Booklet 5 - CH 14, 15, 16

© Copyright Reserved.
ALL RIGHTS RESERVED by Universal Books (Praveen Gupta). No part of this book covered by the copyright herein may be
reproduced, transmitted, stored, or used in any form or by any means graphic, electronic, or mechanical, including but not limited
to photocopying, recording, scanning, digitizing, taping, Web distribution, information networks, or information storage and
retrieval systems, without the prior written permission of the publisher.
14. General Organic Chemistry
Tetravalency of Carbon
Carbon is an essential element of organic compounds; it has four electrons in its outer most shell. The electronic configuration of carbon
atom is 1s2, 2s2, 2px1 2py1 2pz0.
According to the ground state electronic configuration of carbon, it is divalent. Tetravalency of carbon can be explained by promoting one
of the 2s 2 -electrons to the unoccupied 2 p z atomic orbital. So the excited state electronic configuration becomes:
1s2, 2s1, 2px1 2py1 2pz1.
The four valencies of carbon atom are similar and they are symmetrically arranged around the carbon atom. The four valencies of carbon
do not lie in one plane. They are directed towards the corners of a regular tetrahedron with carbon atom at the centre and the angle
between any two valencies is 109o28.
Bonding in Organic Compounds
Carbon must form only covalent bonds, i.e., it should share its valency electrons with other atoms.
According to the modern concept, a covalent bond is formed between two atoms if there is an overlapping of an atomic orbital of one
atom with an atomic orbital of another atom. The overlapping is possible by two ways:
End to End Overlapping
This type of overlapping is possible between s − s, s − p x and px − px atomic orbitals. The molecular bond formed is termed as
sigma ( ) bond.
Sidewise or Parallel or Lateral Overlapping
Such overlapping is possible between p − p atomic orbitals. The molecular bond formed is termed as pi ( ) bond.
Table: 14.1 Difference between Sigma and Pi Bond
 -Bond  -Bond
Formed by end to end overlap of atomic orbitals. Formed by lateral overlap of p-orbitals.
Has cylindrical charge symmetry about bond axis. Has maximum charge density in the cross-sectional plane of the orbitals.
Has free rotation. No free rotation, i.e., frozen rotation.
High energy. Low energy.
Only one  bond can exist between two atoms. One or two  bonds can exist between two atoms.
Sigma bonds are directional. Thus the geometry of the molecule depends  bonds are not directional. Geometry of the molecule does not depend on 
on the  bonds. bonds.
Area of overlapping is higher hence bond is stronger. Area of overlapping is small hence bond is weaker.
 bond can have independent existence.  bond always exist along with a  bond and  bond is formed after the
formation of  bond.
Stuctural Representation of Organic Compounds
Structure of organic compounds can be represented in following ways:
Complete Structural Formula
Each pair of electrons making a covalent bond (single bond) is represented by a solid dash ( ).
Double bond is represented by two dashes ( ) and triple bond is represented by three
dashes ( ).
Example: Structure of ethane
General Organic Chemistry | 2

Condensed Structural Formula
Some or all dashed lines can be omitted from complete structural formula to make condensed structural formula.
Example: CH 3 − CH 3 or C2 H 6 represents ethane.
Bond-line Structural Formula
Carbon-carbon bonds are shown by zig-zag lines and carbon atoms by line ends and intersections.
A single bond is represented by a single line, double bond by two parallel lines and a triple bond
by three parallel lines.
All atoms other than carbon and hydrogen are shown on the line.
Each carbon atom is assumed to have the required number of hydrogen atoms to satisfy the tetravalency of carbon.
Few simple groups can be presented by their short name, e.g. Me for methyl, Et for ethyl, Ph for phenyl group etc.
Example: Structure of dichloroacetic acid (CHCl2COOH)
Wedge and Dash Representation
The 3D structure of organic compound can be represented on paper by this method.
Bonds lying in the plane of the paper indicated by ordinary lines.
A solid wedge indicates a bond lying above the plane of the paper (towards the observer).
A dashed wedge indicates a bond lying below the plane of the paper (away from the observer).
Example: 3D representation of methane molecule
Hybridisation and Geometry of Organic Compounds
Hybridisation
The process of mixing atomic orbitals to form a set of new equivalent orbitals is termed as hybridisation. There are three types of
hybridisation in organic compounds
(1) sp3 Hybridisation (involved in saturated organic compounds containing only single covalent bonds),
(2) sp2 Hybridisation (involved in organic compounds having carbon atoms linked by double bonds) and
(3) sp Hybridisation (involved in organic compounds having carbon atoms linked by a triple bonds).
Table : 14.2 Type of Hybridisation for Carbon Atom
Type of hybridisation sp3 sp2 sp

Number of orbitals used 1s and 3p 1s and 2p 1s and 1p
Number of unused Nil One Two
p-orbitals
Bond Four - Three - Two -
One - Two -
Bond angle 109.5 120 180
Geometry Tetrahedral Trigonal planar Linear
s-character 25% or 1/4 33.33% or 1/3 50% or 1/2
Applications of Hybridisation
(1) Size of the Hybrid Orbitals
Since s - orbitals are closer to the nucleus than p - orbitals, it is reasonable to expect that greater the s character of an orbital
the smaller it is. Thus the decreasing order of the size of the three hybrid orbitals is opposite to that of the decreasing order of
s orbital character in the three hybrid orbitals.
sp3  sp2  sp

(2) Electronegativity of Different Orbitals
• Electronegativity of s-orbital is maximum.
• Electronegativity of hybrid orbitals  % s-character in hybrid orbitals
Orbital sp sp 2 sp 3
% s - character 50 33.33 25
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
s-character in decreasing order and electronegativity in decreasing order
3 2
Thus sp-hybrid carbon is always electronegative in character and sp - hybrid carbon is electropositive in character. sp -
hybrid carbon can behave as electropositive (in carbocation) as well as electronegative (in carbanion) in character.
sp
Electronegative carbon
Electropositive carbon having positive charge
Bond Length Variation in Hydrocarbons

1 1
% of s orbital character  
C − C bond length C − H bond length
Table : 14.3 Bond Length in Hydrocarbons
Bond type (C – H) Bond length Bond type (C – C) Bond length
3 1.112Å 3 3 1.54 Å
sp − s (alkanes) sp − sp (alkanes)
1.103Å 1.34Å
sp2 − s (alkenes) sp2 − sp2 (alkenes)
sp − s (alkynes) 1.08Å sp − sp (alkynes) 1.20Å
Bond Strength in Hydrocarbons
The shorter is the bond length, the greater is the compression between atomic nuclei and hence greater is the strength of that
bond.
Table : 14.4 Bond Strength in Hydrocarbons

Bond type (C – H) Bond energy (kcal/mole) Bond type (C – C) Bond energy (kcal/mole)
3
sp − s (in alkanes) 104 3 3
sp − sp (in alkanes) 80 – 90
sp2 − s (in alkenes) 106 sp2 − sp2 (in alkenes) 122 – 164
sp − s (in alkynes) 121 sp − sp (in alkynes) 123 – 199
Acidity of Hydrocarbons
• Hydrogen present on electronegative carbon is acidic in nature.
• Acidity of hydrogen is directly proportional to the electronegativity of the atom on which hydrogen is present.
H −O − H  NH  CH CH
Thus
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
3
→
Acidity of compounds in decreasing order
• Acidity of hydrocarbon  % of s-character
CH  CH CH 2 = CH 2 CH 3 − CH 3
% s-character 50 33.33 25
pKa 25 44 50
s- character and acidity in decreasing order

1
Acidity  Ka and Acidity  (pKa = − log Ka )
pKa
Order of acidic nature of alkynes is,

HC  CH  HC  C − CH 3
The relative acidic character follows the order:

H 2O  ROH  HC  CH  NH 3  CH 2 = CH 2  CH 3 − CH 3
Obviously, the basic character of their conjugate bases follows the reverse order:
CH3CH2−  CH2 = CH −  NH2−  HC  C−  RO−  HO−
Dipole Moment of Organic Compounds
(1) Due to differences in electronegativity, polarity developes between two adjacent atoms in the molecule (i.e., in a bond). The degree
of polarity of the bond is called dipole moment. Dipole moment is represented by  and its unit is Debye (D).
 = el (1D = 10−10 esu  10−8 cm = 10−18 esu.cm)

Where, e = magnitude of separated charge in e.s.u., l = internuclear distance between two atoms i.e., bond length in cm.
The dipole moment is denoted by arrow head pointing from the positive to the negative end (→).
(2) Dipole moment of the compound does not depend only on the polarity of the bond but also depends on the shape of the molecule.
Dipole moment of symmetrical compound is always zero, (  = 0 ). Symmetrical compounds are those compounds which fulfill
following two conditions,
• Central atom is bonded with the same atoms or groups. Examples : H 2 , BF3 , CS2 , CH2 = CH2 , CH  CH
Symmetrical molecules
• Central atom should have no lone pair of electrons. Examples : CCl4 , CH4 , BH3 , CO2
Symmetrical molecules
(3)   electronegativity of central atom or surrounding atoms present on the central atom of the molecule.
CHF3 CHCl CHBr3 CHI3
⎯⎯⎯⎯ ⎯⎯⎯⎯⎯3 ⎯⎯⎯⎯⎯⎯ ⎯⎯⎯⎯⎯ →
Electroneg ativity in decreasing order
 is also in decreasing order
NH3 PH AsH3 SbH3

⎯⎯⎯⎯ ⎯⎯⎯⎯3⎯⎯⎯⎯⎯⎯⎯ ⎯⎯⎯⎯⎯ ⎯
⎯→
Electroneg ativity of central atom is in decreasing
order  is also in decreasing order
(4) Decreasing order of dipole moment in CH 3 Cl , CH 2Cl 2 , CHCl 3 and CCl 4 is
CH 3 Cl  CH 2 Cl 2  CHCl 3  CCl 4
 = 1.86 D 1.62 D 1.03 0

2
(5) Alkynes has larger dipole moment because the electronegativity of sp − C is more than that of sp − C .
(6)  cis   trans in geometrical isomers.
(7) Dipole moment of the trans derivative of the compound (a)(b)C = C(a)(b) will only be zero if both a and b are same atoms.
Examples :
( or )
If both will not be same atoms then  for trans form may or may not be zero.

If group have non-linear moments, then the dipole moment of the trans isomer will not be zero. If group have linear moments, then
the dipole moment of the trans isomer will be zero.
H 3C CH3 H CH3
Examples : C=C C=C
H H H 3C H
 = 0.33 D  =0D
(8) Dipole Moment of Disubstituted Benzene
• When both groups X and Y are electron donating or both groups are electron withdrawing
X X
Then,  = 12 + 22 + 212 cos
Where,  1 = dipole moment of bond C − X ,  2 = dipole Y or Y

moment of bond C − Y ,  = angle between X and Y.
If value of  will be more, then cos  will be less. Hence, dipole moment will be as
−derivative  m- derivative  p- derivative

⎯o⎯ ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ ⎯→
 in decreasing order
• When one group is electron withdrawing and the other group is electron donating then,
 = 12 + 22 − 212 cos
o − derivative  m- derivative  p- derivative

Hence, dipole moment order as ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ ⎯→
 in decreasing order
Steric Hindrance
On account of the presence of bulkier groups at the reaction centre, they cause mechanical interference and with the result the attacking
reagent finds it difficult to reach the reaction site and thus slows down the reaction. This phenomenon is called steric hinderance or
steric effect.
(1) Tertiary alkyl halides having bulky groups form tertiary carbocation readily when hydrolysed because of the presence of the three
bulky groups on the carbon having halogen. Steric strain around this carbon
(More strained species)
Steric strain is released
CH (less strained species)
3
| 
H 3 C − C − Cl ⎯⎯→ H 3 C − C − CH
3
| |
CH
3 CH
3
(2) Primary alkyl halide having quaternary  -carbon does not form transition state because of the steric strain around  -carbon by the
 -carbon. To release the strain it converts into carbocation.
Bulky group
Strained carbon due to

bulky group present
around this carbon.
(3) Steric strain inhibits the resonance. This phenomenon is known as steric inhibitions of resonance.

Electronic Displacement in Covalent Bonds
Most of the attacking reagents always possess either a positive or a negative charge; therefore for a reaction to take place on the covalent
bond the later must possess oppositely charged centres. This is made possible by displacement (partial or complete) of the bonding
electrons. The electronic displacement in turn may be due to certain effects, some of which are permanent and others are temporary.
Permanent effects are permanently operating in the molecule and are known as polarisation effects, while the temporary effects are
brought into play by the attacking reagent and as soon as the attacking reagent is removed, the electronic displacement disappears; such
effects are known as the polarisability effects.
Electronic displacement
Polarisation effect Polarisability effect

(permanent) (temporary)
Inductive Mesomeric Hyperconjugative Inductomeric Electromeric

effect effect effect effect effect
Inductive Effect
When an electron withdrawing (X) or electron-releasing (Y) group is attached to a carbon chain, polarity is induced on the carbon
atom and on the substituent attached to it. This permanent polarity is due to displacement of shared electron of a covalent bond
towards a more electronegative atom. This is called inductive effect or simply as I – effect.
C − C − C − C Non polar
+ + + + −
C4 C3 C2 C1 X
− − − − +
C4 C3 C2 C1 Y
Important Features of Inductive Effect
• It operates through  bonds.

• It is generally observed in saturated compounds.
• The shared pair of electrons although permanently shifted towards more electronegative atom, yet remains in the same
valence shell.
• As a result of electron shifting, the more electronegative end acquires partial negative charge and the other acquires partial
positive charge.
• The inductive effect is not confined to the polarization of one bond but is transmitted along a chain of carbon atoms through
 bonds. However, the effect is insignificant beyond second carbon in the chain.
• Inductive effect brings changes in physical properties such as dipole moment, solubility, etc. It affects the rates of the
reaction.
Carbon-hydrogen bond is taken as a standard of inductive effect. Zero I effect is assumed for this bond. Atoms or groups which
have a greater electron withdrawing capacity than hydrogen are said to have –I effect whereas atoms or groups which have a greater
electron releasing power are said to have +I effect.

NH3  NO2  CN  SO3 H  CHO  CO  COOH  COCl  COOR > CONH 2  F  Cl  Br  I  OR  OH  −OH  NH 2  C6 H 5  H
–I power of groups in decreasing order with respect to the reference H

ter. alkyl > sec. alkyl > pri. alkyl > CH 3  H
+ I power in decreasing order with respect to the reference H

CH 3 − CH 2 − CH 2 − CH 2 −  CH 3 − CH 2 − CH 2 −  CH 3 − CH 2 −
+ I power in decreasing order in same type of alkyl groups

Applications of Inductive Effect
• Magnitude of Positive and Negative Charges
Magnitude of +ve charge on cations and magnitude of –ve charge on anions can be compared by + I or – I groups
present in it.
1
Magnitude of +ve charge   − I power of the group.
+ I power of the group
1
Magnitude of −ve charge   + I power of the group.
− I power of the group
• Reactivity of Alkyl Halide
+ I effect of methyl group enhances – I effect of the halogen atom by repelling the electron towards tertiary carbon atom.
The reactivity order of alkyl halides is
CH3 CH 3
H 3C C X  H 3C CH X  CH 3 CH 2 X  CH 3 X
CH3
Tertiary > Secondary > Primary > Methyl [order of reactivity of alkyl halides]
• Relative Strength of the Acids
(a) Any group or atom showing +I effect decreases the acid strength as it increases the negative charge on the carboxylate
ion which holds the hydrogen firmly. Alkyl groups have + I effect.
Thus, acidic nature is,
HCOOH  CH 3 COOH  C 2 H 5 COOH  C 3 H 7 COOH  C 4 H 9 COOH
(+I effect increases, so acid strength decreases)
(b) The group or atom having – I effect increases the acid strength as it decreases the negative charge on the carboxylate
ion. Greater is the number of such atoms or groups (having – I effect), greater is the acid strength.
Thus, acidic nature is,
CCl3COOH  CHCl2COOH  CH2ClCOOH  CH3COOH

Trichloro Dichloro Monochloro Acetic acid
acetic acid acetic acid acetic acid
(– Inductive effect increases, so acid strength increases)
(c) Strength of aliphatic carboxylic acids and benzoic acid
R COOH C6 H5 COOH
 
+ I group − I group
Hence benzoic acid is stronger acid than aliphatic carboxylic acids but exception is formic acid. Thus,
HCOOH > C6 H 5 COOH > RCOOH
Acid strength in decreasing order
• Decreasing Order of Acids
NO 2 CH 2 COOH  FCH 2 COOH  ClCH 2 COOH  BrCH 2 COOH ;
F3 C − COOH  Cl 3 C − COOH  Br3 C − COOH  I 3 C − COOH ;
CH3OH  CH3CH2OH  (CH3 )2 CHOH  (CH3 )3 COH

