If this  
is the case, then conjugation is known as positive CH2 = CH – C H2 and C H2 – CH = CH2
 
charge,  conjugation. I and II are resonating structures of allyl

carbanion.
CH 2 = CH – C H2 3. (a) Number of resonating structures of
1 3 conjugated compound = Number of conjugate
It has positive charge,  conjugation. positions.
 Note : This formula is not valid for benzene and fused
CH2 = CH – CH = CH – C H2
benzene system, i.e., naphthalene,
This species has two type of conjugation ,  anthracene etc.
conjugation and positive charge,  conjugation. Structure Number of resonating
structures
(3) Negative charge,  conjugation : If all
conjugate positions have  bonds and only one 
CH 2 = CH – C H2 2
conjugate position has negative charge, then 1 3
conjugation is known as negative charge, 

conjugation
CH 2 = CH – CH = CH – C H2 3
 1 3 5
CH2 = CH – C H2
(b) Number of resonating structures of benzene

derivatives in which key atom is in conjugation
CH2 = CH – CH = CH – C H2
to benzene ring = Three resonating structures
(4) Odd electron,  conjugation : If all conjugate for per benzene ring and one resonating
positions have  bonds and one conjugate structure corresponding to key atom. For
position has odd electron, then conjugation is examples :
known as odd electron,  conjugation.
 
 C 6H 5 – C H C 6H5 – CH – C 6H5
CH2 = CH – C H2 3 2
1 3 1 3  10
4

CH2 = CH – CH = CH – C H2
C 6H 5 – 
C – C 6H5
(5) Lone pair,  conjugation : If all conjugate 3
| 3  10
positions have  bonds and only one conjugate C 6H5
position has lp then conjugation is known as lp, 3
 conjugation. 4. Resonating structures are not the real
 structures of conjugated compounds.
CH2 = CH – N H2 CH2 = CH – 5. The real structure of conjugated compounds
is a hybrid of all resonating structures.
CH 2 = CH – CH = CH – CH = CH –   This phenomenon is known as resonance,
1 3 5 N H2
7 mesomeris or delocalisaton.
(A) Properties of conjugated compounds : Thus, during resonance if one cannonical form
1. Conjugated electrons migrate from one has two real opposite poles, means at one
conjugate positon to the other conjugate terminal there is accomotation of charge &
position at another terminal there is depletion of
charge takes place. Such type of resonance

is called as mesomeric resoance & effect is
C H2 – CH = CH 2
1 3
called as mesomeric effect.
 Thus resonance is nothing but hydridisation
of resonating structrues and resonance
phenomenon will take place in conjugated
compounds.

(I) (II)
(I) and (II) are resonating structures of acyl
cation. (II) will be more stable than (I).
(III) If all structures have formal charge, the
most stable one is that in which the positive
and negative charges reside on the most
electropositive and most electronegative
atoms of the species respectively.

 
O O
|  |
two real opposite poles H – C = OH H – C – H

I to IV are the resonating structures of aniline.
The real structure of aniline will be a (I) and (II) are resonating structures of formic
resonance hybrid of all these four structures. acid. All atoms in (I) and (II) have their
complete octets. In (I) negative charge is on
5. Effect of resonance on the resonating
oxygen but in (II) negative charge is on carbon
structures : Consider structures of benzene: therefore (I) will be more stable than the (II).
(iv) Resonating structure with a greater number
of covalent bonds is more stable.
(v) Increase in charge separation decreases the
stability of resonating structure.

I and II are resonating structures of C6H6.

(a) According to resonating structure I, C, C bond
length between C1 and C2 will be 1.33 Å.
(b) According to reasonating structure II, C, C
bond bond length between C1 and C2 will be
1.54 Å.
(c) According to resonance, bond length between
C1 and C2 will neither be 1.33 nor 1.54 Å but
will be in between 1.33 and 1.54 Å, i.e., bond
length between C1 and C2 is > 1.33 and
< 1.54 Å.
(d) Experimental value is 1.40 Å, this result
coincides with the result obtained by
resonance, hence resonance theory or Hence stability of II and IV will be the same
concept is correct. and both will be more stable than III. The
order of stability of resonating structures in
(B) Contribution of Resonating structures : The
decreasing order will be as follows :
contribution of an individual resonating structure
I > II  IV > III
depends upon its stability and stability depends
on the followign factors : Note :
(i) Neutral species is more stable than the All the resonating structures do not contribute
equally to the real molecule. Their contribution
charged (or dipoler species).
is a direct function of their stability.
(ii) Species having complete octet is more stable
(C) Conditions of Resonating structures :
than the species having incomplete octet.
Resonance structures should fulfil following
conditions:
 (1) All resonating structures must have the same Total number of bonds on central atom
arrangement of atomic nuclei. Resonance =                
differs from tautomerism in this very important Number of resonating structures
aspect. For examples :
 Two bonds
O O
|| | 
Total bonds on
R – C–  R – C = O– H this carbon is 3
One bond
Position of atomic nuclei in (I) and (II) are
same. 3 3
21
Bond order of carbon in benzene = = 1.5
O OH 2
|| |
CH3 – C – C H3 CH3 – C  C H2 (E) + M effect (+R) :
1 1

(I) (II)
C or
Position of hydrogen nuclei in (I) and (II) are
different hence (I) and (II) are not the
When flow of e– pair (movement) starts from the
resonating structures.
group (G). It takes place when G has a lone pair
(2) The resonating structures must have the or an extra electron (in ion).
same numbers of paired and unpaired
e.g. – NH2, – OH, –Cl, –OR etc.
electrons. However, they differ in the way of
distribution of electrons. – M effect (– R) :

= –  – =
–C C G or
Total number of Total number of
paired electrons = 16 paried electrons = 16 When e– pair movement takes place towards G
from the molecule.
unparied electron=one unpaired electron=one
e.g. – NO2 , – C = O, –C  N, –SO3 H etc.
(3) The energies of the different remaining
The v arious resonating structures of
structures must be the same or nearly the
chlorobenzene, aniline and nitrobenzene are
same.
illustrated in following diagrams. Note that – Cl
(4) All atoms that are part of the delocalisation and – NH2 show + M effect and – NO2 show
system must be in a plane or be nearly – M effect.
planar.
(5) All aotms of the resonating structure should
follow the octet rule. For example :
     



(a) (b) (c)

All atoms follow octet rule.


NH3 NH3
  
Nitrogen does not
follow its octet rule
(I) (II) hence (II).is not (d) (e)
resonating
structure of (1).

(D) Resonance and Bond order : Bond order in

conjugated compound or bond order in compounds
which exhibit resonance
  –
(B) C H2 = CH – C H = 0
– 
(C) C H2 = C H – CH = 0
– 
    (D) C H2 = CH – CH = O
Sol. (A) O atom is more electronegative

Ex.15 In which compound delocalisation is not

possible -
(A) 2-butene (B) 1, 3-butadiene
(C) 1, 3, 5-hexatriene (D) Benzene
Sol. (A) 2-butene, no conjugation present
    
Ex.16 Consider the following compound :
C H2 = C H – C H = C H2
1 2 3 4

carbon-carbon bond length between C2 and

C3 will be -
(A) 1.54 Å
(B) 1.3 Å
(C) Less than 1.54 and greater than 1.33 Å
   (D) 1.21 Å
Sol. (C) C2 – C3 are at conjugated position.

Ex.17 + R power of the given groups -


(a) – O (b) – NH2
(c) – OH (d) – NHCOCH3
increasing order is -
  (A) a > b > c > d (B) d > c > b > a
(C) a > c > b > d (D) a > d > c > b
Sol. (A)
Thus, mesomeric effect works at only ortho &
para position, it is absolutely absent on meta Ex.18 In pyridine ; Number of conjugated
position, while inductive effect works at all three
position o–, m –, p however intensity of effect electrons are -
decreases as the distance increases. (A) 6 (B) 8
Note : (C) zero (D) 5
Mesomeric effect always dominant on inductive Sol. (A) Lone pair of N-atom does not take part
effect except halogen (Cl, Br, I only) in resonance.