Methyl Ethyl Iso − propyl Tert − butyl
alcohol Alcohol alcohol alcohol
As compared to water, phenol is more acidic (–I effect) but methyl alcohol is less acidic (+I effect).
OH  H − OH > CH3 OH
Phenol Water Methylalcohol

• Relative Strength of the Bases (Basic Nature of – NH2)
The difference in base strength in various amines can be explained on the basis of inductive effect. The +I effect increases
the electron density while –I effect decreases it.
The amines are stronger bases than NH 3 as the alkyl groups increase electron density on nitrogen due to + I effect while
ClNH 2 is less basic due to –I effect.
“More is the tendency to donate electron pair for coordination with proton, the more is basic nature, i.e., more is the negative
charge on nitrogen atom (due to +I effect of alkyl group), the more is basic nature”.
Thus, the basic nature decreases in the order:
(C2 H 5 )2 NH  CH3 CH2 NH2  CH3 NH2  NH3  ClNH2

Diethyl Ethyl Methyl Ammonia Chloro
amine amine amine amine
The order of basicity is as given below;
Alkyl groups (R–) Relative Base Strength
CH3 R2 NH  RNH2  R3 N  NH3
C2H5 R2 NH  RNH2  NH3  R3 N
(CH3 )2 CH RNH2  NH3  R2 NH  R3 N
(CH3)3 C NH3  RNH2  R2 NH  R3 N
a) The relative basic character of amines is not in total accordance with inductive effect (t  s  p) but it is in the following
order: Secondary > Primary > Tertiary. The reason is the steric hindrance existing in the t-amines.
b) In gas phase or in aqueous solvents such as chlorobenzene etc, the solvation effect, i.e., the stabilization of the conjugate
acid due to H -bonding are absent and hence in these media the basicity of amines depends only on the +I effect of
the alkyl group thus the basicity of amines follows the order : 3o  2o  1o  NH3 .
• Stability of Carbonium Ion
+I effect tends to decrease the (+ve) charge and –I effect tends to increases the +ve charge on carbocation.
(CH3 )3 C  (CH3 )2 CH   CH3 CH2  CH3
• Stability of Carbanion Ion
Stability of carbanion increases with increasing – I effect.
CH3−  CH3 CH2−  (CH3 )2 CH −  (CH3 )3 C −
• Stability of Free Radicals

o o o
Similarly we can explain stability of 1 ,2 ,3 free radicals which is in the same order as carbocations
. . . .
CH3  CH3 CH2  (CH3 )2 CH  (CH3 )3 C
Resonance Effect or Mesomeric Effect
In case of conjugated system (having alternate  and  bonds), the electrons can flow from one part of the system to the other due
to resonance. The flow of electrons from one part of the conjugated system to the other part creates region of low and high electron
density is called resonance effect (R-effect) or mesomeric effect (M-effect).
The mesomeric effect is transmitted through whole of the conjugated system and thus the effect may better be known as
conjugative effect.
Important Features of Mesomeric Effect
• In this effect the electron pair is completely transferred and thus full positive and negative charges developes.

• It affects the physical properties such as dipole moment, solubility etc. Rate of reaction of the substance is also affected.
Types
• + M effect groups: The groups which donate electrons to the double bond or to a conjugated system are said to have
.. ..
+ M effect or + R effect. Examples: − Cl, − Br, − I, − NH2 , − NR2 ,−OH,−OR,−SH,−OCH3 ,− .SR
.
• −M effect groups: The groups which withdraw electrons from the double bond or from a conjugated system towards
itself due to resonance are said to have −M effect or − R effect. Examples:
O
||
− NO2 ,−C  N, − C −,−CHO,−COOH,−SO3 H
The inductive and mesomeric effects, when present together, may act in the same direction or oppose each other. The
mesomeric effect is more powerful than the former. For example, in vinyl chloride due to – I effect the chlorine atom should
develop a negative charge but on account of mesomeric effect it has positive charge.
..  ..
: Cl
..  CH = CH 2 ⎯→ : Cl
.. = CH − CH 2
Application of Mesomeric Effect : It explains,
• Low reactivity of aryl and vinyl halides,
• The acidic nature of carboxylic acids,
• Basic character comparison of ethylamine and aniline,
• The stability of some free radicals, carbocations and carbanions.
Difference between Resonance and Mesomerism
Although both resonance and mesomerism represent the same phenomenon, they differ in the following respect : Resonance
involves all types of electron displacements while mesomerism is noticeable only in those cases where a multiple bond is in
conjugation with a multiple bond or lone pair of electron.
Example:
.–. 
(i) H 2C = CH − CH = CH 2 ⎯→ H 2 C− CH = CH − C H 2
.. ..
:O :O:−
|| .. | 
(ii) R − C − .O.− H ⎯→ R − C = .O.− H
Both (i) and (ii) are the examples of mesomerism and resonance effect. Let us consider the following example:
..  −
H . . : ⎯→ H Cl . Such an electron displacement is the example of resonance only (not the mesomerism).
Cl
Hyperconjugative Effect
When a H − C bond is attached to an unsaturated system such as double bond or a benzene ring, the sigma () electrons of the
H − C bond interact or enter into conjugation with the unsaturated system. The interactions between the electrons of  systems
(multiple bonds) and the adjacent  bonds (single H − C bonds) of the substituent groups in organic compounds is called
hyperconjugation.
The concept of hyperconjugation was developed by Baker and Nathan and is also known as Baker and Nathan effect.
Since there is no bond between the  -carbon atom and one of the hydrogen atoms, the hyperconjugation is also called no-bond
resonance.

Orbital Concept of Hyperconjugation : The orbital concept of hyperconjugation may be explained with the help of propene.
In this, 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 as shown in figure.
 bond
 Hyperconjugation
H–C Bond C C

C
Unsaturated system
Fig. 14.1 Orbital Representation of - Conjugation
Structural Requirements for Hyperconjugation
2
• Compound should have at least one sp -hybrid carbon of either alkene alkyl carbocation or alkyl free radical.
2
•  -carbon with respect to sp hybrid carbon should have at least one hydrogen.
• If both these conditions are fulfilled then hyperconjugation will take place in the molecule.
• Hyperconjugation is of three types.
a)  (C – H),  conjugation : This type of conjugation occurs in alkenes.
CH3

|
C H 3 − CH = CH2 CH3 − C H − CH = CH2 CH3 − C − CH = CH2
 |
CH3 |
CH3
No  - H present so has not hyperconjugation
b)  (C – H), positive charge conjugation : This type of conjugation occurs in alkyl carbocations.
      
C H3 − C H2 C H3 − C H − C H3 CH3 − C − C H 3
 |
CH3

c)  (C – H), odd electron conjugation : This type of conjugation occurs in alkyl free radicals.
.  . 
C H3 − C H2 C H3 − C − C H3

sp 2 |
CH3

• Resonating structures due to hyperconjugation may be written involving “no bond” between the alpha carbon and hydrogen
atoms.

H H H H
| − | − | −
H − C − CH = CH 2 ⎯→ H − C = CH − C H ⎯⎯→ H C = CH − CH 2 ⎯⎯
→ H − C = CH − CH
| | 2 |
H
2
H H H 
• Number of resonating structures due to the hyperconjugation = Number of  -hydrogens + 1.

Table 14.5 Number of Resonating Structures
Structure Number of -hydrogens Number of resonating structures
CH3 − CH = CH2 3 4
CH3 − CH2 − CH = CH2 2 3
CH3 − CH = CH − CH3 6 7
 3 4
CH3 − C H2
 6 7
CH3 − C− CH3
|
H
 9 10
CH3 − C − CH3
|
CH3
Applications of Hyperconjugation
• Stability of Alkenes : Hyperconjugation explains the stability of certain alkenes over other alkenes.
Stability of alkenes  Number of alpha hydrogens  Number of resonating structures
CH3 − CH = CH2  CH3 − CH2 − CH = CH2  CH3 − CH − CH = CH2

|
CH3
Stability in decreasing order
• Carbon-carbon Double Bond Length in Alkenes : As we know that the more is the number of resonating structures,
the more will be single bond character in carbon-carbon double bond.
• Stability of Alkyl Carbocations : Stability of alkyl carbocations  number of resonating structures  number of alpha
hydrogens.
• Stability of Alkyl Free Radicals : Stability of alkyl free radicals can be explained by hyperconjugation. Stability depends
on the number of resonating structures.
• Electron Releasing (or Donating) Power of R in Alkyl Benzene : CH 3 − (or alkyl group) is + R group, ortho-para
directing group and activating group for electrophilic aromatic substitution reaction because of the hyperconjugation.
The electron donating power of alkyl group depends on the number of resonating structures, this depends on the number
of hydrogens present on -carbon. The electron releasing power of some groups is as follows,
CH3
CH3 |
CH3 −  CH3 − CH2 −  CH −  CH3 − C −
CH3 |
CH
3
Increasing inductive effect

Electron donating power in decreasing order due to the hyperconjugation.
• Heat of Hydrogenation : Hyperconjugation decreases the heat of hydrogenation.
• Dipole Moment : Since hyperconjugation causes the development of charges, it also affects the dipole moment in the
molecule.
The increase in dipole moment, when hydrogen of formaldehyde ( = 2.27 D) is replaced by methyl group, i.e.,
acetaldehyde ( = 2.72D) can be referred to hyperconjugation, which leads to development of charges.

H H H+
| | −
H − C = O , H − C − CH = O ⎯→ H − C = CH − O
( = 2.27D) | |
H H
( = 2.72D)
• Orienting Influence of Alkyl Group in o, p -positions and of − CCl 3 group in m -position : Ortho-para directing
property of methyl group in toluene is partly due to + I effect and partly due to hyperconjugation.
Reverse Hyperconjugation
The phenomenon of hyperconjugation is also observed in the system given below,
X
|
− C − C = C ; where X = halogen
|
In such system the effect operates in the reverse direction. Hence the hyperconjugation in such system is known as reverse
hyperconjugation.
−
Cl Cl
| 
Cl − C − CH = CH 2 ⎯→ Cl − C = CH − CH ⎯→
| | 2
Cl Cl
Cl Cl
− |  | 
Cl C = CH − CH ⎯→ Cl − C = CH − CH
2
| 2
Cl Cl

The meta directing influence and the deactivating effect of CX 3 group in electrophilic aromatic substitution reaction can be
explained by this effect.
X X X X
| | − | − | −
X − C− X X−C X X−C X X−C X
| || || ||
 +
Inductomeric Effect
Inductomeric effect is the temporary effect which enhances the inductive effect and it accounts only in the presence of an attacking
reagent.
Example:
H
H H
−Cl −
HO − H − C − Cl ⎯⎯→ HO....... .....C..... .......Cl ⎯⎯ ⎯→ HO − C − H
H H
H H
In methyl chloride the –I effect of Cl group is further increased temporarily by the approach of hydroxyl ion.
Electromeric Effect
The phenomenon of movement of electrons from one atom to another in multi-bonded atoms at the demand of attacking reagent
is called electromeric effect. It is denoted as E-effect and represented by a curved arrow ( ) showing the shifting of electron pair.
 −
E
A = B ⎯⎯ → A− B :
Reagent
(polar)

Important Features of Electromeric Effect
• It is a temporary effect
• It is brought into play instantaneously at the demand of the attacking reagent. However, as soon as the attacking reagent is
removed, original electronic condition is restored.
attacking  −
C = O ⎯⎯ ⎯⎯→ attacking
C− O ⎯⎯⎯⎯ → C=O
reagent reagent
removed
• The electromeric effect is of common occurrence during addition of polar reagents on C = C , C = O and C  N bonds
etc.
• The effect involves the complete transfer of  electrons.
• In this effect the displaced electrons leave their orbitals and take a new position.
• There is complete charge separation and ions are formed.
• Since electromeric effect takes place only at time of attacking reagents, it always facilitates the reaction and never inhibits it.
• In cases where inductive effect and electromeric effect simultaneously operate, usually electromeric effect predominates.
+E Effect
When the transfer of electrons takes place towards the attacking reagent, the effect is called + E effect. E.g. the addition of
acids to alkenes.

C=C + H  ⎯⎯→ C+ − C CH3 CH = CH2 + H + → CH3 − CH− CH3
| Propene
H
Since, − CH 3 group is electron donating, the electrons are transferred in the direction shown. Hence, the attacking reagent is
attached to that atom on which electrons have been transferred.
– E Effect
When the transfer of electrons takes place away from the attacking reagent, the effect is called − E effect. E.g. the addition of
cyanide ion to carbonyl compounds.
..
C = O + CN − ⎯⎯→ C −O−
|
CN
Here, the attacking reagent is not attached to that atom on which electrons have been transferred.
Direction of the Shift of Electron Pair
• When the groups linked to a multiple bond are similar, the shift can occur in either direction.
• When the dissimilar groups are linked on the two ends of the double bond, the shift is decided by the direction of inductive
effect. E.g. in the case of carbonyl group, the shift is always towards oxygen, i.e., more electronegative atom.
 −
C = O ⎯⎯→ C− O :
Cleavage (Fission or Breaking) of Covalent Bonds
Breaking of covalent bond of the compound is known as bond fission. A bond can be broken by two ways, depending upon the nature
of given compound, the nature of attacking reagent and the reaction conditions.
Homolytic Bond Fission or Homolysis
In homolysis, the covalent bond is broken in such a way that each resulting species gets its own electron. This leads to the formation
of odd electron species known as free radical.

. .
A : B ⎯⎯→ A + B
Free radical
The factor which favours homolysis is that the difference in electronegativity between A and B is less or zero.
Homolysis takes place in gaseous phase or in the presence of non polar solvents (CCl 4 , CS 2 ) , peroxide, UV light, heat
( 500o C) , electricity and free radical.
Mechanism of the reaction in which homolysis takes place is known as homolytic mechanism or free radical mechanism.
Heterolytic Bond Fission or Heterolysis
In heterolysis, the covalent bond is broken in such a way that one species (i.e., less electronegative) is deprived of its own electron,
while the other species gains both the electrons.
− 
A : B ⎯⎯→ A: + B [A is more electronegative than B]
Carbanion Carbocation
Thus, formation of opposite charged species takes place. In case of organic compounds, if positive charge is present on the carbon
then cation is termed as carbocation (carbonium). If negative charge is present on the carbon then anion is termed as carbanion.
The factor which favours heterolysis is greater difference of electronegativities between A and B .
Mechanism of the reaction in which heterolysis takes place is known as heterolytic mechanism or ionic mechanism.
The energy required for heterolysis is always greater than that for homolysis due to electrostatic forces of attraction between ions.
Reaction Intermediates
Short lived fragments called reaction intermediates result from homolytic and heterolytic bond fission. The important reaction intermediates
are free radicals, carbocations, carbanions, carbenes, benzyne and nitrenes.
Table: 14.6 Types of Reaction Intermediates
Characteristic Free radical Carbocation Carbanion

Nature Neutral having odd electron Positive charge on C Negative charge on C
2 2
Hybridisation sp sp sp3(non-conjugated)
sp2 (Conjugated)
Structure Planar Planar Pyramidal/Planar
Magnetism Paramagnetic Diamagnetic Diamagnetic
Stability order . . . + + +
Ph3C  Ph2CH 
Ph3C  Ph2CH  PhCH 2  Ph3C  Ph2CH  PhCH2 
+ PhCH2  Allyl
.
CH2 = CH − CH2 
CH 2 = CH − CH 2  3o  2o  CH3  1o  2o  3o
+
. . 3o  2o  1o  CH3
1o  CH 3  CH 2 = CH
Attacking Reagents
The fission of the substrate molecule to create centres of high or low electron density is influenced by attacking reagents. Most of the
attacking reagents can be classified into two main groups.
Electrophiles or electrophilic reagents and Nucleophiles or nucleophilic reagents.
Electrophiles
Electron deficient species or electron acceptor is an electrophile. Electrophiles are Lewis acids.
It can be classified into two categories:
Charged Electrophiles
Positively charged species in which central atom has incomplete octet is called charged electrophile.

 O   
(H 3 O + ) H  , X  , R  , N , N = O, S O3 H , C6 H5 N 2
O ..

All cations are charged electrophiles except cations of IA, IIA group elements, Al + + + and NH4
Neutral Electrophiles
• Neutral covalent compound in which central atom has incomplete octet is neutral electrophile,
. .. ..
BeCl 2 , BH 3 , ZnCl2 , AlX3, FeX 3 , CH3 , CH2 , CX2
• Neutral covalent compound in which central atom has complete or expanded octet and central atom has unfilled –d-sub-
shell is neutral electrophile,
SnCl 4 , SiCl 4 , PCl 5 , SF6 , IF7
• Neutral covalent compound in which central atom is bonded only with two or more than two electronegative atoms is
called neutral electrophile.
..
BeCl 2 , BX 3 , AlX 3 , FeX 3 , SnCl 4 , PCl 3 ; PCl 5 , NF3 , C X 2 , CO2 , SO3 , CS2 ,
• Cl 2 , Br2 and I 2 also behave as neutral electrophiles.
Nucleophiles
Electron rich species or electron donors are called nucleophiles. Nucleophiles are Lewis bases.
It can be classified into three categories:
Charged Nucleophiles
Negatively charged species are called charged nucleophiles.
H, OH, R − O, CH3, X, SH, R − S
Neutral Nucleophiles
• Neutral covalent compound, in which central atom has complete octet, has at least one lone pair of electrons and all
atoms present on central atom should not be electronegative, is neutral nucleophile.
.. .. .. .. .. ..
N H 3, R − N H 2 , R2 N H, R3 N , N H 2 − N H 2 (Nitrogen nucleophile)
.. .. ..
H − O− H, R − O− H, R − O− R (Oxygen nucleophiles)
.. .. ..
.. .. ..
H − S− H, R − S− H, R − S− R (Sulphur nucleophiles)
.. .. ..
.. .. .. ..
P H 3 , R P H 2 , R2 P H, R3 P (Phosphorus nucleophiles)
• Organic compound containing carbon, carbon multiple bond/ bonds behaves as nucleophile.
• Alkenes, Alkynes, Benzene,
CH 2 = CH − CH = CH 2 , CH 2 = CH − C  CH
• Organometallic compounds are nucleophiles.
Ambident Nucleophiles
Species having two nucleophilic centres out of which, one is neutral (complete octet and has at least one lone pair of
electrons) and the other is charged (negative charge) behaves as ambident nucleophile

O
− .. − .. − 
C  N, O− N = O, O− S − OH

O
Organic Ccompounds which Behave as an Electrophile as Well as a Nucleophile (Ambiphile)
Organic compound in which carbon is bonded with electronegative atom (O, N, S) by multiple bond/bonds behaves as electrophile
as well as nucleophile :
O O O O O O
|| || || || || ||  
R − C − H, R − C − R, R − C − OH , R − C − Cl , R − C − OR, R − C − NH2 , R − C  N , R − N  C
During the course of chemical reaction electrophile reacts with nucleophile.

 
Strong Lewis acid is stronger electrophile CO2  N O2  S O3 H . Stronger is an acid, weaker is its conjugated base or weaker
is the nucleophile.
Examples :
HF  H 2 O  NH 3  CH 4 ; F −  OH −  NH2−  CH3−
Increasing order of nucleophilicity.
Comparison of Nucleophilicity and Basicity of Different Species
Both nucleophilicity and basicity depend upon the availability of a lone pair of electrons. If this lone pair of electrons is donated to
a hydrogen atom, it is called basicity and if it is donated to a carbon atom, it is called nucleophilicity. For example,
Nucleophilicity
| |
Nu : − + C : L ⎯⎯→ Nu − C + : L−
/\ /\
Basicity
B :− + H : A B : H + : A−
Difference
• Nucleophilicity depends upon the rate constant of the reaction while basicity depends upon the equilibrium constant (Kb )
• Nucleophilicity governs the kinetics of a reaction while basicity determines its thermodynamics.
These two phenomena are closely related, therefore, at first sight it might appear that nucleophilic power would parallel basic
strength. This is, however, not always true as discussed below:
a) If the nucleophilic atom or the centre is the same, nucleophilicity parallels basicity, i.e., more basic the species, stronger is
the nucleophile. For example,
CH3O−  HO−  CH3COO−  H2O
Basicity and nucleophilicity decrease→
It may be noted here that the nucleophile atom, O is the same in all these species.
This order can be easily explained on the general concept that a weaker acid has a stronger conjugate base.
b) In going from left to right across a period in the periodic table, the basicity and nucleophilicity are directly related, i.e.,
both decrease as the electronegativity of the atom possessing the lone pair of electrons increases. For example,
.. . .
H 3C :−  H 2 N :−  HO −
. . : : F
. .:
−
Basicity and nucleophilicity decrease→
(c) In moving down a group in the periodic table, the basicity and nucleophilicity are inversely related i.e., nucleophilicity
increase while basicity decreases. For example,

— Nucleophilicity decreases →
I , Br , Cl − , F −
− −
PH 3 , NH 3 H 2 S, H 2O
; ;
—Basicity increases →
(i) The main reason for this reversal of basicity and nucleophilicity are the different factors on which basicity and
nucleophilicity depend. Whereas basicity depends on the strength of the H-M (M = F, Cl, Br, I, N, P, O etc.) bond,
nucleophilicity depends upon the electronegativity of the atom/group to which the proton is attached.
(ii) Similarly, NH 3 is a stronger base than PH 3 because N − H (389kJ mol −1) bond is stronger than
P − H(318 kJ mol −1 ) bond but PH 3 is a stronger nucleophile than NH 3 because P is less electronegative
( EN = 2.1) than N ( EN = 3.0) . Likewise H 2 O is a stronger base than H 2 S because O − H (462kJmol −1) bond is
stronger than S − H(360kJ mol −1 ) bond while H 2 S is a stronger nucleophile than H 2 O because S is less
electronegative ( EN = 2.5) than O(EN = 3.5) .
(iii) For the same nucleophilic centre, the basicity increases but the nucleophilicity decreases as the size of the nucleophile
approaching the substrate increases. For example, basicity increases in the order : MeO −  Me 2CHO−  Me3CO−
but nucleophilicity increases in the reverse order : Me3CO−  Me 2CHO−  MeO − due to steric hindrance.
. .
(iv) When the atom bonded to the nucleophilic centre also has a lone pair of electrons (i.e., G− Nu : ), the nucleophilicity
. . . .
increases while the basicity decreases. For example, H − O− O :− (peroxide ion) is more nucleophilic than OH − ion
. . . .
.. ..
but OH − is a stronger base than HOO − . Similarly, NH2 NH2 (hydrazine) is more nucleophilic but less basic than
NH 3 .
Basic Terms of Organic Reactions
In a chemical equation, reactants are written on the left-hand side while the products are written on the right-hand side. The two are
separated by an arrow (→). The reactants normally consist of two species: substrate and reagent
Basic Terms
Substrate
The species, which is attacked by some other chemical species, is called a substrate.
Reagent
The species, which attacks the substrate in order to get the major product, is called a reagent. Thus, Substrate + Reagent →
Products.
Activated complex
Normally, a substance and a chemical reagent form a highly energetic species, called activated complex, before it changes into
the product.
Reaction intermediate
In certain cases, a relatively energetically more stable species than the activated complex may also be formed. It is called
reaction intermediate.
Reaction Path
Thus, a chemical reaction, in general, may follow either of the following two paths:
Path I : Substrate + Reagent → Activated complex → Products
Path II : Substrate + Reagent → Activated complex → Intermediate → Products.
Reaction Mechanism
The detailed step by step description of a chemical reaction is called mechanism of a reaction which is only a hypothesis.

• Concerted Mechanism
If the reaction mechanism involves the breaking and making of bonds simultaneously without the formation of any
intermediate; it is called concerted mechanism.
• Non-Concerted Mechanism
On the other hand, if the reaction mechanism involves the formation of intermediates before the formation of products, it is
called non-concerted mechanism.
Activated Complex
Enthalpy Activated Complex Reactive intermediate
Enthalpy
Reactants Reactants
Products Products
Progress of reaction Progress of reaction
Concerted mechanism Non-concerted mechanism
Fig. 14.2 Concerted and Non-concerted Mechanism
Classification of Organic Reactions
It is convenient to classify the numerous reactions of the various classes of organic compound into four types:
(1) Substitution reactions, (2) Addition reactions,
(3) Elimination reactions, (4) Rearrangement reactions,
Substitution Reactions
Replacement of an atom or group of the substrate by any other atom or group is known as substitution reactions.
Example:
Attacking group Leaving group
(Bromine atom is replaced by hydroxyl group)
Types of substitution reactions:

(1) Nucleophilic substitution reactions, (2) Electrophilic substitution reactions and (3) Free radical substitution reactions
Nucleophilic Substitution Reactions
• Many substitution reactions, especially at the saturated carbon atom in aliphatic compounds such as alkyl halides, are brought
about by nucleophilic reagents or nucleophiles.
R − X + OH − ⎯⎯⎯
→ R − OH + X−
Substrate Nucleophile Leaving group
• Such substitution reactions are called nucleophilic substitution reactions, i.e., S N reactions (S stands for substitution and N
for nucleophile).
• The weaker the basicity of a group of the substrate, the better is its leaving ability.
1
Leaving power of the group 
Basicity of the group
Example :
− − − −
HI  HBr  HCl  HF I Br Cl F
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
Decreasing acidity Increasing basicity

Decreasing leaving ability
• The leaving power of some nucleophilic groups are given below in decreasing order
O O O O O
|| − || − || − || − || −
CF3 − S − O  Br S − O  CH 3 S − O  C6 H5 − S − O  CH3 − S − O
|| || || || ||
O O O O O
O O
− − || − − − − || −
 I  Br  CF3 − C − O  H O  Cl  F  CH 3 − C − O
• In these reactions leaving group of the substrate is replaced by another nucleophile. If reagent is neutral then leaving group
is replaced by negative part of the reagent. Negative part of the reagent is always nucleophilic in character.
+ − − − −
E − Nu
R − L ⎯⎯⎯⎯ → R − Nu + L ; R − L + Nu ⎯⎯→ R − Nu + L
• In S N reactions basicity of leaving group should be less than the basicity of incoming nucleophilic group. Thus strongly basic
nucleophilic group replaces weakly basic nucleophilic group of the substrate.
− −
OH
Example : R − Cl ⎯⎯⎯ → R − OH + Cl .....(A)
( NaOH )
− − −
Basicity of OH– is more than Cl hence OH replaces Cl as Cl .


Cl
R − OH ⎯⎯→
⎯ R − Cl + OH ......(B) [Not possible]
( HCl )
− − − −
Basicity of Cl is less than OH , hence Cl will not replace OH, hence reaction (B) will not occur.
• Unlike aliphatic compounds having nucleophilic group as leaving group, aromatic compounds having same group bonded
directly with aromatic ring do not undergo nucleophilic substitution reaction under ordinary conditions.
The reason for this unusual reactivity is the presence of lone pair of electrons or  bond on the key atom of the functional
group. Another factor for the low reactivity is nucleophilic character of aromatic ring.
• The S N reactions are divided into two classes, SN 2 and SN1 reactions.
Table 14.7: Distinction between SN1 and SN 2 Reactions
Factors SN 2 Reactions SN1 Reactions

Number of steps.  
Two: (i)
Slow
R : L ⎯⎯⎯ → R + + : L−
One: R : L+ : Nu → R : Nu+ : L
Fast
(ii) R + + : Nu− ⎯⎯⎯→ R : Nu
Reaction rate and order. Second order: First order:
Rate  [Substrate] [Nucleophile] or Rate = Rate  [Substrate] or Rate = K1[RL]
K2[RL][: Nu− ]
Molecularity. Bimolecular. Unimolecular.
Transition step of slow step.  − −
 + −
: Nu− − − C − −− : L : Nu − − − C− − − L− − − Nu :
Reacting nucleophile. The nucleophile attacks the carbon of the The nucleophile can attack the carbon of the substrate
substrate exclusively from the back side. both from the back and front sides although the back
side attack predominates.
Stereochemistry. Complete inversion of configuration takes Inversion and retention takes place.
place.
Reactivity order of alkyl halides. Methyl>1°>2°>3° halides. (I  Br  Cl  F ) 3°>2°>1° > methyl halides. (I  Br  Cl  F )
Rearrangement. No rearranged product is formed (except for Rearranged products can be formed.
allylic).
Nature of nucleophiles. Favoured by strong and high concentration of Favoured by mild and low concentration of
nucleophiles. nucleophiles.
Polarity. Favoured by solvents of low polarity. Favoured by solvents of high polarity.
Reaction rate determining By steric hindrance. 
By electronic factor (stability of R ).
factor.
Catalysis. Not catalysed by any catalyst (phase transfer). Catalysed by Lewis and Bronsted acids, e.g.,

Ag, AlCl3 , ZnCl2 and strong HA.

Table 14.8 : Preferred Substitution Mechanism for Various Carbon Structure
Type Representative structure Preferred Mechanism

(L is a leaving group)
methyl CH3 − L SN 2
primary RCH2 − L SN 2
secondary RCH − L SN 2 (with good nucleophiles) or SN1 (with poor nucleophiles and polar solvents)
|
R
tertiary R SN 1
|
R C− L
|
R
allylic CH2 = CHCH2 − L SN 2 (with good nucleophiles) or SN1 (with poor nucleophiles and polar solvents)
benzylic CH2 − L
neopentyl CH3 very slow SN1 and SN 2 ( SN 2 in aprotic solvents, gives acceptable yields)
|
CH3CCH2 − L
|
CH3
vinylic R L inert to both SN1 and SN 2 under normal reaction conditions.

C=C
aromatic
R R
• Effect of Solvent
a) SN 1 reactions are faster in the more polar solvents.
b) SN 2 reaction involving a negative nucleophile is slower in more polar solvent and that involving a neutral nucleophile
is faster in more polar solvent.

c) In addition to these polarity effects, the ability of certain solvents to form hydrogen bonds to the nucleophile also affects
the rate of the SN 2 reaction. Such solvents are termed protic solvents and have a hydrogen bonded to nitrogen or
oxygen ( H 2 O, ROH, RCOOH are some example of protic solvents).

d) Nucleophiles, especially smaller anionic ones, are strongly hydrogen bonded to the solvent molecules in protic solvents.
This makes these nucleophiles less reactive because the solvent molecules block the approach of the electrophile.
Aprotic solvents (like acetone), which can’t have hydrogen bond to the nucleophile (because they do not have hydrogen
bonded to nitrogen or oxygen), increase the reactivity of the nucleophile and are especially favourable for SN 2
reactions.

Table 14.9 : Some Common Solvents for Substitution Reaction
Name Structure
trifluoroacetic acid O These are polar, protic solvents. They are quite good as stabilising ions and are especially
||
CF3 COH favourable for SN1 reactions, although they can also be used for SN 2 reactions with
water favourable substrates.
H2O
methanol CH3OH
increasing ionising power
O
||
acetic acid CH 3COH
CH3CH2OH
ethanol
dimethyl O These aprotic solvents are still relatively polar, so that they can dissolve both the nucleophile
||
sulphoxide CH 3 SCH 3 and the substrate. They are especially favourable for SN 2 reactions because nucleophiles are
(DMSO)
more reactive in these solvents than protic ones.
dimethyl O
||
formamide (DMF) HCN (CH 3 )2
acetone O
||
CH 3CCH 3
Electrophilic Substitutions Reactions

Electrophilic substitution involves the attack by an electrophile. It is represented as SE (S stands for substitution and E stands
for elctrophile). If the order of reaction is 1, it is written as S E1 (unimolecular) and if the order is 2, it is S E 2 (Bimolecular).
14.10 Difference between SE1 and SE 2 Reaction
SE1 Reaction mechanism : Electrophilic substitution in aliphatic compounds SE 2 Reaction mechanism : Electrophilic substitution
is very common in benzene nucleus (aromatic
are very rare; some of the important examples are: compounds) in which -electrons are highly delocalized
(i) Replacement of the metal atom in an organometallic compound by hydrogen and an electrophile can attack this region of high
 
electron density.
: R−M +H → R−H+M In all electrophilic aromatic substitution reactions, it

involves:

− MgBr H 
e.g., CH3 − CH2 − MgBr ⎯⎯⎯⎯ → CH3 − CH 2 ⎯⎯ → CH3 − CH3
Step 1. The formation of an electrophile, E, i.e.,
   
H
CH3 − CH2 − MgBr + H − Br → CH3 − CH 2 ⎯⎯ → CH3 − CH3 + MgBr2 In halogenation; Cl − Cl + FeCl3 → Cl + Fe Cl 4
  
CH3 − CH2 Na + C6 H6 → CH3 − CH3 + C6 H5 Na In nitration; HNO3 + 2H2SO4 → NO2 + 2 HSO4 + H3O
 
(ii) Decarboxylation of silver salt of carboxylic acid by means of bromine: In sulphonation; 2H2SO4 → SO3 + HSO4 + H3O
 + −   
R3C − C− OAg + Br − Br → R3C − C − O+ Br− Br + Ag In Friedel-crafts reaction; R − Cl + AlCl3 → R+ AlCl 4
|| ||
 
O O RCOCl + AlCl3 → RCO+ AlCl 4
→ R3C − Br + CO2 + AgBr Step 2. The electrophile attacks the aromatic ring to
form carbonium ion (or arenium ion) which is stabilized
(iii) Isotopic exchange of hydrogen for deuterium or tritium:
by resonance.
 