Ex.19 Which is the decreasing order of acidity in,

m-effect & Resonance HCOOH (I), CH3COOH(II), CH3CH2COOH(III)
and C6H5COOH(IV) -
Ex.14 Polarisation of electrons in acrolein may be (A) I > II > III > IV
written as - (B) IV > III > II > I
  (C) IV > I > II > III
(A) C H2 = CH – CH = O (D) I > IV > II > III
Sol. (C)
Ex.20 Which of the following is corect for stability Structures = 2 Structures = 4
of phennoxide ion - Hence the benzyl carbocation is more stable
(A) resonating structure of benzene ring than the allyl carbocation.
(B) localization of -electron in phenoxide ion
(C) delocalization of -electrons in phenoxide (4) Stability of Substituted Benzyl
ion Carbocations : Stability of substituted benzyl
(D) all of the above carbocation depnds on the nature of group
Sol. (C) present in the benzene ring : The group may
be +, –, +R or – R
Case I : When ring has group which is –  and
Application of Mesomeric effect :
–R group.
(a) Stability of conjugated species :
(1) Stability of a conjugated compound is more 1
Stability 
than the corresponding non-conjugated Magnitude of ch arg e
compound.
For example : q2
P.E. = K
CH2 = CH–CH = CH – CH3 r
()
P.E.  = charge  = Stability 
Conjugated compound
CH2 = CH – CH2 – CH = CH2 Example :
()
Non - Conjugated compound
Hence () will be more stable than ()
(2) Stability of an aromatic compound is more
than the corresponding non-aromatic
conjugated compound. For example () is
more stable than (V) () () ()
(i) Increase in Increase in (i)Increase in
CH2=CH–CH2=CH–CH=CH2 the magnitude of Positive charge Positive
positive charge by only by – charge by
() (V) – and – R effect – and – R
Aromatic Conjugated non-aromatic effect effect
compound compound (ii) – and –R (ii) –I and – R
Thus stability series of different compounds power is power is
in decreasing order is as follows : maximum minimum
Aromatic compound > conjugated non- Hence () is more stable than () which is more
aromatic compound > non-conjugated stable than ()
compound Case II : When ring has a group which is +  and
(3) Stability of allyl carbocation and benzyl + R group.
carbocation :
Allyl and benzyl carbocation are conjugated
species hence their stability can be
compound by the number or resonating
structures.
 
CH2 = CH – C H2 C6H5 – C H2
(I) (II) (III)
Number of resonating Number of resonating
Positive charge Stabilised Stabilised by Stabilised by Stabilised by Stabilised by –R
is decreased by by +  group +  and –R and – effect – effect and – effect
+  and + R only + R effect (– power (– power is
is minimum) maximum)
group or
Thus o-derivative is more stable than p-derivative
stabilised by +  and
which is more stable than m-derivative.
+ R group
Case III : When group has + R and –  effect.
Hence () is more stable than () which is more
stable than ().
Thus o - derivative is more stable than p-derivative
which is more stable than m-derivative.
Case III : When group has + R effect and –  effect.

Destabilised Stabilised by Destabilised

by+R effect – effect by +R effect
and stabilised stabilised by –
by – effect effect
– power is and – power is
Stabilised by + R effect Stabilised by + R effect maximum minimum
destabilised by –I effect destabilised by –I effect
–I power is maximum (due –I power is minimum (due Thus m - derivative is more stable than o-derivative
to distance) to distance) which is more stable than p-derivative.
Note :
Hence p -derivative is more stable than o-derivative
In case of halo derivative, result depends only
which is more stable than m-derivative.
on inductive effect.
Note :
(B) Acidity of Phenol
Stability of free radical have same order of
arrangement.  
C6H5OH  C6H5 O + H
(5) Stability of Substituted Benzyl carbanions

When group has + R and + 
more is the stability of phenoxide ion more will
be the acidity of phenol
Acidity of Substituted Phenols : Acidity of
substitued phenols depend on the stability of the
phenoxide ion because acidity is the function of
acid anion.
Case I : When group is –R and – group.
+R effect decrease
stability Destabilised only
+I effect also decrease by+ R and +  effect
stability (+  power is minimum)
+I power is maximum

Hence m -deriv ativ e is more stable than

p-derivative which is more stable than o-derivative.
Phenoxide ion Stabilised by Stabilised by
Case II : When group has – R and –  effect.
is stabilised by –  effect only –R and – effect
–R and – effect and – power is
and –I power minimum–R power
is maximum is minimum.
–R power is
maximum
 Thus according to stability of anions o-derivative Anion is stabilised by -R and – effect of NO 2
will be more acidic than p-derivative which will be group
more acidic than m-derivative. But result is as
follows in case of nitrophenols, p-derivative is
more acidic than o-derivative which is more acidic
than m-derivative. In o-derivative , there is
hydrogen bonding which decrease acidity. Thus
order of acidity is as follows :
p-derivative > o-derivative > m- derivative > phenol.

Acidity in decreasing order

(V)

(C) Acidity of aromatic acids Thus decreasing order of the stability of these
Acidity of substituted acids Ortho substituted anions is follows :  > >  > V
banzoic acid is always a stronger acid than
m- and p-derivative due to the ortho effect. We know that ortho derivative is the most acidic
Case I : When group is –R and –  group. therefore decreasing order of acidity of these
acids is as follows :
o-derivative>p-derivative>m-derivative>benzoic acid

Acidity in decreasing order

(D) Basicity of nitrogen containing compounds :
(i) Basicity of Aromatic Amines : Basicity
of nitrogen containing compounds  Electron
density on nitrogen.
 Carbon becomes electron In aromatic amines, lone pair of elecrons present
O O deficient due to resonance
 on nitrogen is delocalised, hence electron density
C O effect of NO2group. This decrease due to resonance.
 N electron deficient carbon withdraws
electron from the the carboxylate Thus :

O group by inductive effect. 1
Basicity  Number of resonating structures
Thus, anion is stabilised by –R and – effect and
–  power is maximum. Structure Number of resonating
structures

O ••
C 6H5 NH2 4
C O
••
C 6H5 – N H – C6H5 7
NO2
••
C 6H5 – N– C 6H5
()
| 11
Anion is stabilised only by – effect of NO group C 6H5

Basicity in decreasing order

(ii) Basicity of other Nitrogen Containing
Compounds : Basicity depends on the
following factors :
(1) Electronegativity of nitrogen

1
Basicity  Electronegativity of nitrogen

()
 Example :  
group () (II) –  group
hence amines are more basic than hydroxyl
amines.
(a)

() is more basic than ()

•• •• ••
R – N H2 R – CH = N H R – C N –  group +  group
hence () is more basic than ()
(b)
(3) Resonance : Delocalisation of lone pair of
Electronegativity in increasing order Basicity in electrons present on nitrogen decreases basicity.
decreasing order
sp3 ••
(c) CH3 – CH2 – CH3 – N H2

sp 2 ••
CH3–CH = CH – N H2
sp ••
CH3–C  CH – N H2 () ()
hence () is more basic than ()
(iii) Basicity of substituted Anilines : Para
Electronegativity of carbons substituted aniline is more basic than ortho
attached to amino group is in increasing order substituted aniline and the effect is known as
hence basicity is in decreasing order. para effect.
Case I : When group has –R has – effect.

(d)

Hence  is more basic than 

(2) Inductive effect

Basicity  + I power of the group on nitrogen

1
Basicity  –  power of the group on nitrogen

•• ••
R – N H2 N H2 – OH Thus order of basicity is as follows :
 aniline > m-derivative > p-derivatives > o-derivative Arrange these compounds in decreasing order
of their basicity :
Basicity in decreasing order (A) a>b> c > d (B) b > c > a > d
Case-II Effect of cross conjugation on (C) d > a > c > b (D) d > a > b > c
basicity :
Sol. (C) (+ M) nature of CH3 group increase

CH3 – CH3 – Ex.23 Which free radical is the most stable -

Due to delocalisation and – I effect of CO group,  
amides are less basic than amines. (A) C6H5 – C H2 (B) CH2 = CH – C H2

 
C6H5 – – (C) CH3 – C H – CH3 (D) CH3 – C– CH3
In this amide there is cross conjugation which |
increases basicity; thus C6H5CONH2 is more CH3
basic than CH3CONH2.  bond of C = O group
is in conjugation to benzene ring as well as lp of Sol. (A) more resonance in (A).
NH2 group.
Case-III Basicity of different nitrogen Ex.24 Which carbocation is the most stable -
compounds in decreasing order :

Guanidine  Aliphatic a min es 

NH3  Aromatic a min es   min e 
Amide  Cyanide (A) (B)
               
Basicity in decrea sin g order


Application of mesomeric effect CH2

Ex.21 Consider the follownig carbocations - (C) (D)

  Cl
(a) CH3 – C H2 (b) CH2 = C H
Sol. (B) + m effect of OH is highest, which
 
(c) CH2 = CH – C H2 (d) C6H5 – C H2 decrease magnitude of charge thus stability
increases.
Stability of these carbocations in decreasing
Ex.25 Which of the following carboxylic acids is
order is - most acidic in character -
(A) d > c > a > b (B) d > c > b > a (A) o-methyl benzoic acid
(C) c > d > b > a (D) c > d > a > b (B) m-methyl benzoic acid
(C) p-methyl benzoic acid
Sol. (A) d have more resonating structure than (D) Benzoic acid
(C) Sol. (A) due to ortho effect.