R−H +D R−D+H
H E H E H E
 
 
R−H +T R−T +H
Benzene +
Resonance forms

Step 3. Carbonium ion loses the proton to form
substitution product.
E E
H
+ Fast
+ H+
The bromination of benzene in the presence of FeBr3 is

an example of electrophilic substitution reaction.
Similarly, Nitration, sulphonation and Friedel-Crafts
reaction…..etc., in benzene nucleus are the other
examples of electrophilic substitution reactions.
Free Radical Substitution Reactions
Free radical substitution reactions involve the attack by a free radical. These reactions occur by free radical mechanism which
involves Initiation, Propagation and Termination steps. Examples:
• Chlorination of Methane
The chlorination of methane in the presence of ultraviolet light is an example of free radical substitution. (homolysis)
UV
CH4 + Cl2 ⎯⎯⎯→ CH3 Cl + HCl
Methane light Methyl chloride
The reaction does not stop with the formation of CH 3 Cl :
CH 3 Cl + Cl 2 → CH 2 Cl 2 + HCl
CH 2 Cl 2 + Cl 2 → CHCl 3 + HCl
CHCl 3 + Cl 2 → CCl 4 + HCl
Reactivity of halogens for free radical substitution is in the order : F2  Cl 2  Br2  I 2
• Arylation of Aromatic Compounds (Gomberg Reaction)
The reaction of benzene diazonium halide with benzene gives diphenyl by a free radical substitution reaction.
Alkali
C6 H 5 − H + C6 H 5 N 2 X ⎯⎯ ⎯→ C6 H 5 − C6 H 5 + N 2 + HX
Benzene diazoniumhalide Diphenyl
• Wurtz Reaction
Ethyl bromide on treatment with metallic sodium forms butane, ethane and ethylene by involving free radical mechanism.
Ether
C2 H5 Br + 2Na + Br − C2 H5 ⎯⎯ ⎯→ C2 H5 − C2 H5 + 2NaBr
•
C2H5 − Br + Na ⎯⎯
→C 2 H5 + NaBr
• •
C 2 H5 + C 2 H5 ⎯⎯
→C 2 H5 − C 2 H5 (Butane)
•
2CH3 − C H 2 ⎯⎯⎯⎯⎯⎯
Disproportionation
⎯→CH3 − CH3 + CH 2 = CH 2
Ethane Ethylene
• Allylic Bromination by NBS (N-Bromosuccinimide)
NBS is a selective brominating agent and it normally brominates the ethylenic compounds in the allylic
(CH 2 = CH − CH 2 −) position. This type of reaction involving substitution at the alpha carbon atom with respect to the
double bond is termed allylic substitution. It is also used for benzylic bromination. Some examples are:

CH2 − CO CH 2 − CO
CCl 4
CH3 − CH = CH2 + N − Br ⎯⎯⎯→ Br − CH 2 − CH = CH 2 + NH
Propene Allyl bromide
CH2 − CO CH 2 − CO
NBS Succinimide
Addition Reactions
These reactions are given by those compounds which have at least one  bond,
O
||
i.e., (  C = C , − C  C−,− C −, C  N ). In such reaction there is loss of one  bond and gain of two  bonds. Thus product of the
reaction is generally more stable than the reactant. The reaction is a spontaneous reaction.
Types of addition reactions
Addition reactions can be classified into three categories on the basis of the nature of initiating species.
(1) Electrophilic additions, (2) Nucleophilic additions, (3) Free radical additions
Electrophilic Addition Reactions (AE)
• Such reactions are mainly given by alkenes and alkynes.
• Electrophilic addition reactions of alkenes and alkynes are generally two step reactions.
• Alkenes and alkynes give electrophilic addition with those reagents which on dissociation gives electrophile as well as
nucleophile.
• If the reagent is a weak acid then electrophilic addition is catalysed by strong acids (generally H 2 SO 4 ).
Nucleophilic Addition Reactions (AN)
When the addition reaction occurs on account of the initial attack of nucleophile, the reaction is said to be a nucleophilic
addition reaction. Due to presence of strongly electronegative oxygen atom, the  -electrons of the carbon-oxygen double
bond in carbonyl group (> C = O ) get shifted towards the oxygen atom and thereby such bond is highly polarised.
This makes carbon atom of the carbonyl group electron deficient.
 − + −
C=O  C− O  C− O
Example: The addition of HCN to acetone is an example of nucleophilic addition.
CH3 CH3 OH
C = O+ HCN → C
CH3 CH3 CN
Acetone Acetone cyanohydrin
The mechanism of the reaction involves the following steps:

 −
• Step 1. HCN gives a proton ( H ) and a nucleophile, cyanide ion (CN ) .
HCN → H  + CN −
• Step 2. The nucleophile (CN − ) attacks the positively charged carbon so as to form an anion [ H  does not attack the
negatively charged oxygen as anion is more stable than cation].
−
CH3 CH 3 CH 3 O
− −
CN C = O → CN C−O or C
CH CH 3 CH 3 CN
3
• Step 3. The proton (H + ) combines with anion to form the addition product.

CH3
CH3 | CH 3 OH
− 
CN C − O+ H → NC − C − OH or C
CH3 | CH 3 CN
CH3
In C = O compounds, the addition of liquid HCN gives cyanohydrin and the addendum is CN − ion and not HCN directly
(addition is catalysed by bases or salts of weak acids and retarded by acids or unaffected by neutral compounds).
−
+ − − O  OH
+ H −CN →  − CN H
C = O ⎯⎯⎯⎯⎯ C − O ⎯⎯⎯→ C ⎯⎯⎯→ C
( A.R.) CN CN
Nucleophilic addition (AN) reactions on carbonyl compounds will be in order:
H H 3C H3C
C=O  C=O  C=O
H H H3C
Decreasing order of nucleophilic addition in some species.

O O
|| ||
C6 H5CH 2COCH3  CH3COCH3  C6H 5 − C − CH 3  C6H 5 − C − C6H 5 − CHO  −COCH3  −COCl  −COOCH3  −CONH 2  −COOH
Free Radical Addition Reactions
Those reactions which involve the initial attack by a free radical are known as free radical reactions. Addition of hydrogen
bromide to alkenes (say, propylene) in the presence of peroxide (radical initiator) follows free radical mechanism. Free radical
reactions generally take place in non-polar solvents such as CCl 4 , high temperature, in presence of light or a free radical
producing substance like O 2 and peroxides. Example:
• Addition of Chlorine to Ethylene

hv or heat
H 2C = CH2 + Cl2 ⎯⎯ ⎯⎯ ⎯→ H 2 C − CH2
(light) | |
Cl Cl
Ethylene (di) chloride
• Addition to Conjugated Dienes
If a conjugated diene, such as 1, 3-Butadiene, reacts with a limited amount of electrophilic reagent so that addition can occur
at only one of the double bonds, two addition products are formed. One is a 1, 2-addition product, which is as a result of
addition at the 1-and-2-positions. The other is a 1, 4-addition product –the result of addition at the 1-and 4-positions.
CCl 4
CH 2 = CH − CH = CH 2 + Cl2 ⎯⎯ ⎯→ CH 2 − CH − CH = CH 2 + CH2 − CH = CH − CH2
1, 3- Butadiene 1 mol | | | |
1 mol Cl Cl Cl Cl
3, 4 - Dichloro-1- butene 1, 4 - Dichloro- 2- butene
(1, 2- addition product) (1, 4 - addition product)
Addition at the 1-and 2-positions is called 1, 2-addition or direct addition. Addition at the 1- and 4-positions is called 1, 4-
addition or conjugate addition. When we refer to the addition at the 1-and 2-positions or at the 1-and 4-positions, we mean
that the addition occurs at the 1-and 2-or 1-and 4-positions of the four-carbon conjugated system. The 1-position is one of the
sp 2 carbons at the end of the conjugated system; it is not necessarily the first carbon in the molecule.
1 2 3 4
R − CH = CH− CH = CH− R
conjugatedsystem

common nomenclature 1 2 3 4 5 6
CH3 − CH = CH− CH = CH− CH3
conjugated system 1 2 3 4
HBr
CH3 − CH− CH = CH − CH2 − CH3 ⎯⎯⎯
|
Br
1, 4 - addition product
HBr
⎯⎯⎯→ CH3 − CH − CH2 − CH = CH − CH3
|
Br
1, 2- addition product
The more stable product is 1, 4-addition product.
Elimination Reactions
Elimination reactions are formally the reverse of addition reactions and involve the removal of the two groups (Generally, one being
a proton) from one or two carbon atoms of a molecule to form an unsaturated linkage or centre.
(1) Elimination reaction is given by those compounds which have a nucleophilic group as leaving group,
  R R
 
i.e., X, OH, OR, N 2 , N 3 , H 3 O, N R, S
R R
(2) Elimination reactions are generally endothermic and take place on heating.
• Types: Depending upon the relative positions of the atoms or groups eliminated, these reactions are classified as - and -
elimination reactions:
(3) -Elimination Reactions or 1,1-Elimination Reactions
A reaction in which both the groups or atoms are removed from the same carbon of the molecule is called - elimination
reaction. This reaction is mainly given by gem dihalides and gem trihalides having at least one - hydrogen.
.. − 
Alc. KOH /
CHX3 ⎯⎯⎯⎯⎯ → CX 2 + X + H
Product of the reaction is halocarbenes or dihalocarbenes, which are key intermediates in a wide variety of chemical and
photochemical reactions.
-Elimination Reactions or 1, 2-Elimination Reactions
A reaction in which functional group (i.e., leaving group) is removed from - carbon and other group (Generally hydrogen
atom) from the - carbon is called - elimination reaction. In this reaction there is loss of two  bonds and gain of one  bond.
Product of the reaction is generally less stable than the reactant.
 −
Consider the following reactions, CH3 − CH 2 − CH 2 − L → CH3 − CH = CH 2 + H + L
 
Types of - Elimination Reactions
In analogy with substitution reactions, - elimination reactions are divided into three types:
• E1 (Elimination Unimolecular) Reaction
Consider the following reaction,
CH3
− CH3
|
C2 H5 O /  −
CH3 − C− Cl ⎯⎯⎯⎯⎯⎯ → CH 2 =C + C2 H5OH + Cl
|
CH3
CH3
a) Reaction velocity depends only on the concentration of the substrate; thus, reaction is unimolecular reaction.
Rate  [Substrate]

b) Product formation takes place by the formation of carbocation as reaction intermediate (RI).
c) Since reaction intermediate is carbocation, rearrangement is possible in E 1 reaction.
d) Reaction is carried out in the presence of polar protic solvent.
e) The E1 reaction occurs in two steps,
Step 1.
CH3 CH3
| | + −
  −
CH3 − C− Cl → CH3+ − C-- --- Cl ⎯⎯⎯⎯→
Slow step
CH3 −C − CH3 + Cl
| | |
CH3 CH3 CH3
( RI )
(TS1 )
Step 2.
 
  CH3
..  
  Fast
B + H − CH2 − C − CH3 →  B - - - - H - - - -CH2 - - - - C − CH3  ⎯⎯⎯→ B H + CH2 = C
| |
CH3  CH3  CH3
 
 TS 2 
• E2 (Elimination Bimolecular) Reaction
Consider the following reaction,
Base( B)
 
CH3 − CH2 − CH2 − Br ⎯⎯ ⎯⎯→ CH3 − CH = CH2 + H + Br

a) Reaction velocity depends only on the concentration of the substrate and the base used; thus reaction is bimolecular
reaction. Rate [Substrate] [Base]
b) Since the reaction is a bimolecular reaction, the product formation will take place by formation of transition state (TS).
c) Rearrangement does not take place in E2 reaction but in case of allylic compound rearrangement is possible.
d) Reaction is carried out in the presence of polar aprotic solvent.
e) E2 reaction occurs in one step,
..
B H H  B − - - - - H +  H 
| |   |  −
Slow step
CH3 − C − C − H ⎯⎯⎯⎯→  CH3 − C C − H  ⎯⎯⎯
Fast
→ CH3 − CH = CH2 + BH + Br
| |  |  
H Br  H Br 
 TS 
• Orientation in - Elimination Reactions
If substrate is unsymmetrical, then this will give more than one product. Major product of the reaction can be known by two
empirical rules:
a) Saytzeff Rule

According to this rule, major product is the most substituted alkene i.e., major product is obtained by elimination of H
from that - carbon which has the least number of hydrogen. Product of the reaction in this case is known as Saytzeff
product.
Cl
2 |
Alc. KOH / 
CH3 − CH − CH − CH3 ⎯⎯ ⎯ ⎯ ⎯
⎯→ CH3 − C = CH − CH3
|  1 − HCl |
CH3 CH
3
Saytzeff p roduct
b) Hofmann Rule
According to this rule, major product is always least substituted alkene i.e., major product is formed from - carbon
which has maximum number of hydrogen. Product of the reaction in this case is known as Hofmann product.
If bases are large, due to steric hindrance, less substituted alkenes are preferred (Hofmann product)
CH3 Br CH3
| | |
Ko- Ter-Bu
CH3 − C − CH2 − CH − CH3 ⎯⎯⎯⎯
⎯→ CH3 − C− CH2 − CH = CH2
| 2  1 (Large base) |
CH3 CH3
Hofmann product
(i) In E1 reactions, product formation always takes place by Saytzeff rule.
(ii) In E2 reactions, product formation takes place by Saytzeff as well as Hofmann rule. In almost all E2 reactions
product formation take place by Saytzeff rule.
• Examples of  - Elimination Reactions
a) Dehydrohalogenation is removal of HX from alkyl halides with alcoholic KOH or KNH 2 or ter- BuOK (Potassium
tertiary butoxide) and an example of - elimination, e.g.
Alc. KOH Alc. KOH

CH3 − CH2 X ⎯⎯ ⎯⎯→ H 2C = CH2 ; CH3 − CH − CH3 ⎯⎯ ⎯⎯→ CH3 CH = CH 2
(− HX ) Ethene | (− HX ) Propene
X
Alc.KOH
CH3 − CH2 − CH − CH3 ⎯⎯ ⎯⎯→ CH3 − CH = CH − CH3 + CH3 − CH2 − CH = CH2
| (− HX ) 2- Butene (Major) 1- Butene(Minor)
X
b) Dehydration of alcohol is another example of elimination reaction. When acids like conc. H 2 SO 4 or H 3 PO 4 are
used as dehydrating agents, the mechanism is E1 . The proton given by acid is taken up by alcohol.
Dehydration is removal of H 2 O from alcohols:
Conc. H2SO4 , 170C

e.g. CH3 − CH2 − OH ⎯⎯ ⎯⎯⎯⎯⎯ ⎯→ H 2C = CH2
(− H 2O)
Conc. H2SO4 , 170C

CH3 − CH2 − CH2 − OH ⎯⎯ ⎯⎯⎯⎯ ⎯ ⎯→ CH3 − CH = CH2
Propan - 1- ol (− H2O) Propene
(i) Dehydration of alcohols is in the order: Tertiary  Secondary  Primary

(3) (2) (1)
(ii) 2° and 3° alcohol by E1 process and 1° alcohol by E2 process. Alcohols leading to conjugated alkenes are more
easily dehydrated than the alcohols leading to non-conjugated alkenes.
CH2 = CH − CH − CH3 is easily dehydrated than CH3 − CH2 − CH − CH3 and also
| |
OH OH
OH OH OH
> >
in CH OH , heat
c) Dehalogenation : It is removal of halogens, e.g., CH2 − CH2 + Zn dust ⎯⎯ ⎯3⎯ ⎯⎯→ H 2C = CH2
| | (- ZnBr2 ) Ethylene
Br Br
Ethylene bromide
Cu, 300C
d) Dehydrogenation : It is removal of hydrogen, e.g., CH3 − CH − CH3 ⎯⎯ ⎯⎯ ⎯→ CH3 − C− CH3
| (− H 2 ) ||
OH O
Isopropyl alcohol Acetone

Table 14.11 : Summary of Elimination Mechanism
E1 E2
Mechanism Two-step One step

–
 alkene –
R − L → R → alkene
Nature of R–X Secondary, tertiary Primary alkyl halide, secondary, tertiary

Carbocation is the intermediate which can
undergo rearrangement to more stable
carbocation.
Kinetics First order rate = k[ RL] –

Second order rate = k[RL][B]
Competes with SN 1 SN 2
Stereochemistry No preferred conformations trans-coplanar elimination (trans-diaxial in

cyclohexane)
Regiochemistry Saytzeff's rule : favours more highly substituted Saytzeff's rule and Hofmann's rule (favours less
alkene. substituted alkene in Hofmann elimination).
Conjugated product always preferred Conjugated product always preferred
Competition with Some E1 always accompanies SN1 E2 favoured by strong bases, steric hindrance
substitution and higher temperature
Table 14.12 : Overall Summary of S N1 , S N 2 , E1 and E2 Reaction
Alkyl halide Poor Nucleophile Weak basic Strongly basic Unhindered Strongly Basic hindered
(e.g., H2O,ROH) nucleophile Nucleophile (e.g., RO–) Nucleophile (e.g., t-BuO–)
Methyl CH3X no reaction SN 2 SN 2 SN 2
Primary no reaction SN 2 SN 2 E2
(unhindered)
RCH2X
Primary (hindered) no reaction SN 2 E2 E2

R X
Secondary SN1 , E1 (slow) SN 2 E2 E2
R X
Tertiary E1 or SN1 SN1 , E1 E2 E2

X

Rearrangement Reactions
The reactions, which involve the migration of an atom or group from one site to another within the molecule (nothing is added
from outside and nothing is eliminated) resulting in a new molecular structure, are known as rearrangement reactions. The new
compound is actually the structural isomer of the original one.
It is convenient to divide rearrangement reactions into following types:
Rearrangement or Migration to Electron Deficient Atoms (Nucleophilic Rearrangement)
Those rearrangement reactions in which migrating group is nucleophilic and thus migrates to electron deficient centre which
may be carbon, nitrogen and oxygen.
B:
Y − B
| | | | | |
−Y
− C − C − ⎯⎯⎯→ − C− C− → − C− C −
| | | |
X: X
Bridged or non-classical carbocation
X= Nucleophilic species, Y = Electronegative group, B = Another nucleophile.

Rearrangement or Migration to Electron Rich Atoms (Electrophilic Rearrangement)
Those rearrangement reactions in which migrating group is electrophile and thus migrates to electron rich centre.
Rearrangement or Migration to free Radical Species (Free Radical Rearrangement)
Those rearrangement reactions in which the migrating group moves to a free radical centre. Free radical rearrangements are
comparatively rare.
Aromatic Rearrangement
Those rearrangement reactions in which the migrating group moves to aromatic nucleus. Aromatic compounds of the type (I)
undergo rearrangements in the manner mentioned below:
X–Y X–H X–H

Y
→ +
(I) Y
The element X from which group Y migrates may be nitrogen or oxygen.
Isomerism
Organic compounds having same molecular formula but differing from each other at least in some physical or chemical properties or both
are known as isomers and the phenomenon is known as isomerism.
The difference in properties of isomers is due to the difference in the relative arrangements of various atoms or groups present in their
molecules. Isomerism can be classified as follows:
Isomerism
Constitutional or Structural Isomerism Configurational or Stereo Isomerism

Without referring to space, the isomers differ in the The isomerism arises due to different arrangement of atoms or
arrangement of atoms within the molecule is called groups in space. It deals with the structure of molecules in three
structural isomerism. Thus, structural isomers have:
dimensions. Thus, stereoisomers have:
Chain Position Ring chain Functional Meta Tauto - Geometrical Optical Conformational
isomerism isomerism isomerism isomerism merism merism isomerism isomerism isomerism

Constitutional or Structural Isomerism
Chain, Nuclear or Skeleton Isomerism
This type of isomerism arises due to the difference in the nature of the carbon chain (i.e., straight or branched) which forms
the nucleus of the molecule.
Examples :
C4H10 : CH3 − CH2 − CH2 − CH3 , CH 3 − CH − CH 3

n−Butane |
CH3
Isobutane(2 - Methyl pro pane)
CH3
|
C5H12 : (Three) CH3 − CH2 − CH2 − CH2 − CH3 , CH 3 − C H − CH 2 − CH 3 , CH3 − C − CH3
| |
n− Pentane
CH3 CH3
Isopentane (2 - Methylbutane) Neopentane (2,2 - Dimethylpropane)
• Except alkynes chain isomerism is observed when the number of carbon atoms is four or more than four.
• Chain isomers differ in the nature of carbon chain, i.e., in the length of carbon chain.
• The isomers showing chain isomerism belong to the same homologous series, i.e., functional group, class of the compound
(Cyclic or open) remains unchanged.
• Chain and position isomerism cannot be possible together between two isomeric compounds. If two compounds are chain
isomers then these two will not be positional isomers.
Position Isomerism
It is due to the difference in the position of the substituent atom or group or an unsaturated linkage in the same carbon chain.
Examples
C3 H6 Cl2 : CH3 − CCl2 − CH3 , CH3 − CH2 − CH − Cl2 , CH3 − C H − C H 2 , C H 2 − CH 2 − C H 2

| | | |
2, 2−Dichloro propane, 1,1−Dichloro propane
(gemdihalide) (gemdihalide) Cl Cl Cl Cl
1, 2 − Dichloro propane 1, 3 − Dichloro propane
( , - dihalide)
(Vicdihalide)
C4 H 8 : CH3 − CH2 − CH = CH2 ; CH3 − CH = CH − CH3

1- Butene 2- Butene
C3 H 6 O2 : CH3 − CH − CHO ; CH2 − CH2 − CHO

| |
OH OH
2 − Hydroxy propanal
C7 H7 NO 2 :
CH3 CH3 CH3

NO2
NO2
o-Nitrotoluene m-Nitrotoluene
NO2
p-Nitrotoluene
• Aldehydes, carboxylic acids (and their derivatives) and cyanides do not show position isomerism.
• Monosubstituted alicylic compounds and aromatic compounds do not show position isomerism.
• Structural isomers which differ in the position of the functional group are called regiomers.
Functional Isomerism
This type of isomerism is due to difference in the functional group present in the isomers. The following pairs of compounds
always form functional isomers with each other:

• Alcohols and Ethers (CnH2n+2O)
C2H6O : CH3 − CH2 − OH ; H 3 C − O − CH 3

Ethyl alcohol Dimethylether
C3H8O : CH3 − CH2 − CH2 − OH ; C2 H 5 − O − CH3

n − Propyl alcohol Ethyl methylether
C4H10O : CH3 − CH 2 − CH 2 − CH 2 − OH ; C2 H 5 − O − C2 H 5
n−Butyl alcohol Diethyl ether
• Aldehydes, Ketones and Unsaturated Alcohols …etc. (CnH2nO)
O
||
C3H6O : CH3 − CH2 − CHO ; CH 3 − C − CH 3 ; CH 2 − CH− CH3 ; CH2 = CH − CH2 OH
Propionaldehyde Acetone Allylalcohol
O
1, 2−Epoxy propane
H OH
O
1, 3- Expoxy propane Cyclopropanol
• Acids, Esters and Hydroxy Carbonyl Compounds …etc. (CnH2nO2)
C2H4O2 : CH3COOH ; HCOOCH3

Acetic acid Methyl formate
O
||
C3H6O2 : CH3 − CH2 − COOH ; CH3COOCH3 ; CH3 CHCHO ; CH3 − C − CH2 − OH
Propionic acid Methyl acetate | 1− Hydroxy propan- 2- one
OH
• Alkynes and Alkadienes (CnH2n-2)
C4H6 : CH3 − CH2 − C  CH ; H2C = CH − CH = CH2 ; CH3 − C  C − CH3 ; H2C = C = CH − CH3

1− Butyne 1,3 − Butadiene 2−Butyne 1, 2− Butadiene
• Alcohols and Phenols
CH2OH OH
CH3
C7H8O:
Benzyl alcohol o-Cresol
• Oximes and Amides
O
||
C2H5NO: CH3 − CH = NOH ; CH3 − C − NH2
Acetaldoxime Acetamide
Ring-chain Isomerism
This type of isomerism is due to different modes of linking of carbon atoms, i.e., the isomers possess either open chain or
closed chain structures.

H2
C
CH2 − CH2
H 2C CH2 | CHCH3
C6H12 : | | ; C H 2 − CH2 ; CH3CH2CH2CH2CH = CH2
H 2C CH2 Methylcyclopentane 1−Hexene
C
H2
Cyclohexane
• Ring – chain isomers are always functional isomers.
Metamerism
This type of isomerism is due to the difference in the nature of alkyl groups attached to the polyvalent atoms or functional
group. Metamers always belong to the same homologous series. Compounds like ethers, thio-ethers ketones, secondary
amines, etc. show metamerism.
Examples:
CH3 C2 H 5
C5H13N : C3 H7 − N ; C2 H 5 − N
CH3 CH 3
Dimethyl propylamine Diethyl methylamine
C6H15N : C3 H7 − NH − C3 H7 ; C2 H5 − NH − C4 H9
Dipropylamine Butylethylamine
• Point to Remember: If same polyvalent functional group is there in two or more organic compounds, then chain or position
isomerism is not possible, there will be metamerism e.g.,
(a) CH3 − C− CH2 − CH2 − CH3 ; CH3 CH2 − C− CH 2CH3 are metamers and not position isomers.
|| ||
O O
(Pentan − 2− one) (Pentan − 3 − one)
(b) CH3 − C − CH 2 CH 2 CH3 ; CH3 − C − C H − CH3 are metamers and not chain isomers.
|| || |
O O CH3
(Pentan − 2− one) (3 - Methylbutan- 2- one)
• Alkenes does not show metamerism.
Tautomerism
• The type of isomerism in which a substance exists in two readily interconvertible different structures leading to dynamic
equilibrium is known as tautomerism and the different forms are called tautomers (or tautomerides).
• It is caused by the wandering of hydrogen atom between two polyvalent atoms. It is also known as Desmotropism (Desmos
= bond and tropos = turn). If the hydrogen atom oscillates between two polyvalent atoms linked together, the system is a
dyad and if the hydrogen atom travels from first to third atom in a chain, the system is a triad.
a) Dyad System
Hydrocyanic acid is an example of dyad system in which hydrogen atom oscillates between carbon and nitrogen atoms.
H −C  N C N−H
b) Triad System
Keto-enol system: Polyvalent atoms are oxygen and two carbon atoms.
Examples :
O H OH
|| | |
− C− C − C = C−
| |
(Keto) (Enol)
Acetoacetic ester (Ethyl acetoacetate) :

O OH
|| |
CH3 − C− CH2COOC2 H5 CH3 − C = CHCOOC2 H5
Keto form (92.1%) Enol form (7.9%)

• Acetoacetic ester gives certain reactions showing the presence of keto group (Reactions with HCN , H 2 NOH , H 2 NNHC 6 H 5
, etc.) and certain reactions showing the presence of enolic group (Reactions with Na , CH 3COCl , NH 3 , PCl 5 , Br2 water and
colour with neutral FeCl 3 , etc.).
• Enolisation is in Order:
CH 3 COCH 3  CH 3 COCH 2 COOC 2 H 5  C 6 H 5 COCH 2 COOC 2 H 5  CH 3 COCH 2 COCH 3  CH 3 COCH 2 CHO
• Acid Catalysed Conversion:
O OH OH
|| H | |
−H
CH3 − C− CH2 − R CH3 − C − C H − R ⎯⎯⎯→ CH3 − C = CH − R
Keto  | (Enol form)
H
(Intermediate)
• Base Catalysed Conversion:

−
O O O OH
|| || | |
OH H2O
CH3 − C− CH2 − R CH3 − C− C H − R ⎯⎯→ CH3 − C = CH − R ⎯⎯⎯→ CH3 − C = CH − R
Keto form
– H2O − − OH (Enol)
• Triad System Containing Nitrogen:
O
Nitrous acid exists in 2 forms: H −O− N =O H−N
Nitrite form O
Nitro form
O O
Nitro acinitro system: CH3 − CH2 − N CH3 − CH = N
O OH
Nitro form (i) Aci form (ii)
• Characteristics of Tautomerism
a) The tautomeric forms remain in dynamic equilibrium. Hence, their separation is a bit difficult.
b) The two tautomeric forms differ in their stability. The change of one form into another is also catalysed by acids and
bases.
c) Keto=enol tautomerism is exhibited only by such aldehydes and ketones which contain at least one  -hydrogen.
For example: CH 3 CHO, CH 3 CH 2 CHO, CH 3 COCH 2 COCH 3 etc.
d) Tautomerism is not possible in benzaldehyde (C 6 H 5 CHO ) , benzophenone (C6 H 5 COC 6 H 5 ) , tri methyl acetaldehyde,
(CH 3 ) 3 C − CHO and chloral CCl 3 − CHO as they do not have  − H .
Configurational or Stereo Isomerism
Geometrical or Cis-trans Isomerism
• The compounds which have same molecular formula but differ in the relative spatial arrangement of atoms or groups in
space are known as geometrical isomers and the phenomenon is known as geometrical isomerism.
• The isomer in which same groups or atoms are on the same side of the double bond is known as cis form and the isomer in
which same groups or atoms are on the opposite side is called trans-isomer.
Examples:
H − C− COOH H − C− COOH H 3C − C − COOH H3C − C− COOH

|| || || ||
H − C − COOH HOOC − C − H H − C − COOH HOOC − C − H
Fumaric acid (trans) Mesaconic acid(trans − isomer)
Maleic acid (cis)
; Citraconic acid (cis - isomer)
• Conditions for Geometrical Isomerism
Compound will show geometrical isomerism if it fulfills the following two conditions:
a) There should be frozen rotation about two adjacent atoms in the molecule.

C=C frozen rotation about carbon, carbon double bond in alkenes.
frozen rotation about carbon-carbon single bond in cycloalkanes.
C = N − frozen rotation about carbon, nitrogen double bond in oxime and imine.
b) Both substituents on each carbon should be different about which rotation is frozen.
If these two conditions are fulfilled, then compound will show geometrical isomerism.
The compounds of the following type will not show geometrical isomerism.
a − C− a x − C− a a − C− a
|| || ||
x −C−y a−C−a x −C− x
• Distinction between Cis- and Trans- isomers
a) By Cyclization Method
Generally, the cis-isomer (e.g. maleic acid) cyclises on heating to form the corresponding anhydride while the trans-
isomer does not form its anhydride.
H − C− COOH H − C− CO
|| Heat
⎯⎯ ⎯→ || O + H 2O
H − C − COOH 403 K H − C − CO
Maleic acid(cis) Maleic anhydride
Note that the two reacting groups (–COOH) are near to each other.
H − C− COOH Heat
|| ⎯⎯⎯→ No anhydride
HOOC − C − H
Fumaric acid (trans)
Note that the two reacting groups (–COOH) are quite apart from each other, hence cyclisation is not possible.
b) By Hydroxylation (Oxidation by means of KMnO4 , OsO4 or H2O2 in presence of OsO4 )
Oxidation (Hydroxylation) of alkenes by means of these reagents proceeds in the cis-manner. Thus the two geometrical
isomers of an alkene lead to different products by these reagents. For example,
H − C − COOH OH
Alk. KMnO4 / OH− H COOH
|| ⎯⎯ ⎯⎯⎯⎯⎯→
H COOH
H − C − COOH OH
Maleicacid (cis) meso− Tartaric acid
OH OH
H − C − COOH H
Alk. KMnO4 / OH− COOH HOOC H
|| ⎯⎯⎯⎯⎯⎯⎯→ +
HOOC − C− H HOOC H H COOH
Fumaricacid (trans)
OH OH
(+) − Tartaric acid (−)− Tartaric acid
c) By Studying their Dipole Moments
The cis-isomer of a symmetrical alkene (Alkenes in which both the carbon atoms have similar groups) has a definite
dipole moment, while the trans-isomer has either zero dipole moment or less dipole moment than the cis-isomer. For
example, 1,2-dichloroethylene and butene-2.
H − C− Cl H − C− Cl H − C − CH 3 H − C − CH3
|| || || ||
H −C−Cl Cl−C−H H − C − CH3 CH3 −C − H
cis− Dichloroethylene trans− Dichloroethylene cis − Butene − 2 trans − Butene − 2
(  =1.9 D) (  =0.0 D) (  0 D) (  = 0. 0 D )