Ex.22 Consider the following compounds - 1.3 Electromeric Effect

It is temporary effect and operates only in
 - electrons (i.e. multiple bonded compounds)
in presence of some attacking reagents. It means,
it is externally induced in a molecule.
In polar bonds, in presence of attacking reagents,
a complete transfer of electron (one of  e– pair)
(a) (b) (c) (d) to more electronegative atom takes place. e.g. in
in presence of nucleophile like CN–,
HSO3–,  electrons shifts over to O.
 (ii)  (C – H), positive charge conjugation :
+ CN– -------- – O–
This type of conjugation occurs in alkyl
or carbocation.
   
+ H+ + Br– -------- + –C C H3 – C H2 C H3 – C H – C H 3

(H+ ion presence results in polarisation)  
C H3 – C – C H3
Electromeric effect  |
C H3

Ex.26 Electromeric effect -
(A)comes into play at the demand of (iii)  (C – H), odd electron conjugation : This
attacking reagent type of conjugation occurs in alkyl free
(B)involves displacement of electrons in a radicals -
sigma bond
   
(C)comes into play in the molecule when at C H3 – C H2 C H3 – C – C H3
least one atom has unshared pair of 
sp2 |
electrons C H3

(D) involves the distortion of the electron cloud
Sol. (A) (D) Resonating structures due to
Ex.27 Which statement is correct for electromeric hyperconjugation may be written involving “no
effect - bond” between the alpha carbon and hydrogen
(A) It is a temporary effect atoms.
(B) It is the porperty of  bond
(C) It takes place in presence of reagent,
i.e., electrophile or nucleophile
(D) All are correct
Sol. (D)

1.4 Hyperconjugation
When (C – H) sigma electrons are in conjugation
to pi bond, this conjugation is known as
 (C – H),  conjugation, excessive conjugation
or hyperconjugatioon.
Structural requirement for hyperconjugation:
(A) Compound should hav e at least one
sp2-hybrid carbon of either alkene alkyl
carbocation or alkyl free radical.
(B) -carbon with respect to sp2 hybrid carbon
should have at least one hydrogen.
If both these conditions are fulfilled then H
hyperconjugation will take place in the | 
moelucle. H – C  CH – C H2
(C) Hyperconjugation is of three types :
H
(i)  (C – H),  conjugation : This type of
conjugation occurs in alkenes. In the above resonating structures there is no
covalent bond between carbon and hydrogen.

From this point of view, hyperconjugation may be
C H3 – CH = CH2 CH3 – C H – CH = CH2 regarded as “ no bond resosnance ”.

|
CH3 Application of Hyperconjugation :
CH3 (A) Stability of Alkenes : Hyperconjugation explains
|
CH3 – C – CH = CH2 the stability of certain alkenes over other alkenes:
| (i) Stability of alkenes  Number of alpha
CH3 hydrogens  Number of resonating structures
 CH3–CH=CH2 CH3–CH2–CH=CH2 (i) Number of resonating structures in increasing
CH3– CH –CH = CH2 order
| (ii) Stability is in increasing order
CH3 (E) Electron releasing (or donating) power of R
 in alkyl benzene : CH3 – (or alkyl group) is
+R group, ortho-para directing group and
Stability in decreasing order
activating group for electrophilic aromatic
substitution reaction because of the
hyperconjugation.


Number of alpha hydrogens in decreasing order
stability of alkenes in decreasing order
(B) Carbon-carbon double bond length in The electron donating power of alkyl group will
alkenes: As we know that the more is the depends on the number of resonating structures,
number of resonating structures, the more will be this depends on the number of hydrogens present
single bond character in carbon-carbon double on -carbon. The electron releasing power of
bond. some groups are as follows -
The bond length between carbon-carbon double
bond  number of resonating structures. CH3
|
(C) Stability of Alkyl Carbocations : Stability of CH3 CH3 – CH2 CH3 – C –
alkyl carbocations  number of resonating |
structures  number of hydrogens. CH3

  
C H3 CH3 – C H2
Electron donatnig power in decreasing order due
to the hyperconjugation
 
CH3 – C H – CH3 CH3 – C – CH3 Reverse Hyperconjugation :
| The phenomenon of hyperconjugation is also
CH3
observed in the system given below :

(i) Number of -hydrogens in increasing order X
|
(ii) Stability in increasing order – C– C = C
|
(D) Stability of Alkyl free radicals : Stability of
alkyl f ree radicals can be explained by where X - halogen
hyperconjugation. Stability depends on the In such system the effect operates in the reverse
number of resonating structures. direction. Hence the hyperconjugation in such
structure system is known as reverse hyperconjugation.
    
C H3 CH3– C H2 CH3– C H –CH3 CH3– C – CH3 Cl
| 
CH3 C l – C  C H – C H2
|
0 4 7 10 Cl
No of resonating
structures

 Cl
 | 
C l C  CH – C H2 as -
|
Cl

 
Cl
| 
Cl – C  CH – C H2

Cl

The meta directing influence and dectivating effect
of CX3 group for electrophilic aromatic substitution  ....
reaction can be explained by this effect.

Ex.30 Resonance energy of benzene is

36 Kcal mol–1 but that of toluene is 37.5
Kcalmol–1. Why ?

Sol. Greater resonance energy of is caused

by hyperconjugation effect of CH3.

Hyperconjugation
Ex.31 W hich of f ollowing has maximum
Ex.28 Which of the following alkenes will react hydrogenation energy.
fastest with H2 under catalytic hydrogenation (A) CH3 – CH2 – CH = CH2
conditions -
(B) CH3 – CH = CH – CH3
cis

(A) (B)
(C)

(D) All have the same

Sol. (A)
(C) (D) Due to lower no. of  'H' it is unstable than
others.

Sol.(A)
Ex.32 W hich of the following is most stable
carbocation.
Ex.29 M effect of -CCl3 can be explained on the + +
basis of (A) CH3 – CH2 (B) CH3 – CH – CH3
+ +
(A) – effect (C) CH3 – C – CH3 (D) (CH3 – CH2)3 C
(B) + R effect |
(C) negative hyper conjugative effect CH3
(D) none 
Sol. (C) There is a negative hyperconjugative in Sol. (C) Because CH3 – C – CH3 has '9'  H
|
CH3
atoms which is maximum in all f our
examples.
2. BOND FISSION (C) The energy required for heterolytic bond
fission is always greater than that for
Breaking of covalent bond of the compound is homolytic bond fission due to electrostatic
known as bond fission. A bond can be broken by force of attraction between ions.
two ways:
3. REACTION INTERMEDIATES
2.1 Homolytic Fission :
Reaction intermediates are generated by the
Occurs in gas phase or in non-polar solvents and
breaking of covalent bond of the substance. They
is catalysed by reagents. In such fission free
radicals are formed. Here the bond pair is equally are short -lived species and are highly reactive.
shared after the fission. There are six important types of reaction -
intermediates.
AB  A° + B° (free radicals) (1) Carbocation (2) Carbanion
Condition for Homolytic Bond Fission : (3) Free radical (4) carbene
Homolysis takes place in the presence of (5) Nitrene
peroxide, UV light, heat ( 500°C), electricity and
free radical. The process is known as initiation of 3.1 Carbocations
free radical reaction. (1) An organic species which has a carbon
(i ) Peroxide
atom bearing six electrons in its outermost
A : B (    Aº + Bº orbit and has a positive charge is called a
ii) h
( iii)  carbocation.
( iv ) Electricity
or (2) Carbocations can be classified into the
( v ) Free Radical
following groups :
• • (A) Alkyl carbocations : When positive charge
CH3 – H  h
 C H3 + H is present on the alkyl carbon, carbocation
 is known as alkyl carbocation.
methyl free radical  Stability of alkyl carbocations can be
(i) Homolytic bond fission gives free radical as explained by
the reaction intermidiate. (i) Inductive effect and
(ii) Reaction mechanism of the reaction is known (ii) Hyperconjugation
as free radical or homolytic mechanism. Stability of carbocation depend on the + I &
2.2 Heterolytic fission : – I group as follows :
Occurs in polar solvents, catalysed by acids or Stability  + I power of group
bases, greatly influenced by polarity of solvents.  According to these two effects the stability
Here, the ions are formed. In an organic order is as follows :
compound such as R - G, two types of ions are
formed.
R - G  R+ + G –    
R  C R R  CH  R R  C H2 C H3
(R+ is known as carbonium ion )
|
R - G  R– + G + R
(R– is known as carbanion ion )
Stability in decreasing order
The factor which favours heterolysis is a greater
difference of electronegativity between A and B. 1
Thus Stability   I power of group
(A) Heterolytic bond fission gives carbocation or
carbanion as reaction intermediate.    
I – CH 2 Br – CH 2 Cl – CH 2 F – CH 2
(B) Mechanism of the reaction in which
heterolytic bond fission takes place is known
as heterolytic mechanism or ionic –I power of halo group increases
mechanism. Stability increases (due to p-poverlapping)