In trans-isomer of the symmetrical alkenes, the effect produced in one half of the molecule is cancelled by that in the
other half of the molecule. In case of unsymmetrical alkenes, the cis-isomer has higher dipole moment than the
corresponding trans-isomer.
For Example:
H 3C − C − Cl CH3 − C− Cl
|| ||
CH3 −CH2 −C −Cl Cl −C −CH2CH3
cis − 2, 3 − Dichloropentene − 2 trans − 2,3 − Dichloropentene− 2
(High dipolemoment)
(Less dipolemoment)
Similar is the case with hexene-2.
H 3C CH 2 CH 2 − CH3 H CH 2 CH 2 − CH 3
C=C C=C
H H CH 3 H
cis − Hexene − 2(more polar) trans − Hexene − 2(Less polar)
d) By Studying other Physical Properties
The cis-isomer of a compound has higher boiling point due to higher polarity, higher density and higher refractive
index than the corresponding trans-isomer (Auwers-skita rule).
CH3 − C− H CH3 − C − H
|| ||
CH3 − C− H H − C − CH3
cis− 2−Butene trans − 2 − Butene
b.p 4C 1 C
m.p. −139C − 106 C
H − C − Cl H − C − Cl
|| ||
H − C − Cl Cl − C − H
cis −1, 2 − Dichloroethene trans −1, 2 − Dichloroethene
60C 48C
− 80C − 50C
The trans-isomer has higher melting point than the cis-isomer due to symmetrical nature and more close packing of the
trans-isomer.
Stability : Trans-isomer is more stable than cis-isomer due to symmetrical structure.
• Note: Cis-trans isomers are configurational isomers but not mirror images, hence cis and trans isomers are always
diastereomers (explained later in this chapter).
• E and Z System of Nomenclature
‘Cis’ and ‘Trans’ designations cannot be used if four different atoms or groups are attached to the carbon atoms of a double
bond.
a d
C=C
b e
In such cases, E and Z system of nomenclature is used. This system is based on a priority system developed by Cahn, Ingold
and Prelog. In this system, the two atoms or groups attached to each of the doubly bonded carbon are put in order of
preference on the basis of sequence rules.
a) Sequence Rules
The symbol ‘E’ is assigned to an isomer in which the atoms or groups of higher preference are on the opposite side (E
from German word Entgegen = across or opposite).
The symbol ‘Z’ is assigned to an isomer in which the atoms or groups of higher preference are on the same side (Z from
German word, Zusammen = together).
1 2 1 1
C=C C=C
2 E − isomer
1 2 Z − isomer 2
In the above structures, 1 signifies higher preference and 2 signifies lower preference. Preference in most of the cases
‘Z’ corresponds to cis-form and ‘E’ to trans-form. However, there are many exceptions.

b) Preference Order
The following rules are followed for deciding the precedence order of the atoms or groups;
(i) Higher priority is assigned to the atoms of higher atomic number. For example, the order of preference in the
following atoms, H , Cl , I , Br is : I (at. no. 53)> Br (at. no. 35)>Cl (at. no. 17)>H (at. no. 1).
(ii) If isotopes of the same element are attached, the isotope with higher mass number is given higher order of
preference. For example, deuterium (12 D) is assigned higher priority in comparison to hydrogen (11 H) .
(iii) In the groups, the order of preference is also decided on the basis of atomic number of first atom of the group. For
example, in the following set,
−Cl ,−OH ,−COOH ,− NH − CH 3 ,−SO 3 H

.
The order of the precedence is :
− Cl  − S O3 H  − O H  − N HCH 3  − C OOH
    
( at.no17) (at.no.16) (at.no.8) (at.no.7) (at.no. 6)
When the order of preference of the groups cannot be settled on the first atom, the second atom or the subsequent
atoms in the groups are considered. For example, in the set −CH 2 − CH 3 ,−CH 3 ,−COOH , the order cannot be
decided on the basis of first atom as it is same in all the groups. However, in −CH 2 − CH 3 , the second atom is
carbon, in −CH 3 , the second atom is hydrogen while in −COOH , the second atom is oxygen. Hence, the order
of preference is :
−C O OH  −CH2 − C H3  − CH3
  
(at.no.8) (at.no.6) (at.no.1)
(iv) A doubly or triply bonded atom is considered equivalent to two or three such atoms. For example,
N
|
The group C = O is equal to C− O and the group −C  N is equal to − C− N .
| |
O N
• Number of Geometrical Isomers in Polyenes
When a compound has n double bonds and ends of a polyene are different, the number of geometrical isomers = 2n
C6 H 5 − CH = CH − CH = CH − CH = CH − CH = CH − Cl
The given compound has four double bonds and the two ends are different (One is C6 H 5 and other is Cl). Therefore,
number of geometrical isomers = 2n = 24 = 16 .
When the ends of polyene are same.
a) Case I : When number of double bonds (=n) is even then the number of geometrical isomers = 2n −1 + 2[(n / 2)−1]
Cl − CH = CH − CH = CH − CH = CH − CH = CH − Cl
n = 4 , even
Number of geometrical isomers = 2n−1 + 2(n / 2)−1 = 23 + 21 = 8 + 2 = 10 .
b) Case II : When number of double bonds (=n) is odd.
 n+1 
 2  −1
Number of geometrical isomers = 2n−1 + 2  
C6 H 6 − CH = CH − CH = CH − CH = CH − C6 H5
(n = 3, odd)
Number of geometrical isomers = 22 + 22−1 = 22 + 21 = 4 + 2 = 6 .

• Geometrical Isomerism in Nitrogen Compounds
a) Geometrical Isomerism due to C = N − Bond.
The important class of compounds exhibiting geometrical isomerism due to C = N − bond are oximes, nitrones,
hydrazones and semicarbazones. But the most common compound is oxime.
Oximes : In aldoxime, when hydrogen and hydroxyl groups are on the same side, the isomer is known as syn.
(analogous to cis) and when these groups are on the opposite side, the isomer is known as anti (analogous to trans)
C6 H 5 − C − H C6 H5 − C − H
|| ||
N − OH HO − N
Syn - benzaldoxime Anti− benzaldoxime
In ketoximes the prefixes syn and anti indicate which group of ketoxime is syn or anti to hydroxyl group. For example
CH3 − C − C2 H5
|| this compound will be named as;
N −OH
Syn-ethyl methyl ketoxime  HO and C2 H 5 are syn or
Anti-methyl ethyl ketoxime  HO and CH 3 are anti.
Similarly consider the following structure
C2 H 5 −C −CH3
||
N −OH
Syn − methyl ethyl ketoxime
or Anti− ethyl methyl ketoxime
b) Geometrical Isomerism due to N = N Bond.
C H −N
6 5 || C6 H5 − N
||
C H −N N −C6 H5
6 5
Syn-azobenzene Anti − azobenzene
• Geometrical Isomerism Shown by Cumulatrienes
Cumulatrienes (Trienes with three adjacent double bonds) show only geometric isomerism. This is because their molecule
is planar, as such the terminal − CH 3 groups and H- atoms lie in the same plane. Therefore, in this case their planar structure
can exist in two diastereoisomeric forms, cis- and trans- but no enantiomeric forms are possible.
H 3C CH3 H 3C H
C=C=C=C C=C=C=C
H H H CH3
cis − Hexa − 2,3, 4 − triene trans − Hexa − 2,3,4 − triene
• Geometrical Isomerism in Cycloalkanes
Disubstituted cycloalkanes show geometrical isomerism.
CH3
OH
H OH H
H CH3
H OH HO
H
H Cis-1,2-cyclohexanediol
Cis-1,2-dimethylcyc Trans-1,2-cyclopent-
lopropane anediol

Optical Isomerism
• Definition
Compounds having similar physical and chemical properties but they have the ability to rotate the plane of polarised light
either to the right (Clockwise) or to the left (Anticlockwise) are termed as optically active or optical isomers and the property
is called optical activity or optical isomerism.
The optical activity was first observed in inorganic substances like quartz, rock-crystals and crystals of potassium chlorate
(KClO 3 ) , potassium bromate (KBrO3 ) and sodium periodate ( NaIO 4 ) .
• Measurement of Optical Activity
The measurement of optical activity is done in terms of specific rotation which is defined as the rotation produced by a
solution of length of 10 centimetre (One decimetre) and unit concentration (1 g/mL) for the given wavelength of the light at
the given temperature.

Specific rotation,   t C = obs
lC
Where  obs is the rotation observed, l is the length of the solution in decimeters and C is the number of grams in 1mL of
solution. The specific rotation of the sucrose at 20°C using sodium light (D-line, =5893Å) is +66.5° and is denoted as:
 20
D
C
= +66.5 (C = 0.02 g / mL water)
+ sign indicates the rotation in clockwise direction.
• Types of Optical Isomers
On the basis of the study of optical activity, the various organic compounds were divided into four types :
a) d-form: The optical isomer which rotates the plane of the polarised light to the right (Clockwise) is known as
dextrorotatory isomer (Latin: dexter = right) or d-form or indicated by +ve sign.
b) l-form: The optical isomer which rotates the plane of the polarised light to the left (Anticlockwise) is known as
laevorotatory isomer (Latin; laevo = left) or l-form or indicated by –ve sign.
c) dl-form: The optical powers of the above two isomers are equal in magnitude but opposite in sign. An equimolar
mixture of the two forms, therefore, will be optically inactive due to external compensation. This mixture is termed as
racemic mixture or dl-form or () mixture.
d) meso form: Optical isomer with a plane of symmetry is called meso form. It is optically inactive due to internal
compensation, i.e., the rotation caused by upper half part of molecule is neutralised by lower half part of molecule.
• Chirality
a) Definition: A molecule (or an object) is said to be chiral or dissymmetric, if it does not possess any element of symmetry
and not superimposable on its mirror image. This property of the molecule to show non-superimposability is called
chirality.
b) Chiral and Achiral Molecule:
A molecule (or an object) which is superimposable on its mirror image is called achiral (symmetric).
To understand the term chiral and achiral let us consider the alphabet letters ‘P’ and ‘A’ whereas ‘P’ is chiral, ‘A’ is
achiral as shown in fig.
Mirror Mirror
Non-superimposable Superimposable
(Chiral or dissymmetric) (Achiral or symmetric)

c) Elements of Symmetry: There are three elements of symmetry,
(i) Plane of Symmetry: It may be defined as a plane which divides a molecule in two equal parts that are related
to each other as an object and mirror image. e.g.,
COOH
|
H − C − OH
| Plane of symmetry
H − C − OH
|
COOH
(ii) Centre of Symmetry: It may be defined as a point in the molecule through which if a line is drawn in one
direction and extended to equal distance in opposite direction, it meets another similar group or atom, eg.
Centre of symmetry
CH3 CH3 CH 3 H
| NH − CO | | NH − CO |
C C and C • C
| CO − NH | | CO − NH |
H H H CH 3
Cis − Dimethyl diketo piperazine Trans − Dimethyl diketo piperazine
Since trans form contains a centre of symmetry, it is optically inactive.

(iii) Alternating Axis of Symmetry: A molecule is said to possess a n-fold alternating axis of symmetry if an
orientation indistinguishable from the original is obtained when molecule is rotated 360/n degrees around an axis
passing through the molecule and the rotated molecule is reflected in a mirror that is perpendicular to the axis of
rotation.
Reflection perpendicular
to axis rotation
Cl H H F Cl H
H F 180o rotation Cl H F
H
F H around axis
H Cl H
H Cl F
F H H Cl
• Symmetric, Asymmetric and Dissymmetric Molecules
a) Symmetric Molecules: If any symmetry is present in the molecule then molecule will be symmetric molecule.
b) Dissymmetric Molecules: Molecule will be a dissymmetric molecule if it has no plane of symmetry, no centre of
symmetry and no alternating axis of symmetry.
c) Asymmetric Molecules: Dissymmetric molecule having at least one asymmetric carbon is known as asymmetric
molecule. All asymmetric molecules are also dissymmetric molecules but the reverse is not necessarily true.
COOH
| CHO
H — C  — OH |
| H — C  — OH
H — C  — OH |
| CH 3
C6 H 5 No plane of symmetry

No plane of symmetry Dissymmetric molecule
 
Dissymmetric molecule Asymmetric molecule

Asymmetric molecule

• Chiral or Asymmetric Carbon Atom
a) A carbon bonded to four different groups is called a chiral carbon or a chirality centre. The chirality centre is indicated
by asterisk. e.g.,
a CH3
| |
d −C −b*
HO − C * − H
| |
c COOH
Lactic acid
b) Carbons that can be chirality centres are sp 3 -hybridised carbons; sp 2 and sp -hybridised carbons cannot be chiral
carbons because they cannot have four group attached to them.
c) Isotopes of an atom behave as different group in stereoisomerism.
D H1
| |
H — C* — T Cl 35 — C* — Cl 37
| |
Br H2
• Enantiomer
Optical isomers which are nonsuperimposable mirror images of each other are called enantiomers.
• Racemic Mixture
An equimolar mixture of two enantiomers is called a racemic mixture (or racemate,  form, (dl) form or racemic
modification). Such a mixture is optically inactive because the two enantiomers rotate the plane polarised light equally in
opposite directions and cancel each other’s rotation. This phenomenon is called external compensation.
a) Racemic mixture can be separated into (+) and (–) forms. The separation is known as resolution.
b) The conversion of (+) or (–) form of the compound into a racemic mixture is called racemisation. It can be caused
by heat, light or by chemical reagents.
c) Racemic mixture is designated as being (  ) or (dl).
Table 14.13: Comparison between Racemic Modification and Meso-Compound
Racemic Modification Meso Compound
Racemic modification is a mixture of the two enantiomers of a substance It is a single molecule.

in equal proportions.
The loss of optical activity due to external compensation. The loss of activity is due to internal compensation.
The loss of optical activity may be partial or complete depending upon The loss of optical activity is complete.
the relative proportions of the enantiomers.
• Optical Activity of Compounds Containing one Asymmetric Carbon

  
CH3 − C HOH − COOH ; CH 2 OH − C HOH − CHO ; C6 H 5 − C HCl − CH3
Lactic acid Glyceraldehyde 1- Chloro-1- phenylethane
Any molecule having one asymmetric carbon atom exists in two configurational isomers which are nonsuperimposable
mirror images.
COOH COOH
| |
H — C — OH HO — C — H
| |
CH3 CH3
(I) (II)

Thus (I) and (II) are enantiomers. Pair of (I) and (II) is known as enantiomeric pair.
• Diastereomers
Optical isomers which are neither mirror images nor superimposable to each other are called diastereomers.
• Properties of Diastereomers
a) Diastereomers have different physical properties, e.g., melting and boiling points, refractive indices, solubilities in
different solvents, crystalline structures and specific rotations.
b) Because of differences in solubility they often can be separated from each other by fractional crystallisation; because of
slight differences in molecular shape and polarity, they often can be separated by chromatography.
c) Diastereomers have different chemical properties towards both chiral and achiral reagents. However, since the
diastereomers have the same functional groups, their chemical properties are not very dissimilar.
• Optical Activity of Compounds Containing two Asymmetric Carbons
a) Case I : When molecule cannot divisible into two identical halves.
The number of optical isomers possible in this case is four. Further there will be two pairs of enantiomers and two
racemic mixtures.
Example : Dibromocinnamic acid exists in following four optically active forms:
COOH COOH COOH COOH

| | | |
H − C− Br Br − C− H H − C− Br Br − C− H
| | | |
H − C− Br Br − C− H Br − C− H H − C− Br
| | | |
C6 H 5 C6 H 5 C6 H 5 C6 H 5
(I) (II) (III) (IV)
First pair of enantiomers Second pair of enantiomers
Racemic Mixture 1: Equimolar mixture of (I) and (II); Racemic Mixture 2: Equimolar mixture of (III) and (IV)
b) Case II : When molecule is divisible into two identical halves.

Number of optical isomers= 2
Number of meso forms = 1
Total number of configurational isomers = 3
Example: Tartaric acid exists in the following three forms;
COOH COOH COOH

| | |
H − C − OH HO − C − H H − C − OH
| | | Plane of symmetry
HO − C − H H − C − OH H − C − OH
| | |
COOH COOH COOH
(I) (II) (III)
meso form
• Enantiomeric Excess
A sample of an optically active substance that consists of a single enantiomer is said to be enantiomerically pure or to
have an enantiomeric excess of 100%. An enantiomeric pure sample of (+)-2-butanol shows a specific rotation of 13.52o
. On the other hand, a sample of (+)–2-butanol that contains less than an equimolar amount of (–)-2-butanol will show a
specific rotation that is less than + 13.52o but greater than 0o .
Such a sample is said to have an enantiomeric excess less than 100%. The enantiomeric excess is defined as follows :
(moles of one enantiomer – moles of other enantiomer) 100

% Enantiomeric excess = Total number of moles of both enantiomers
The enantiomeric excess can be calculated from optical rotation

Observed specific rotation
% Enantiomeric excess =  100
Specific rotationof pure enantiomer
Enantiomeric excess is also known as optical purity.
Table 14.14: Comparison of Enantiomers and Diasteriomers
Enantiomers Diastereomers
They are non-superimposable mirror image They do not have any such relationship
They have identical physical properties They have different physical properties
Identical chemical properties Similar but not identical chemical properties
They can not be separated from each other by physical methods They can be easily separated by methods such as fractional
crystallisation
They are optically active in nature A few diastereomers which are also geometrical isomers may
be optically inactive
• Calculation of Number of Optical Isomers
a) If molecule is not divisible into two identical halves and molecule has n asymmetric carbon atoms then
Number of optically active forms = 2n = a
Number of enantiomeric pair = a/2
Number of racemic mixture = a/2
Number of meso form = 0
b) If molecule is divisible into two identical halves, then the number of configurational isomers depends on the number of
asymmetric carbon atoms.
• Case I : When compound has even number of asymmetric carbon atoms, i.e., n = 2, 4, 8, 10, 12, ..... :
a) Number of optically active forms = a = 2n −1
b) Number of enantiomeric pairs = a / 2
c) Number of racemic mixture = a / 2
d) Number of meso forms = m = 2(n / 2)−1
e) Total number of configurational isomers = a + m
Example:
* *
COOH − CHOH − CHOH − COOH
(I) (II)
Two identical halves (I) and (II) having n = 2
Thus the number of optical Isomer = a = 2 2 −1 = 2
Number of meso form = m = 2(n / 2)−1 = 2(2 / 2)−1 20 = 1
Total number of configurational isomers = 2 + 1 = 3
• Case II : When compound has odd number of carbon atoms, i.e., n = 3, 5, 7, 9, 11, ...... :
a) Number of optically active forms = a = 2n −1 − 2(n −1) / 2
b) Number of enantiomeric pairs = a / 2
c) Number of racemic mixture = a / 2

d) Number of meso forms = m = 2(n −1) / 2
e) Total number of configurational isomers = a + m
Example:
* * *
CH2OH − CHOH− CH OH − CHOH− CHOH
(I) (II)
Compound has two identical halves and has three asymmetric carbons
n−1
Thus, a = 2n−1 − 2 2 = 22 − 21 = 4 − 2 = 2
n−1
m= 2 2 = 21 = 2
Hence total number of configurational isomers = 2 + 2 = 4
• Optical Activity in Compounds Containing no Asymmetric Carbon
Although the largest number of known optically active compounds are optically active due to the presence of chiral carbon
atom, some compounds are also known which do not possess any chiral carbon atom, but on the whole their molecules are
chiral; hence they are optically active. Various types of compounds belonging to this group are allenes, alkylidene
cycloalkanes, spiro compounds (spirans) and properly substituted biphenyls.
a) Allenes: Allenes are the organic compounds of the following general formulae.
C=C=C
Allenes exhibit optical isomerism provided the two groups attached to each terminal carbon atom are different, i.e.,
a a a x
C=C=C or C=C=C
b b b y
b) Alkylidene Cycloalkanes and Spiro Compounds: When one or both of the double bonds in allenes are replaced
by one or two rings, the resulting systems are respectively known as alkylidene cycloalkanes and spirans.
H 3C H
=C
H COOH
1-Methylcyclohexylidene-4- acetic acid
(Alkylidene cycloalkane)
a CH2 CH2 a
C C C
b CH2 CH2 b
Spirans
c) Biphenyls : Suitably substituted diphenyl compounds are also devoid of individual chiral carbon atom, but the
molecules are chiral due to restricted rotation around the single bond between the two benzene nuclei and hence they
must exist in two non-superimposable mirror images of each other. Such types of stereoisomerism which is due to
restricted rotation about single bond, is known as atropisomerism and the stereoisomers are known as atropisomers.
Examples:
COOH O2N F HOOC
NO2 HOOC COOH F

Note: The above discussion leads to the conclusion that the essential condition for optical isomerism is the molecular dissymmetry
or molecular chirality and not the mere presence of a chiral centre. However, it may be noted that the molecules having only one
chiral centre are always chiral and exhibit optical isomerism.
• Fischer Projection Formulae
The arrangement of the atoms or groups in space that characterises a stereoisomer is called its configuration.
Emil Fischer (1891) provided an easy method to represent the three dimensional formulae of various organic molecules
on paper. Fischer projection is, thus, a planar representation of the three dimensional structure.
By convention, the following points are followed in writing the Fischer formula.
a) The carbon chain of the compound is arranged vertically, with the most oxidised carbon at the top.
b) The asymmetric carbon atom is in the paper plane and is represented at the interaction of crossed lines.
c) Vertical lines are used to represent bonds going away from the observer, i.e., groups attached to the vertical lines are
understood to be present behind the plane of the paper.
d) Horizontal lines represent bonds coming towards the observer, i.e., groups attached to the horizontal lines are
understood to be present above the plane of the paper.
Asymmetric Carbon atom
• Name of Optical Isomers
Following three nomenclatures are used for optically active compounds:
a) D. L. System of Nomenclature : This nomenclature is mainly used in sugar chemistry or optically active polyhydroxy
carbonyl compounds. This nomenclature was given by Emil Fischer to designate the configurations of various sugars
relative to the enantiomeric (+) and (–) glucose as reference.
All sugars whose Fischer projection formula shows the OH group on the chiral carbon atom adjacent to the terminal
CH 2 OH group on the right hand side belong to the D -series. Similarly if OH is on the left hand side, then the sugars
belong to the L -series.
| |
H — C — OH HO — C — H
| |
CH2OH CH 2 OH
D − series L− series
Examples:
CHO CHO
| |
H — C — OH HO — C — H
| |
CH 2 OH CH 2 OH
D(d ) glyceraldehyde L(l ) glyceraldehyde
or or
D(+ ) glyceraldehyde L(−) glyceraldehyde
(i) It must be noted that there is no relation between the sign of rotation (+, – or d, l) and the configuration (D and
L) of an enantiomer.

(ii) Any compound that can be prepared from, or converted into D(+) glyceraldehyde will belong to D-series and
similarly any compound that can be prepared from, or converted into L(–) glyceraldehyde will belong to the L-
series.
This nomenclature is also used in  -amino acids.
b) Erythro and Threo system of Nomenclature : This nomenclature is used only in those compounds which have
(i) Only two chiral carbons and
(ii) The following structure, R − Cab − Cbc − R
i.e., out of six substituents on two asymmetric carbons, at least two should be same.
When two like groups in Fischer projection formula are drawn on the same side of the vertical line, the isomer is called
erythro form; if these are placed on the opposite sides, the isomer is said to be threo form.
R R CH 3 CH 3
| | | |
a—C—b a—C—b H — C — Cl H — C — Cl
| | ; | |
c—C—b b—C—c H — C — Br Br — C — H
| | | |
R R  C6 H 5 C6 H 5
Erythro form Threo form Erythro form Threo form
c) R, S Nomenclature (Absolute Configuration)
The order of arrangement of four groups around a chiral carbon (stereocentre) atom is called the absolute configuration
around that atom. System which indicates the absolute configuration was given by three chemists R.S. Cahn, C.K.
Ingold and V. Prelog. This system is known as (R) and (S) system or the Cahn-Ingold-Prelog system.
• Nomenclature: The letter (R) comes from the latin rectus (means right) while (S) comes from the latin sinister (means
left). Any chiral carbon atom has either a (R) configuration or a (S) configuration. Therefore, one enantiomer is (R) and other
is (S). A racemic mixture may be designated (R) (S), meaning a mixture of the two. (R) (S) nomenclature is assigned as
follows :
Step I : By a set of sequence rules given below the atoms or groups connected to the chiral carbon are assigned a priority
sequence.
• Sequence Rules for Order of Priority
a) Rule 1 : If all four atoms directly attached to the chiral carbon are different, priority depends on their atomic number.
The atom having the highest atomic number gets the highest priority, i.e., (1). The atom with the lowest atomic number
is given the lowest priority, i.e., (2), the group with next higher atomic number is given the next higher priority (3) and
so on. Thus,
Cl 3
| |
F — C — I  4 — C —1
| |
Br 2
F Cl Br I
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
Increasing atomic number

COOH 4
| |
H 2 N — C — Br  3— C —1
| |
OH 2
C N O Br
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
Increasing priority with atomic number
b) Rule 2 : If two or more than two isotopes of the same element is present, the isotope of higher atomic mass receives
the higher priority.
Increasing priority
3 2 1
c) Rule 3 : If two or more of the atoms directly bonded to the chiral carbon are identical, the atomic number of the next
atoms are used for priority assignment. If these atoms also have identical atoms attached to them, priority is determined
at the first point of difference along the chain. The atom that has attached to it an atom of higher priority has the higher
priority.
I 2 H and Br
| 
I − H 2C − H 2 C − C − C H 2 − Br
 |
2 H and C CH2 − CH2 − CH3

2 H and C
In this example the atoms connected directly to the chiral carbon are iodine and three carbons. Iodine has the highest
priority. Connected, to the three carbons are 2H and Br, 2H and C and 2H and C. Bromine has the highest atomic
number among C,H and Br and thus CH 2 Br has highest priority among these three groups (i.e., priority no. 2).The
remaining two carbons are still identical (C and 2H) connected to the second carbons of these groups are 2H and I and
2H and C. Iodine has highest priority among these atoms, so that −CH 2 − CH 2 − I is next in the priority list and
CH 2 − CH 2 − CH 3 has the last priority.
I 1
|
I − CH 2 − CH 2 − C− CH 2 − Br  3 2
|
CH2 −CH2 −CH3 4
d) Rule 4 : If a double or a triple bond is linked to chiral centre the involved atoms are duplicated or triplicated
respectively.
O N O O
| | || |
− C = O is equivalent to − C− O ; − C  N is equivalent to − C − N ; − C− OH is equivalent to − C− OH
| | | |
N O
By this rule, we obtained the following priority sequence :
Increasing priority
• Step 2 : The molecule is then visualised so that the group of lowest priority (4) is directed away from the observer (At this
position the lowest priority is at the bottom of the plane). The remaining three groups are in a plane facing the observer. If
the eye travels clockwise as we look from the group of highest priority to the groups of second and third priority (i.e.,
1 → 2 → 3 with respect to 4) the configuration is designated as R. If arrangement of groups is in anticlockwise direction, the
configuration is designated as S.

Example 1:
2 2
1 3 3 1
4 4
Clockwise arrangement of Anticlockwise arrangement of
1 , 2 and 3  R 1 , 2 and 3  S
Example 2: Let us apply the whole sequence to bromochlorofluoro methane.
F 3
|
Br − C − H  1 4
|
Cl
2
In this Fischer projection the least priority number is not at the bottom of the plane.
In such cases the Fischer projection formula of the compound is converted into another equivalent projection formula in
such a manner that atom or group having the lowest priority is placed vertically downward. This may be done by two
interchanges between four priority numbers. The first interchange involves the two priority numbers, one is the least
priority number and other is the priority number which is present at the bottom of the plane. In the above case first
interchange will takes place between 2 and 4.
3 3
First interchange
1 4 1 2
Between 2 and 4
2 4
(A) (B)
First interchange of two groups at the chiral centre inverts the configuration and this gives enantiomer of the original
compound. Thus (A) and (B) are enantiomer. The second interchange involves the remaining two groups.
3 1
Second interchange
1 2 3 2
between remaining
4 groups, i.e., 1 and 3 4
(B) (A)
Arrangement of 1, 2 and 3 are

clockwise, hence configuration is R
Example:
H O
CHO C
| | O
H − C− OH  H − C− OH 
| |
CH2OH CH2OH
D-glyceraldehyde

2 2
First interchange
4 1 3 1
Between 3 and 4
3 4
1
Second interchange
3 2
Between 1 and 2
4

Clockwise
R-configuration
1
2
(i) First interchange between 3 and 4 2 3
1 4 2
(ii) Sec. interchange between 1 and 2 4
3

Anticlockwise
S-configuration
Glyceraldehyde has one asymmetric carbon, hence it has two configurational isomers (I) and (II).
CHO CHO
| |
H − C − OH HO − C − H
| |
CH 2 OH CH2 OH
( R) glyceraldehyde (S) glyceraldehyde
(I ) (II)
One can draw a number other configurations for glyceraldehyde but each of them will be a repetition of either (I) or (II). In
this connection it is important to note that if two projection formulae differ by an odd number of interchanges (1, 3, 5, 7,
…..) of positions of groups on the chiral carbon, they are different. But if the two differ by an even number of interchanges
(2, 4, 6, …..) they are identical.
• R and S Configurations of the Compounds with more than One Chiral Carbon Atom
If a compound has two or more chiral atoms, separate configurations (R or S) are assigned to these carbon atoms on the
basis of sequence rules which have already discussed. Let us assign the configuration to (–) tartaric acid with two chiral
atoms.
1
COOH
| COOH
HO − 2 C − H |
|  HO − C 2 − H
|
H − 3 C − OH
| CH(OH )COOH
4
COOH
Let us first assign configuration to carbon atom 2:
COOH COOH
| |
HO − C− H  HOOC(HO)HC − C 2 − OH
| |
CH(OH)COOH H
Thus the configuration of carbon atom C − 2 is ' 2S '
assign configuration of C3 .
CH(OH )COOH CH(OH )COOH

| |
H − C − OH  HO − C 3 − COOH
| |
COOH H
C − 3 is 3S thus expressed as 2S, 3 S tartaric acid.

• Resolution of Racemic Modifications
The separation of racemic mixture into its enantiomers is known as resolution. The following methods are used for
resolution.
a) Resolution by Mechanical Separation: Since (+) and (–) forms have opposite crystalline shapes, this property can
be used in the separation of the two forms from a racemic mixture.
b) Biochemical Separation: When a living organism is added to or developed to a racemic mixture, they eat up one of
the enantiomers preferentially leaving the other behind. Thus, resolution of forms can be done using this specific property
of living organisms.
• Asymmetric Synthesis and Walden Inversion
a) Asymmetric Synthesis: The synthesis of an optically active compound (asymmetric) from a symmetrical molecule
(having no asymmetric carbon) without resolution to form (+) or (–) isomer directly is termed asymmetric synthesis.
O
||
For example the reduction of pyruvic acid (CH3 − C − COOH) in presence of nickel catalyst gives () lactic acid
(racemic mixture). On the other hand, pyruvic acid is reduced to (–) lactic acid only by yeast.
CH 3 CH 3
| |
2H
⎯⎯⎯ → H − C − OH + HO − C − H
' Ni ' | |
COOH COOH
CH 3 (+ )Lactic acid ( −)Lactic acid
|
Reduction mixture
C=O ⎯⎯⎯⎯⎯
→
|
COOH CH 3
(Pyruvic acid) |
(2-Keto propanoic acid) 2H
⎯⎯⎯ → HO − C − H
Yeast |
COOH
(−)Lactic acid
b) Walden Inversion: The conversion of (+) form into (–) form and vice-versa is called Walden inversion. When an
atom or group directly linked to an asymmetric carbon atom is replaced; the configuration of the new compound may
be opposite to (inverse) that of the original, i.e.,
COOH COOH COOH
| | |
PCl5 AgOH
H− C − OH ⎯⎯⎯→ Cl − C− H ⎯⎯⎯⎯→ HO − C− H
| | |
CH2COOH CH2COOH CH2COOH
(+) Malic acid (−) Chlorosuccinic acid (−) Malic acid
COOH COOH COOH

| | |
PCl5 AgOH
OH − C− H ⎯⎯⎯→ H − C− Cl ⎯⎯⎯⎯→ H − C− OH
| | |
CH2COOH CH2COOH CH2COOH
(−) Malic acid (+) Chlorosuccinic acid (+) Malic acid
Conformational Isomerism
This type of isomerism is found in alkanes and cycloalkanes and their substituted derivatives. We will study this topic in detail
in next chapter “Hydrocarbons”.