 If -atom with respect to carbocationic carbon

has one or more than one lone pair of
electrons then lone pair of electrons strongly
 stabilises a cabocation due to the
delocalisation. 
C6H5  C C6H5 C6H5– –C6H5 C6H5– 2
Alkoxy and amino groups are important |
substituents for such type of carboacations. C6H5
No of 10 7 4
 resonating
is more stable than R  C R
| Structures
R

is more stable than R  C R (i) Number of resonating structures in decreasing
| order.
R (ii) Stability in decreasing order
(iv) Phenyl methyl carbocations are more stable
(B) Vinyl Carbocation : When positive charge
is present on vinylic carbon then carbocation than allyl carbocations due to the number of
resonating structure.
is known as vinyl carbocation ; CH 2 = . (E) Aromatic Carbocations :
This carbocation is the least stable because (i) Cations in which positive charge is present
positiv e charge i s present on the on carbon of aromatic system is known as
electronegative carbon. aromatic carbocation.
(ii) Aromatic carbocations are so stable that
(C) Allyl carbocation : (CH2 =CH – 2) even their solid states are known. For
(i) When positive charge is present on the allylic example tropolium carbocation as tropolium
carbon of the allyl group, the carbocation is bromide is a yellow solid. It fact tropolium
known as allyl carbocation. carbocation is about 1011 times more stable
(ii) Allyl carbocations are more stable than the than triphenyl methyl carbocation.
alkyl carbocations due to the resonance. Allyl (iii) Cations obeying Huckel (4n + 2) rule are
carbocations are stabilised by delocalisation stable because they are aromatic and there
(or resonance). is complete delocalisation of positive charge.
(D) Phenyl methyl carbocations : (3) Stability of different types of
(i) When positive charge is present on benzyl carbocations in decreasing order :
carbon, carbocation is known as phenyl
methyl carbocation.
(ii) Phenyl methyl carbocations are of three types:

C6H5 – 2 C6H5 – – C6H5

Benzyl Carbocation Diphenyl methyl   
(C6H5)3 C > (C6H5)2 C H > C6H5 – C H2 
or carbocation
  
Phenyl methyl (2°– carbocation) CH2 = CH – C H2  R – C – R > R – C H – R
carbocation |
(1°–carbocation) R
 
 > R – C H2 > CH2 = C H
C 6H5  C C6H5
| (4) Characteristics of carbocations (except
CH6H5 vinyl carbocation) :
(i) It has three pairs with empty p-orbital. Its
Triphenyl methyl hybridisation is sp2.
carbocation (ii) Shape of carbocation is trigonal planar.
(3°–carbocation)
(iii) Stability of phenyl methyl carbocations can
be explained by resonance.
Structure :
 Note : Triphenyl methyl carbocation has % s-character of carbanionic carbon
propeller shape.
(iii) There are six electrons in the outermost CH3 – CH2 = CH
orbit of carbocationic carbon hence its    
octet is incomplete. All the six electrons
sp3 sp2 sp
are paired.
(iv) It is charged electrophile.
(v) It is diamagnetic in character. (i) % s-character in increasing order
(vi) It is formed by heterolytic bond fission. (ii) Stability in increasing order.
(vii) It reacts with nucleophiles. (B) Inductive effect : Stability of carbanions
(5) Reactions which take place by the depends on the + or – group as follows :
formation of carbocation as reaction
intermediate : In the following type of 1
reactions product formation takes place by (a) Stability    power of group
the formation of carbocation as reaction
intermediate.  

(i) SNI reactions C H3 R C H2 R C R
(ii) EI reactions
(iii) Electrophilic addition reaction of alkenes R
and alkynes.
3.2 Carbanions (i) + power in increasing order
Anion of carbon is known as carbanion. (ii) Stability in decreasing order.
Carbanion carries three bond pairs and one lone (b) Stability of carbanions  – power of the
pair, thus making the carbon atom negatively group
charged. So carbanion may be represented as
For example :

Br
(1) Characteristic of Carbanions :
Cl F
(i) Hybridisation and geometry : Alkyl carbanion
has three bond pairs and one lone pair. Thus
hybridisat ion is sp 3 and geometry is (i) – power of halo group is in increasing order
pryamidal. (ii) Stability in increasing order.
(C) Delocalistion or Resonance : Allyl and
banzyl carbanions are stabi lised by
delocalisation of negative charge.
Note : Geometry of allyl and benzyl cabanion
is almost planar and hybridisation is sp2. CH2 = CH – C6H5 –
(ii) There are eight electrons in the outermost 2 4
orbit of carbanionic carbon hence its octet is
complete. (C6H5)2 – (C6H5) –
(iii) It behaves as charged nucleophile. 7 10
(iv) It is diamagnetic in character because all
eight electrons are paired.
(i) Number of resonating structures is in
(v) It is formed by heterolytic bond fission. increasing order
(vi) It reacts with electrophiles.
(ii) Stability is in increasing order
(2) Stability of carbonions : The stability of (D)Stabilisation by Sulphur and Phosphorous:
carbanion may be explained by Attachment of carbanionic carbon of a sulphur
(A) Electronegativity of carbanionic carbon : and phosphorus atom causes an increase in
carbanion stability.
StabilityElectronegativity of carbaionic carbon
The cause of stabi lity is due to the
 delocalisation of negative charge of carbanion (i) Condensation reactions of carbonyl
by vaccant d-orbital (p–d bonding) of compounds, i.e., aldol condensation, Perkin
phosphorus and sulphur. reaction, reformatsky reaction etc.
(E) Stabilisation by >C=O, –NO 2 and CN (ii) Condensation reactions of ester; Claisen
groups present on carbanionic carbon : condensation.
These groups stabi lise carbanion by (iii) Wittig reaction.
resonance effect 3.3 Carbon Free Radical
(1) Carbon free radicals are odd electron species
in which carbon atom bears the odd electron.
. (2) Homolytic bond fission of a covalent single
bond gives rise to free radicals.
Carbanion Enolate ion
(3) There are seven electrons in the out most
() () orbit of carbon of carbon free radicals.
(4) Owing to the presence of an odd electron; a
carbon radical is paramagnetic in nature. Due
to this reason free radicals are highly
reactive.
() () (5) The structure of the carbon free radicals are
Contribution of structure () will be more very difficult to predict. They have planar to
than () because in () negative charge is pyramidal geometry depending upon the
present on electronegative oxygen. groups and atoms attached to the carbon
(F) Stability of Aromatic Carbanions : atom having odd electron. For example,
(i) Anions in which negative charge is present methyl free radical is planar. On the other
on carbon of aromatic system is known as hand trif luoro methyl f ree radicals is
aromatic carbanions. pyramidal. Alkyl free radicals have also
(ii) Aromatic carbanions are most stable pyramidal geometry.
carbaions. (6) Free radicals are neutral electrophiles.
(iii) Anions obeying Huckel rule are stable (7) Free radical generally reacts with free radical.
because they are aromatic and there is (8) Stability :
complete delocalisation of negative charge. (A) Stability of Alkyl free redicals : Stability
of alkyl free radicals can be explained by
hyperconjugation and number of resonating
structures due to the hyperconjugation. The
Cyclopentadienyl anion decreasing order of stability of alkyl free
(3) Stability of different type of carbanions radicals is as follows :
in decreasing order : tertiary > secondary > primary > CH3
Aromatic carbanion > Benzyl carbanion > Both electron withdrawing group such as
carbonyl, cyano and nitro and electron-
Allyl carbanion > CH  > CH2 = > donating groups such as methoxy and
Alkyl carbanion dimethyl amino have a stabilising effect on a
radical at an adjecent carbon due to
resonance.
(B) Stability of Allyl and Benzyl free radicals:
(i) Stability of these radicals can be explained
by delocalisation or resonance.
Structure :
(D) Reactions in which product formation   
(C6H5)3 C > (C6H5)2 CH > C6H5– C H2 >
takes place by formation of carbanion
as reaction intermediate : In the 10 7 4
following reactions product formation takes
place by the formation of carbanion as
reaction intermediates :
 (C) presence of even number of electrons

CH2 = CH – C H2 (D) assiociated with high stability
Sol. (B) Presence of odd electrons
2
No. of resonating structure : Ex.35 Most stable carbonium ion is :

(A) CH3— 2 (B) H2CHCI 2

(i) Number of resonating structures in decreasing
order (C) H2CH2CI (D) H2—CH2NO2
(ii) Stability in decreasing order Sol. (A) + I group stabilise carbocation
(ii) Allyl and benzyl radical are more stable than
Ex.36 Which of the following statements does not
alkyl radicals. Triphenyl methyl radical and apply to free radical chain reaction :
similar radicals are stable enough to exist in (A) it may be initiated by ultraviolet rays
solution at room temperature. (B) one mole of product is obtained for each
Stability of different free rad icals in mole of free radical produced in the
decreasing order : initiation step
(C) it is not affected by changes in polarity
  
(C6H5)3 – C> (C6H5)2 – CH > C6H5 – CH2 > of solvent
(D) it is inhibited by the presence of certain
  reagents
CH2 = CH  C CH3 > CH2 = CH – C H –CH3 > Sol. (C)
| Ex.37 Which of the following statement is correct:
CH3
 (A) allyl carbonium ion (CH2=CH—
CH2 = CH – C H2 > Ter alkyl free radical > See 2) is
more stable than propyl carbonium ion

(B) propyl carbonium ion is more stable than
alkyl free radical > P-alkyl free radical > C H3
allyl carbonium ion
Stability of the same type of alkyl free radical  (C) both are eqully stable
Number of carbons in alkyl free radical
(D) none of these
Free radical reactions : Chemical reaction
Sol. (A) allyl carbocation is resonance stablised
which takes place in the presence of peroxide,
heat h, electricity or free radical is known as
free radical reaction. Ex.38 W hich one is a 1° carbocation of the
 Amount of energy needed for homolysis of a following:
covalent bond depends upon the stability of
(A) CH3 2 (B) CH3 H—C2H5
resulting free radical as reaction intermidiate
(R) (C) (CH3)2 H (D)(CH3)3
1 Sol. (A)
Energy needed  Stability of free radical as R
Ex.39 Which of the following is the correct order of
stability of free radicals :
Reaction Intermediate (A) benzyl > allyl > 3° > 2°
(B) allyl > benzyl > 3° > 2°
Ex.33 The number of electrons present in the
 (C) allyl > 3° > 2° > benzyl
valency shell of carbon of CH 3 C H2 ion (D) benzyl > 3° > 2° > allyl
bearing +ve charge :
(A) 8 (B) 7 (C) 6 (D) 4
Sol. (C) Carbocation consist 3 bond pair in outer
most orbit. Sol.(A)

3º & 2º
CH 2  CH  CH2
Ex.34 Which one is the characteristic feature of a
free radical :
4-R.S 2-R . S NO-R . S
(A) presence of negative or positive charge
(B) presence of unpaired electron 3º is more stable than 2º
Ex.40 Which one of the following is sec-allylic except cations of A, A group elements,
carbocation :
Al+++ and .

(A) C H2 –CH = CH2 (B) Neutral electrophiles : It can be classified
 into three categories :
(B) CH3–CH = CH – C H
2 (B) Neutral covalent compound in which central
 atom has incomplete octet is neutral
(C) C6H5 –CH = C H electrophile,


(D) CH3– C H –CH = CH2 BrCl 2, BH3, ZnCl, AlX3, FeX3, C H3 ,
Sol. (D) +ve charge containing carbon joined with
two other carbon, also it is alternate position •• ••
of double bond. C H2 , C X2
(B)Neutral covalent compound in which central
Ex.41 Which among the following statements is atom has complete or expended octet and
correct ? central atom has unfilled -d-shell is neutral
  electrophile
(a) C F2 is more stable than C Cl2
SnCl 4, SiCl 4, PCl 5, SF 6, F 7
  (B)Neutral covalent compound in which central
(b) C Cl2 is more stable than C Br2
atom is bonded only with two or more than
 two electronegativ e atoms is neut ral
(c) Singlet C H2 is more stable than triplete electrophile.
•• BeCl 2, BX3, AlX3, FeX3, SnCl 4, PCl 3
C H2
••
(d) singlet carbene has planar geometry PCl 5, NF 3, C X 2 , CO 2, SO 3,CS2, CX4
(A) a, b and d (B) b and d
Note :
(C) a, b and c (D) b,c and d
Sol. (A) (i) Cl 2, Br 2 and I 2 also behave as neutral
electrophiles.
(ii) Electrophiles are Lewis acids.
4. REACTION REAGENTS
4.2 Nucleophiles
Organic reagents can be classified in two Nucleophiles can be classified into three
categories : categories :
(A) Electrophile : Electron deficient species or (A) Charged nucleophiles : Negatively charged
electron acceptor is electrophile. species are charged nucleophiles.
(B) Nucleophile :  Electron rich species or
electron or electron donor is nucelophile. , O , R – , C 3, , H, R–
4.1 Electrophiles (B) Neutral nucleophiles : It can be classified
It can be classified into two categories : into two categories :
(A) Charged electrophiles (E ) (IB) Neutral covalent compound, in which central
(B) Neutral electrophiles (E) atom has complete octet, has at least one
lone pair of electrons and all atoms present
(A) Charged electrophiles : Positively charged
on central atom should not be
species in which central atom has incomplete
electronegative, is neutral nucleophile.
octet is charged electrophile
, R– , R2 , R3 , –NH2
H  , X  R , , = O, (Nitrogen nucleophile)

H– –H, R– –H, R– –R

Note : All cations are charged electrophiles (Oxygen nucleophiles)

H– –H, R– –H, R – – R
(Sulphur nucleophiles)
  Nucleophile strength increases down a
H3, R H2, R2 H, R3
(Phosphorus nucleophiles) column of the periodic table (in solvents that
can have hydrogen bond, such as water and
(B) Organic compound containing carbon, alcohols). For example :
carbon multiple bond/bonds behave as
nucleophile. <
Alkenes, Alkynes, Benzene, R3N < R3P
CH2 = CH –CH = CH2, CH2 = CH – C  CH
(C) Ambident nucleophile : Species having two < < <
nucleophilic centres, one is neut ral
(complete octet and has at least one lone increasing nucleophilic strength
pair of electrons) and other is charged decreasing base strength
(negative charge) behaves as ambident  Steric bulk decreases nucleophilicity . For
nucelophile. example :

   –     < H

Note : weaker nucleophile stronger nucleophile

(A)Organometallic compounds are Stronger base weaker base
necleophiles.
(B)Nucleophiles are Lewis bases. Reaction reagent
Org anic comp ounds whi ch behave as
electrophile as well as nucleophile : Ex.42 Which among the following species is an
Organic compound in which carbon is bonded ambident nucleophile :
with electronegative atom (O, N, S) by multiple (A) Ethene (B) Benzene
bond/bonds behaves as electrophile as well as (C) Cyanide ion (D) Acetone
nucleophile. Sol. (C) Cyanide ion is an ambident nucleophile
O O O O
|| || || || Ex.43 A nucleophile is :
R CH, R CR, R  C  OH , R  C  Cl (A) electron-rich species
O O (B) electron-deficient species
|| || (C) a Lewis acid
R  C  OR , R  C  NH2 , R–CN, (D) Positively charged species
Sol. (A) A nucleophile is electron-rich species
R– 
Note : During the course of chemical reaction Ex.44 Which is not a nucleophile –
electrophile reacts with nucleophile.
(A) NH3 (B) R—O—R
Nucleophilicity versus basicity (C) BF 3 (D) HOH
 If the nucleophilic atoms are from the same Sol. (C) BF 3
period of the periodic table, strength as a
nucleophile parallels strength as a base. For Ex.45 Which behaves both as a nucleophile and
example :
electrophile :
H2O < NH3
(A) CH3NH2 (B) CH3OH
   (C) CH3CN (D) CH3CI
CH3OH  H2O < CH3 CO 2 < CH3 O  O H
Sol. (C) CH3CN
increasing base strength
increasing nucleophile strength
5. REACTION MECHANISM exclusive replacement of tertiary hydrogen atom.
Chlorine, on the other hand is less selective
There are mainly three categories into which major
than bromine Fluorine is even less selective than
organic reactions are classified (for understanding
of the reaction mechanisms). chlorine and gives equal % age of substituted
products. (Refer to reactions of alkanes in next
3.1 Substitution Reactions
chapter)
3.2 Addition Reactions
Wurtz reaction
3.3 Elimination Reactions
2 C2H5Br + Na  2C2H5° + NaBr
5.1 Substitution (Displacement) Reaction :
C2H5° + C2H5°  C4H10
The replacement of an atom or group from a
molecule by a different atom or group is called
as substitution reaction. (b) Nucleophillic Substitution
e.g. RX + NaOH (aq)  ROH + NaX They are divided into two categories
(i) SN2 mechanism :
AlCl3
C6H6 + RX  These are Biomolecular reactions. When rate
 C6H5R + HCl
of reaction depends upon concentration of
both substrate (organic compound) and the
These reactions are further divided into three
types depending upon the mechanism. nucleophile, the reaction is said to follow SN2
(a) Free - radical (b) Nucleophillic (2nd order) mechanism
(c) Electrophillic e.g. consider the hydrolysis of CH3Cl
Mechanism of Substitution Reactions H3C+ – Cl– + OH–  H3C – OH + Cl–
(a) Free radical substituion : The nucleophile OH – attacks from the
Halogenation in alkanes opposite side of Cl atom, and a transition
state results where both OH– & Cl – are
Cl2 h  
CH4  partially bonded to carbon atom.
 CH3Cl + HCl
Transition state :
(Cl° free radical is generated & attacks methane)
h  
Cl2   2 Cl°
(CH3° free radical is produced and forms CH3Cl  HO – CH3 + Cl–
by attacking Cl2)
Cl° + CH4  CH3° + HCl
CH3° + Cl 2  CH3Cl + Cl° (ii) SN1 mechanism :
(Cl° free radical attacks again and a sort of chain These are Unimolecular reactions. When the
reaction occurs ) rate of nuceleophillic substitution depends
Cl° + CH3Cl  Cl CH2° + HCl only on the concentration of the substrate,
CICH2°+ Cl2  CH2Cl 2 + Cl° the reaction is first order and is respresented
(The chain propagates like this till the formation by SN1.
of CCl4) e.g. : hydrolysis of tertiary butyl bromide
NOTE 1 : It follows two step process :
The chlorination of ethane, C2H6 gives two  heterolytic fission forming carbonium ion.
isomers in presence of sunlight.
C 2H 6 Cl2 h  
bCH g C  X bCH g C
3 3 3 3

 X
  C 2 H5 Cl + HCl
(Slow step)
Cl2 h  
C2H5Cl   CH3CHCl2 + CH2 Cl – CH2Cl  Attack of nucleophile on planar carbonium
The Bromine is less reactive toward alkanes (in ion.
general) than chlorine. But bromine shows ability
to identity among different types of hydrogen atom bCH g C
3 3

b g C  OH
 OH  CH3 3

(i.e. primary, secondary and tertiary). It gives (fast step)

NOTE: 1
 Stronger is the nucleophile, more is the
chance of SN2 mechanism.
(large & easily polarised groups are stronger
nucleophiles) (planar)
 more is the concentration of nucleophile, more
is the chance of SN2 mechanism.
 presence of a polar medium, favours SN1
mechanism.  Now Nu– can attack from either side (as
(polar medium favours heterolytic fission) carbonium ion R+ is planar)
 ease of SN1 mechanism : benzyl > allyl >
30 > 20 > 10 > methyl > phenylhalide
(depends upon stability of carbonium ion)
 ease of SN2 mechansim : Phenyl > methyl >
1° > 2° >3°>allyl>benzyl halides.

NOTE: 2
In SN2 mechanism, Nu– attacks from back
side i.e. side opposite to halide atom.


50% of configurations are (+) type

optically active Transition state

(+) configuration

50% of configurations are (-) type :

optically active
(–) configuration
Hence in SN1 mechanism, a racemic mixture
This means in SN2 mechanism, the inversion
is formed. The above discussion provides an
of molecules takes place i.e.if the original
reactant molecules is dextro–rotatory (+), the evidence for SN1 & SN2 mechanisms.
product formed is levo–rotatory (–). NOTE : 4
So in S N 2 mechansim, the nucleophile The nature of solvent also affects the
attacks the substrate from back side and mechanism of the reaction e.g. more polar
forms an intermediary transition state and solvent favours SN1 mechanism because of :
forms a molecule with opposite configuration.
 The formation of carbonium ions is easy
This means that there is complete inversion
which is also refers to a Walden Inversion.  The ions formed are easily solvated.
NOTE : 3 The ionising power of solvent depends upon
 In SN1, first carbonium ion is formed which is its dielectric constant. e.g. the order of
sp2 hybridised & planar. ionising power of some solv ents is
H2:O HCOOH CH3 OH  C 2H5 OH CH3 COOH
(c) Electrophillic Substitution :
Substitution in benzene ring f ollows
electrophillic substitution.
e.g. bromination of benzene. + H+
FeBr
C 6H6  Br2  
3
 C 6H5Br  HBr

Mechanism :
NOTE:1
 Formation of electrophile :
In benzene derivatives (C6H 5 – G), the

Br  Br  FeBr3  Br  FeBr4 functional group G can also be classified on
basis of their polar nature as : Activating or
 Br+ attacks benzene due to nucleophillic
Deactivating.
character of ring :
An activating group (or an electron donating
group) is one which makes benzene more
Br H
reactive than benzene itself. Such groups are
+
+ : – NH2, –OH, –OR. etc.
+ Br
A de–activating group is one which makes
benzene less reactive than benzene itself.
Such groups –COOH, –C=O, –CHO, NO2, –
CN etc.
Br
NOTE: 2
The presence of activating groups in benzene
+ H•
ring increases the ease of electrophillic
substitution, whereas the deactivating groups
do just the opposite.
Br H Br H
NOTE: 3
+
Directive influence of substituents on
Benzene
+
The various groups are classified as electron
donating and electron withdrawing. Those
Br H Br H
+ that withdraw electrons inductively (polar
+ effect) are said to exert an –  effect and
those withdraw electrons conjugatively are
said to exert a – M effect. Similarly +  and
aromatic carbonium ion is resonance stabilised + M effect terms are used for electron
 elimination of proton : donating. The following table illustrates the
directive influence of various functional groups
over benzene for second substitution.
 Very strong  O bg
 I, ( ) M
NR2
NHR
Strong
(activating)
NH2
OH
bg
 I  bg
M o, p  Directors

OR
OCOR
Moderately strong
b
activating g NHCOR
C 6H5
bg
 I  bg
 M o, p  Directors

b
Weak activating g CH3
CR3 bg
 I o, p  Directors
F(~ H)
Cl,Br,I
b
Weak de  activating g CH2 Cl
bg
 I () M o, p  Directors
CH  CH  COOH
CH  CH  NO 2
COR
CHO
COOR
b
Strong de  activating g CONH2
COOH bg
 I  bg
 M m  Directors
SO 3H
CN
NO 2
NH3
b
Very strong de  activating g NR3
bg
 I m  Directors

5.2 Addition Reactions

So the major product formed is CH3–HC(Br)–
Reactions in which atoms or groups of atoms are CH3 (Markonikoff’s addition). In all addition
added to a molecule are called addition reactions. reactions, same mechanism is followed.
These are also classified into three types  reactivity of Halogen acids for addition reaction:
depending upon mechanism HI > HBr > HCl
(a) Electrophillic (b) Nucleophillic  reactivity of Halogen : Cl2>Br2>I 2
(c) Free radical NOTE :
Mechanism of Addition Reactions : If an electron withdrawing group is present at one
(a) Electrophillic Addition Reactions : end of alkene, then the addition is reversed. For
Addition of HBr on ethylene example consider addition of
 HBr  H++Br– HCl to 3,3,3 –trichloro propene.
 electrophile (H+) attacks the “ = ” bond Cl3–C–CH=CH2+HCl 
Cl3CH2CH2Cl + Cl3–C–CH(Cl)CH3
(major) (minor)
CH2  CH3 – C+H2
The reason for this is the stability of intermediate
(carbonium ion) carbonium ion.– I ef fect producing group
Seeing incoming electrophile (H + ) decreases stability of carbonium (C+) ions. Try
electromeric effect occurs, and  electron to compare the two possible carbonium ions
cloud is displaced towards one of the carbon formed.
atoms. (I) Cl3–C–CH2–C+H2 (II) Cl3–C–C+H–CH3
 nucleophile (Br–) attacks carbonium ion. In (I) three Cl atoms are at a greater distance
CH3–C+H2+Br–  CH3CH2Br from C+ site, whereas in (II), three Cl atom are
In case of CH3CH=CH2 near to C+ site. Hence –I effect de–stabilises the
CH3  HC+ CH3
carbonium ion (II) to a much greater extent than

CH3 CH  CH2  H  (2° carbonium, more stable) it does in (I).
CH3  CH2  H2 C  (b) Free radical addition :
(10 carbonium, less stable) In presence of peroxide, addition of HBr follows
anti–Markonikoff’s addition (peroxide effect).
 HBr + peroxide  Br° (similar to SN2 mechanism)
(free radical addition takes place) Nucleophile in this case is C2H5O– (ethanolic
KOH) which forms a transition state with (1°)
CH 3CH Br  CH2 alkyl halides.
(1° radical, less stable)
CH3 CH  CH2  Br 0 
CH3HCCH2Br
(2° radical, more stable)
So the major product is CH3–CH2–CH2–Br (anti–
markonikoff’s addition).
NOTE :
HCl and HI do not add similarly in presence of
peroxides. The reaction with HCl fails because of
high H–Cl bond energy. It is not possible to
extract Cl° (radical in this manner). HI does not
add because C–I bond is not of suffcient energy
to promote attack of 1° radical.
(c) Nucleophillic addition reaction :
Addition of CN– to aldehydes & ketones
O
The reactions follows E2 mechanism, just
C 
O 
 CN 
 C like SN2 mechanism and follows saytzeff rule

CN
In presence of CN – (nucleophile)  e’s of
bond are shifted towards more
electronegative oxygen atom (electromeric effect).


CO C  O  CN


 
OH
 CN
 C  O H C NOTE :
CN CN  The reaction rate increases with increasing
5.3 Elimination Reactions : strength of the base :
These reactions involve loss of atoms or group of
atoms from a molecule to form multiple bonds. b g
CH3 COO   HO   C 2H5 O   CH3 3 CO   NH2
CH3CH2X + (alc.) KOH  CH2= CH2 + HCl  The ease of elimination follows :
CH3CH2OH + H2SO 4  CH2= CH2+ H2O C – I > C – Br > C – Cl > C – F
In general, loss of atoms or group occurs from  The order of reactivity is : 3° > 2° > 1°
adjacent carbon atoms to yield an alkene.  The elimination occurs more easily when the
Mechanism of elimination reactions : halides are already unsaturated. e.g.
Elimination reactions are divided into two classes elimination occurs readily in
based on their mechanisms. CH2=CH-CH2CH2Br than in
E2 : bimolecular elimination CH3CH2CH2CH2Br.
E1 : unimolecular elimination  The nature of products of E2 elimination of a
Dehydrohalogenation of alkyl halides : compound having two chiral carbons depends
upon stereochemistry of starting isomers.
 dehydrohalogenation of 1° halides follows E2 Consider dehydrohalogenation of meso
mechanism. compound diphenyl dichloro ethylene.
 CH3
| 
(CH3 )3 C  OH
CH3  C  CH2 CH3  (CH3 ) 3 C  OK    b
H Cl |
Br
C=C
C6H5
C 6H5

bCH3 g2  C  CHCH3  CH2  CbCH3 g CH2CH3

Optically Inactive meso cis isomer Minor Major

6. INTERMOLECULAR FORCES OF PHYSICAL

PROPERTIES
C 6H5 In organic compounds, there exists only covalent
H
bonds. The molecules in organic compounds are
C=C held together through very weak forces which are
of three types : –
C6H5 Cl 6.1 Dipole–Dipole :

e
In a molecule having polar bonds A  B

, j
optically active trans isomer there is an interaction among bond dipole. These
(d l configuration) interactions are called as dipole–dipole
 dehydrohalogenation of 3° halides follows E1 interactions. Due to these molecules are held
mechanism quite strongly.
(similar to SN1 mechanism) 6.2 Hydrogen Bond : (H–F,H–O,H–N)
1st Step : W hen Hydrogen is bonded with F,O,N the
heterolytic fission forming 3° carbonium ion polarisation of H–F,H–O & H–N bond is strong,
(highly stable). hence the dipole–dipole interaction is very–very
strong. Hence the molecules having H–bonding
(CH3)3–C–X  (C3)3–C++X– (slow step)
have abnormally high intermolecular forces.
2 nd step :
6.3 Vander waal forces :
loss of proton (H+) from carbonium ion.
The charge distribution in non–polar molecules
(CH3)2– C+– CH2– H  (CH3)2– C = CH2 can be symmetrical at one particular instant and
(fast step) un–symmetrical at some other, since the
NOTE: electrons are always in motion. At that instant,
When two different alkenes may be formed, the a non polar molecules (s) may be a weak–dipole.
one having more alkylation about double bond is At the moment, the momentary dipole induces
formed consider 2–bromobutane : another short–lived dipole in a nearby molecule
CH3CH2CH(Br)CH3+alc.KOH  and both dipoles will be attracted to each other.
Such interactions are called Vander waal
CH3CH=CHCH3 is major product.
Interactions (forces).
 CH3CH2CH=CH2
Vander waal forces are proportional to -
is minor product.
(a) Surface area of a molecule : Greater is
This is referred to as Saytzeff Rule. The exception the surface area, greater is the number of
to Saytzeff rule comes when the proton to be interactions & hence stronger Vander waal
removed is sterically hindered. e.g. consider forces.
2–bromo – 2 – methyl butane :
(b) Molecular weight of a molecule : Due to
greater number of electrons, greater is Vander
waal force.
The physical properties like M.P. (melting points)
 B.P. (boiling points) and solubilities depend
mainly on nature of bond present in the molecule,
nature of intermolecular forces & molecular weight
of molecule.
6.4 Melting Point : (b) Intra–molecular H–bonding :
 Organic solids, having molecules which are
covalently bonded, and are held together by
vanderwaals molecular forces and by dipole–
dipole interactions, are generally low melting
solids.
 The size and shape of a solid is also a factor
determining its melting point.
(a) Solids composed of large molecules have
high M.Ps. In large molecules, vanderwaal Such H–bonding occurs between different
forces are also stronger. atoms with–in the same molecule (generally
(b) more symmetric a molecule is, the higher is in ring structures). This bonding is also called
its m.p.e.g. neopentane Vs n–pentane. as Chelation. It lowers the melting & boiling
points and solubility. As interaction exist in
CH3 molecules with–in, intermolecular forces
weakens, e.g., compare H–bonding in
| o–nitrophenol and p-nitrophenol. In
CH3  C  CH3 Vs CH3  CH2  CH2  CH2  CH3 o–nitrophenol, intramolecular H–bonding
| occurs, which lowers the boiling point. In
p–nitrophenol, intermolecular H–bonding
CH3 occurs, which increases the boiling point.
neo  pentane n  pentane  Shape also effects the B.P. e.g., branching
always lowers the boiling point. Among the
As neo–pentane is more symmetric & isomers of pentane, n-pentane has highest
compact, its, m.p. is high. neo–pentane B.P. due to larger surface area of zig–zag
packs more efficiently in its crystal lattice chain of carbon atoms.
and hence has higher lattice energy as
compared to non-symmetric n-pentane. 7. SOLUBILITY
(c) In case of geometric isomers, greater
symmetry of trans isomers results is high
The solubility of a compound depends not
m.p. for them.
only on the polarities of solute & solvent, but
e.g.(cis) maleic acid Vs (trans) fumaric acid also on temperature & pressure. Solubility
H  C  COOH follows the rule of “ like dissolves like.”
H  C  COOH
|| ||  The compounds containing –OH groups,
H  C  COOH HOOC  C  H –NH2, –COOH are soluble is H2O due to
maleic acid fumaric acid H–bonding. Not only alcohols, acids and
(m. p.  150 C) b
m. p.  250 C g amines are soluble in water, but to some
extent, ethers are also soluble in water.
In carboxylic acids, even number of carbon atoms
results in higher melting point than in molecules  Another factor important in solubility is the
having odd number of carbon atoms. The cause size of solute molecule e.g. alkanes are
is the symmetry of even’ members. almost insoluble in water, but lower ones
(CH4) are sparingly soluble in water due to
6.5 Boiling Points :
their molecular size being similar to that of
 In organic liquids, the intermolecular forces water molecules.
(cohesive forces) are Vander waal forces,
 In general, one can say that the functional
dipole–dipole interactions which are generally
group f av ours solubility whereas the
weak and hence are low boiling liquids.
hydrocarbon part opposes solubility. The
 In liquids having H–bonding show abnormally larger is the hydrocarbon part, lower is the
high boiling points. Actually Hydrogen bonding solubility of a compound.
influences b.p. in two different manners.
(a) Intermolecular H–bonding :
Such H–bonding enhances the intermolecular
forces & hence high boiling points.
 SOLVED EXAMPLE
Ex.8 Which one of the following orders is correct
Ex.1 Most stable carbanion–
regarding the –I effect of the substituents ?
(A) (CH3)3C– (B) (CH3)2CH– (A) –NR2 < –OR > –F
(C) CH3CH2 – (D) (C2H5)3C– (B) –NR2 > –OR > – F
Sol. Primary carbanion is most stable (C) –NR2 < –OR < –F
(Ans. C) (D) –NR2 > –OR < –F
Ex.2 Which one of the following is strongest Sol. see series of –I effect (Ans. C)
acid -
Ex.9 Which one of the following compounds will
(A) 2-chloropentanoic acid be most easily attacked by an electrophile ?
(B) 3-chloropentanoic acid
(C) 5-chloropentanoic acid
(D) 4-chloropentanoic acid (A) (B)
Sol. 2-chloropentanoic acid, due to more effective
– I effect. (Ans. A)

Ex.3 The most stable carbanion is– (C) (D)

(A) CH3CH2C H2 (B) CH3—CC– Sol. –OH group show (+M) effect and also +m
effect is greater from (–CH3) group.(Ans. D)
(C) CH3CH=C H (D) CH3— C =CH2
Sol. When highly electronegative atom carry –ve Ex.10 The weakest acid among the following–
charge than it is highly stable. (Ans. B) (A) CH3COOH (B) CH3CO2OH
(C) ClCH2COOH (D) CH3CH2COOH
Ex.4 Correct order of nucleophilicity–
O
(A) CH3– < NH2– < OH– < F – ||
(B) F– < OH– <CH3– < NH2– Sol. CH3  C  O  O  H peroxide is week acid.
(C) OH– < NH2– < F– < CH3– (Ans. B)
(D) F– < OH– < NH2– < CH3– Ex.11 The correct order of boiling point for primary
Sol. For same periods nucleophilicity  Basic (1º), secondary (2º) and tertiary (3º) alcohols
Strength. Thus if more E.N. atom consist – is–
ve Charge than stability  & basic strength (A) 2º > 1º > 3º (B) 3º > 2º > 1º
. Thereby nucleophilicity  (Ans. D) (C) 1º > 2º > 3º (D) 2º > 3º > 1º
Sol. On increase branching surf ace area
Ex.5 Hydrogen bonding is maximum in– decrease, thus boiling point decrease.
(A) Ethanol (B) Diethyl ether (Ans. C)
(C) Ethyl chloride (D) Triethylamine Ex.12 Which of the following is most acidic ?
Sol. Due the presence of O–H bond. (A) m-chlorophenol (B) benzyl alcohol
(Ans. A) (C) phenol (D) cyclohexanol

Ex.6 Benzoic acid is less acidic than salicylic acid

because of–
(A) Hydrogen bond (B) Inductive effect Sol.
(C) Resonance (D) none of these
Sol. It is due to ortho effect. (Ans. D)

Ex.7 In a reaction of C6H5Y, the major product

(>60%) is m-isomer, so the group Y is–
(A) –COOH (B) –Cl
(C) –OH (D) –NH2
Sol. –COOH have (–M effect) (Ans. A) –I (Cl) > –  (–C6H5CH2) (Ans. A)
Ex.13 Among the following the strongest base is– Ex.16 In the following compounds–
(A) C6H5NH2 (B) p-NO2–C6H4NH2
(C) m–NO2–C6H4NH2 (D) C6H5CH2NH2

(I) (II) (III) (IV)

Sol. the order of acidity is–
(A) III > IV > I > II (B) I > IV > III > II
(C) II > I > III > IV (D) IV > III > I > II

Sol.
(+I) Primary amine
(Ans. D)
Aromatic primary amine is more basic than
aniline.
Because lone pair delocalised..
Ex.14 Strongest acid out of the following–
(A) CH3COOH (B) ClCH2COOH
(C) CH3CH2COOH (D) (CH3)2CHCOOH
Sol. Acidic strength  –I power of Cl group.
(Ans. B)
Ex.15 Increasing order of acid strength among (Ans. D)
p-methoxyphenol, p-methylphenol, and at meto position +m effect absent thus only
p-nitrophenol is– – effect of –NO 2 is taken in (iii)
(A)p-nitrophenol, p-methoxyphenol, (iv) > (iii) > (i) > (ii)
p-methylphenol
(B)p-methylphenol, p-methoxyphenol, Ex.17 Most powerful leaving group in following–
p-nitrophenol (A) NH2– (B) OH–
(C) CH3 – (D) F–
(C)p-nitorphenol, p-methylphenol,
p-methoxyphenol Sol. Weak base are always better leaving group .
(D)p-methoxyphenol, p-methylphenol, (Ans. D)
p-nitorphenol

Ex.18 (I) (II)

Sol. (III) (IV)

Increasing order of stability is–

(A) I < III < II < IV (B) IV < III < II < I
(Ans. D) (C) III < IV < II < I (D) II < IV < III < I
Sol. (I)  have higher no of covalent bond
+ m (–OCH3) > + m (–CH3)
(II)  have complete octet
(i) < (ii) < (iii) (III)  more E.N. atom consist –ve charge
(Ans. B)
 of acidic strength
Ex.19 Increasing order of acidity in para methyl (I), Ex.21 The compound that is most reactive towards
chloro (II), amino (III), and nitro (IV) benzoic electrophilic nitration is–
acids is–
(A) III < II < I < IV (B) I < II < IV < III (A) Toluene (B) Benzene
(C) III < I < II < IV (D) II < I < III < IV (C) Benzoic acid (D) Nitrobenzene

Sol.

Sol.

Operating
group  +m –  (Ans. A)
 – COOH, & –NO2 group are deactivating
thus they are less reactiv e towards
electrophile nitration then benzene.
 – CH3 group is activating thus it is most
reactive towards electrophic nitration then
benzene.

operating Ex.22 The most unlikely representation of resonance

group  +m –m structures of p-nitrophenoxide ion is–
+ m (CH3) < + m (NH2) (Ans. C)

Ex.20 Increasing order of basic strength of following

compounds is
C6H5NH2, (CH3)3N, (C6H5)2NH, C6H5NHCH3
(I) (II) (III) (IV) (A) (B)

(A) III < IV < I < II (B) III < I < IV < II
(C) I < III < II < IV (D) II < IV < III < I
CH3
|
••

Sol. CH3  N
|
CH3 (C) (D)
(a) lone pair delocalised lone pair localised
(I) (II)

Sol. In III structure, outermost orbit of N–atom

have 10 e which is invalid condition for
lone pair delocalised lone pair delocalised resonance, thus it most unlikely structure.
(III) (IV) (Ans. C)
Thus II is more basic. Ex.23 Consider the following three halides -
(b) Now than apply the theory of power of (1) CH3 – CH2 – Cl
delocalisation which is highest in III, thus it (2) CH2 = CH – Cl
is least basic.
(c) 2° amine is more basic than 1° (3) C6H5 – Cl
thus (IV) is more basic than (I) due to Arrange C – Cl bond length of these
+  effect of –CH3 group. compound in decreasing order -
 (III) < (I) < (IV) < (II) (Ans. B) (A) 1 > 2 > 1 (B) 1 > 3 > 2
(C) 3 > 2 > 1 (D) 2 > 3 > 1
Sol. (Ans. A)
Ex.24 Arrange the following in increasing basic Ex.27 Which one of the carbaions is most stable?
strength-

(a) CH3NH2 (b) (A) (B)

(c) Cl – CH2 – NH2 (d)  – CH2 – NH2

(e) NH3
Correct answer is -
(C) (D)
(A) (a) < (b) < (c) < (e) < (d)
(B) (a) < (b) < (c) < (d) < (e)
(C) (b) < (c) < (d) < (e) < (a)
 
(D) (c) < (b) < (e) < (d) < (a) CH2
 
CH2
–
Sol. CH3 NH2 Sol. NO2
–M
–I –M
NO2
+  – 

 CH2  +
CH2  +
–  –  CN
–M –M
CN
        1
As magnitude of +ve charge  basic strength  Stability  Magnitude of charg e ,
(Ans. C) thus 1 is most stable. Ans.(A)

Ex.25 Arrange in increasing pK a Ex.28 What is the correct increasing order of bond
(a) CH3CH2COOH lengths of the bonds indicated as I, II, III and
(b) CH3CH2CH2COOH IV in following coumpounds -
(c) CH3COOH
Correct answer is-
(A) (c) < (a) < (b)
(B) (b) < (a) < (c) (A) I < II < III < IV (B) II < III < IV < I
(C) (a) < (c) < (b) (C) IV < II < III < I (D) IV < I < II < III
(D) (b) < (c) < (a) Sol. Ans.(D)
Sol. (Ans. A)
Ex.29 Which one of the following chlorides gives
Ex.26 Arrange in increasing basic strength white precipitate with AgNO3 most readily -
(a) Cl – CH2 – COOH (A) CH2 = CH – CH2Cl
(b) Cl – CH2 – CH2– CH2 – COOH (B) CH2 = CH – Cl
(c) Cl – CH2 CH2 COOH
(C) CH3 – CH2Cl
Correct answer is-
(D) (C6H5)2 CH – Cl
(A) (a) < (c)< (b)
(B) (b) < (a) < (c)
(C) (c) < (b)< (a) Sol. Ans.(D)
(D) (a) < (b) < (c)
Sol. (Ans. A)