14. General Organic Chemistry – Multiple Choice
Questions
7. Which of the following intermediate have the complete octet
Bonding and Hybridisation in Organic
around the carbon atom
Compounds
(a) Carbonium ion (b) Carbanion ion
1. Each carbon atom in benzene is in the state of hybridization
(c) Free radical (d) Carbene
3 2
(a) sp (b) sp 8. Which of the following solvents are aprotic
(c) sp (d) s 3 p (1) NH3 (2) SO2
2. Which is an acidic hydrocarbon (3) CH3CN (4) CH3CO2H
(a) CH3CH2CH2CH3 (b) CH3C  CCH3 (a) 1, 2, 3 (b) 1, 3, 4
(c) CH3C  CH (d) CH2 = CH − CH = CH2 (c) 2, 3 (d) 1, 3
9. Choose the correct order arranged in decreasing order of

+ −
3. Hybridisation in CH3 and CH3 are basicity
(a) CH  C−  CH3O−  OH −
(a) sp and sp 2 respectively
(b) sp 2 and sp 2 respectively (b) OH −  CH3O−  CH  C−
(c) sp 2 and sp 3 respectively (c) CH3O−  OH −  CH  C−
(d) sp 3 and sp 3 respectively (d) CH3O−  CH  C−  OH −
4. Graphite is soft while diamond is hard because 10. Electronegativity of carbon atoms depends upon their state of
hybridisation. In which of the following compounds, the
(a) Graphite is in powder form carbon marked with asterisk is most electronegative
(b) Diamond has sp 2 hybridization but graphite has sp 3 (a) CH3 − CH2 − *CH2 − CH3
hybridization
(b) CH3 − *CH = CH − CH3
(c) Graphite is in planar form while diamond is in tetrahedral
form
(c) CH3 − CH2 − C  *CH
(d) Graphite is covalent and diamond is ionic
(d) CH3 − CH2 − CH = *CH2
5. The shapes of methane, ethene and ethyne molecules are,
respectively 11. Number of  electrons present in naphthalene is
(a) Tetrahedral, planar and linear (a) 4 (b) 6
(b) Tetrahedral, linear and planar (c) 10 (d) 14
(c) Pyramidal, planar and linear 12. Carbon atoms in the compound (CN )4 C 2 are
(d) Tetrahedral, pyramidal and planar (a) sp hybridized

6. In ethane, ethene and ethyne molecules, carbon atoms are
(b) sp 2 hybridized
present in hybrid states of
(c) sp and sp 2 hybridized
(a) sp3 − sp2, sp2 − sp2, sp2 − sp
(d) sp , sp 2 and sp 3 hybridized
(b) sp3 − sp, sp3 − sp2, sp3 − sp
13. Number of unhybridised orbitals in vinyl acetylene are
(c) sp3 − sp3, sp2 − sp2, sp − sp
(a) 2 (b) 3
2 3 2 2 3
(d) sp − sp , sp − sp, sp − sp
(c) 4 (d) 6

14. Which one of the following is more acidic 3. The temporary effect in which there is complete transfer of a
shared pair of pi-electrons to one of the atoms joined by a
(a) Butane (b) 1-butene multiple bond on the demand of an attacking reagent is called
(c) 1-butyne (d) 2-butyne (a) Inductive effect

(b) Positive resonance effect
15. Cyclic hydrocarbon molecule ‘A’ has all the carbon and
(c) Negative resonance effect
hydrogen in a single plane. All the carbon-carbon bonds are
(d) Hyperconjugation
of same length less than 1.54Å, but more than 1.34Å. The
C − C bond angle will be (e) Electromeric effect
4. Benzene is unreactive because
(a) 109o 28 (b) 100 o (a) It has double bonds
(b) It has carbon-carbon single bond
(c) 180 o (d) 120 o
(c) Carbon are sp 2 hybridised
16. The hybridisation state of carbon in fullerene is
(d)  electrons are delocalised
2
(a) sp (b) sp 5. ‘ C − C ’ bond length in benzene lies between single and
double bond. The reason is
(c) sp 3 (d) sp 3 d (a) Resonance (b) Isomerism
(c) Metamerism (d) Inductive effect
17. The compounds containing sp hybridized carbon atom are
6. Orbital interaction between the sigma bonds of a substituent
group and a neighbouring pi orbital is known as
H3C CHO
N (a) Hyperconjugation
(i) (ii)
N (b) Inductive effect
CH3
(c) Steric effect
(d) Dipole-dipole interactions
(iii) H 3 C − CN (iv) H 2 C = C = CHCH 3
(e) Electric quadruple interactions
(a) (i) and (ii) (b) (iii) and (iv) 7. Which is the most stable carbocation
(c) (ii) and (iii) (d) (i) and (iv) (a) Iso-propyl (b) Triphenylmethyl cation
(c) Ethyl cation (d)  -propyl cation
Dipole Moment, Resonance and Reaction
Intermediates 8. Relative stabilities of the following carbocations will be in the
order
  
1. Which has highest dipole moment
CH 3 CH 3 C H 2 CH 2 OCH 3
H H 3C H (i) (ii) (iii)
(a) C=O (b) C=C (a) (iii) > (ii) > (i) (b) (iii) < (ii) < (i)
H H 3C H
(c) (ii) > (iii) > (i) (d) (iii) > (i) > (ii)
H CH3 Cl CH3 9. Chloroacetic acid is a stronger acid than acetic acid. This can
be explained using
(c) C=C (d) C=C
H 3C H H 3C Cl (a) −M effect (b) −I effect
(c) + M effect (d) + I effect
2. Polarisation of electrons in acrolein may be written as
10. Among the following structures, which is not permissible
− + resonance form
(a) CH2 = CH − CH =O
+ . .−
− + (a) CH 3 − N − O : (b) CH2 = N = O
(b) CH2 = CH − CH = O ..
| | .. :
CH3 CH3
(c) CH2 − = CH + − CH = O
+ .. − +
(c) CH2 = N − O
.. : (d) :C H3 − N = O
.. :
(d) CH2 + = CH − CH = O − | |
CH3 CH3

11. In which of the following compounds the carbon marked with 18. The compound, which gives the most stable carbonium ion
asterisk is expected to have greatest positive charge on dehydrogenation
(a) *CH3 − CH2 − Cl (b) *CH3 − CH2 − Mg +Cl − CH3

|
(a) CH 3 − CH − CH 2OH (b) CH3 − C − OH
* |
(c) CH3 − CH2 − Br (d) * CH3 − CH2 − CH3 CH3
|
CH3
12. Ionic species are stabilised by the dispersal of charge. Which
(c) CH 3 − CH 2 − CH 2 − CH 2 OH
of the following carboxylate ion is the most stable
(d) CH 3 − CH − CH 2 − CH 3
O O |
|| || CH 3
(a) CH3 - C- O- (b) Cl − CH2 − C − O−
19. The stability of Me 2 C = CH 2 is more than that of
O O
|| || MeCH 2 CH = CH 2 due to
F
(c) F − CH2 − C − O− (d) CH − C − O−
F (a) Inductive effect of the Me group
13. Strongest acid is (b) Resonance effect of the Me group

(c) Hyperconjugative effect of the Me group
(a) HC  CH (b) C2H6
(d) Resonance as well as inductive effect of the Me group
(c) C6 H6 (d) CH3OH
20. The descending order of stability of the carbonium ions
14. Aromatic properties of benzene are proved by + + +
C6 H 5 CH2 , p − (CH3O)C6 H 4 C H 2 , p − ( NO2 )C6 H 4 CH2
(a) Aromatic sextet theory (b) Resonance theory (I) (II) (III)
+
(c) Molecular orbital theory (d) All of these p − (CH3 )C6 H 4 CH 2
and (IV) is
15. Carboxylic acids are easily ionised. The main reason of this
statement (a) IV > II > I > III (b) II > IV > III > I
(a) Absence of -hydrogen (c) II > IV > I > III (d) IV > II > III > I
(b) Resonance stabilisation of carboxylate ion 21. Among the following, which is least acidic
(c) Reactivity of -hydrogen (a) p–nitrophenol (b) p–chlorophenol
(d) Hydrogen bond (c) Phenol (d) o–cresol

22. Given
16. Which among following statements are true with respect to OMe NO2
electronic displacement in a covalent bond
(i) (ii) (iii)
(1) Inductive effect operates through  bond
(2) Resonance effect operates through  bond OH OH OH

The decreasing order of the acidic character is
(3) Inductive effect operates through  bond
(a) (i) > (ii) > (iii) (b) (ii) > (i) > (iii)
(4) Resonance effect operate through  bond
(c) (ii) > (iii) > (i) (d) (iii) > (ii) > (i)
(5) Resonance and Inductive effect operate through  bond
23. What is the correct order of decreasing stability of the
(a) 3 and 4 (b) 1 and 2 following cations
 
(c) 2 and 4 (d) 1 and 3 CH3 − CH − CH3 CH3 − CH − OCH3
(e) 2 and 3 I II
17. Which of the following is the most stable compound 

CH3 − CH − CH2 − OCH3
+ + III
(a) Ph3C (b) Ph2CH
(a) II  I  III (b) II  III  I
+ +
(c) Ph3C CH2 (d) PhCH2
(c) III  I  II (d) I  II  III

24. Which of the following free radicals is most stable 30. Electrophilic addition reactions proceed in two steps. The first
step involves the addition of an electrophile. Name the type
of intermediate formed in the first step of the following
(a) (b) addition reaction. H3C − HC = CH2 + H + ⎯⎯→
(a) 2° carbanion (b) 1° carbocation

(c) (d)
(c) 2° carbocation (d) 1° carbanion
25. What will be the decreasing order of stability of following
31. The addition of HCl to an alkene proceeds in two steps. The
carbocations
first step is the attack of H + ion to C = C portion which can
+ + be shown as
CH2 CH2
+
(a) H + C=C (b) H + C=C
(c) H + C=C (d) All of these are possible

+
N(CH3)3 NO2
32. The correct order for homolytic bond dissociation energies (
(1) (2) (3) H in kcal/mol) for CH 4 ( A), C 2 H 6 (B) and CH 3 Br(C) is
+
(a) C  B  A (b) B  A  C
(c) C  A  B (d) A  B  C
33. The reaction of methyltrichloroacetate (Cl 3 CCO 2 Me) with

(4) (5)
sodium methoxide (NaOMe) generates
(a) 3 > 5 > 4 > 1 > 2 (b) 1 > 2 > 3 > 5 > 4
(a) Carbocation (b) Carbene
(c) 5 > 4 > 3 > 2 > 1 (d) 1 > 2 > 3 > 4 > 5
(c) Carbanion (d) Carbon radical
26. Which kind of fission is favoured by sunlight 34. Which of the following compound possesses the “C – H” bond
(a) Heterolytic fission (b) Homolytic fission with the lowest bond dissociation energy
(c) Both (a) and (b) (d) None of these (a) n-pentane (b) Toluene
27. Strongest nucleophile is (c) 2, 2 – dimethyl propane (d) Benzene
(a) RNH2 (b) ROH Organic Reactions and their Mechanism

(c) C6 H5O− (d) CH3O−
1. Following reaction, (CH3 )3 CBr + H2O → (CH3 )3 COH
28. Covalent bond can undergo fission in two different ways. The +HBr is an example of
correct representation involving a heterolytic fission of
(a) Elimination reaction (b) Free radical substitution
CH 3 − Br is
(c) Nucleophilic substitution (d) Electrophilic substitution

(a) CH3 − Br ⎯⎯→ CH3 + Br 2. Which of the following applies in the reaction
alc. KOH
 CH3 CHBrCH2CH3 ⎯⎯ ⎯⎯→
(b) CH3 − Br ⎯⎯→ CH3 + Br
(i) CH 3 CH = CHCH 3 (major product)
(c) CH3 − Br ⎯⎯→ CH3 + Br 
(ii) CH 2 = CHCH 2 CH 3 (minor product)
(d) CH3 − Br ⎯⎯→ CH3 + Br (a) Markonikoff's rule (b) Saytzeff's rule
29. Which of the following compounds are not arranged in order (c) Kharasch effect (d) Hofmann's rule
of decreasing reactivity towards electrophilic substitution
3. CH3 Br + OH ⎯⎯→ CH3 OH + Br , this reaction proceeds
(a) Fluoro benzene > chloro benzene > bromo benzene
by S N 2 − mechanism. Its rate is dependent on the
(b) Phenol > n-propyl benzene > benzoic acid concentration of
(c) Chloro toluene > para-nitro toluene > 2-chloro-4-nitro
(a) CH3 Br, OH (b) CH3Br only
toluene
(d) Benzoic acid > phenol > n-propyl benzene (c) OH only (d) CH3 Br, CH3OH

4. Which of the following is not true for SN1 reaction CH3 CH3
| |
9. H 3 C − C − Br + KOH (aq.) → H 3 C − C − OH + KBr
(a) Favoured by polar solvents | |
CH3 CH3
(b) 3o-alkyl halides generally react through SN 1 reaction
above reaction is
(c) The rate of the reaction does not depend upon the molar
(a) SN1 (b) SN 2
concentration of the nucleophile
(d) 1o-alkyl halides generally react through SN1 reaction (c) E1 (d) Both (a) and (b)
5. The following reaction 10. The most common type of reaction in aromatic compounds is
H CH3 (a) Elimination reaction

| |
Alcoholic
CH3 − C − C − CH3 ⎯⎯⎯⎯→ (b) Addition reaction
| | KOH
-H 2O, − KX
CH3 X (c) Electrophilic substitution reaction
CH3
| (d) Rearrangement reaction
CH3 − C = C − CH3
| 11. Addition of HCl to vinyl chloride gives 1, 1-dichloroethane
CH3 because of
is an example of (a) Mesomeric effect of Cl
(a)  − elimination (b)  − elimination (b) Inductive effect of Cl
(c) Hofmann elimination (d) None of these (c) Restricted rotation around double bond
6. SN1 reaction is faster in (d) None of these
CH3 12. The following compound will undergo electrophilic

(a) CH 3CH 2Cl (b) CH − Cl substitution more readily than benzene
CH3
(a) Nitrobenzene (b) Benzoic acid
CH3
|
(c) CH3 − C − Cl (d) CH3 − CH − Cl (c) Benzaldehyde (d) Phenol
| |
CH3 CH 2 13. Which one of the following species will be most reactive in
|
CH3 SN 2 reaction
7. To which of the following four types does this reaction belong

Cl
B− + R − A → B − R + A− Cl
(a) (b)
(a) Unimolecular electrophilic substitution
(b) Bimolecular electrophilic substitution Cl Cl
(c) Unimolecular nucleophilic substitution (c) (d)

(d) Bimolecular nucleophilic substitution 14. Order of reactivity towards nucleophilic substitution reaction
of the compounds
8. CH 3 CH 2 − Cl
The above reaction proceeds through
(a) Nucleophilic substitution

(i) (ii) (iii) (iv)
(b) Electrophilic substitution
(a) (i) > (ii) > (iii) > (iv) (b) (ii) > (i) > (iii) > (iv)
(c) Free radical substitution
(c) (iv) > (iii) > (ii) > (i) (d) (iii) > (iv) > (ii) > (i)
(d) More than one of the above processes

15. Which of the following requires radical intermediate 21. Dehydrohalogenation in presence of OH − is correctly
represented by
(a) CH3 − CH = CH 2 + HBr → CH3 − CH − CH3
| Br Br
Br (a) (b)
CN H H
(b) CH3 − CHO + HCN → CH3 − CH OH– OH–
OH

(c) CH 3 − CH = CH 2 + HBr → CH 3 − CH 2 − CH 2 − Br Br OH-  Br
(c) (d) OH-
+
H H
(d) CH3 CHO + NH2OH ⎯⎯⎯→ CH3 − CH = N − OH H
16. Which gives monosubstituted product 22. The enantiomeric pair among the following four structures
HO H OH
(a) o -dinitrobenzene (b) m -dinitrobenzene (I) (II)
H H
(c) p -dinitrobenzene (d) Nitrobenzene
HO HO H
17. The species responsible for nitration is (III) (IV)
H H
(a) NO2+ (b) NO3 (a) I and II (b) I and IV
(c) II and III (d) II and IV

(c) NO2 (d) All the above
23. The major product formed in the reaction
18. In electrophilic aromatic substitution reaction, the nitro group
is meta directing because it Br
(a) Decreases electron density at meta position Cl NaCN

⎯⎯ ⎯⎯→ Product is
DMSO,Heat
(b) Increases electron density at meta position
I
(c) Increases electron density at ortho and para position Br CN
(d) Decreases electron density at ortho and para positions (i) Cl (ii) Cl
19. Find the product of the given reaction

CN CN
Br CN
H+
⎯⎯⎯→
CN Cl

(iii) (iv)
I I
(a) (b)
(a) (i) (b) (ii)
(c) (iii) (d) (iv)
24. The major product of the following reaction is

(c) (d) Me
Me
=
HO
OH
F H+
20. Treatment of D D with NaNH / liq . NH gives

2 3 Me
O
NH2 NH2
Me Me
H H D D (a) (b)
(a) (b)
F NH2 H
D H D NH2 O Me
H H
(c) (d) + (c) Me
(d)
Me Me

25. For the transformation 30. The order of SN1 reactivity in aqueous acetic acid solution
Br for the compounds
O
||
N2Cl H 3C − C − CH 2 − Cl H 3C − CH 2 − CH 2 − Cl
1 2
The reagent used is
(H3C)3 C − Cl
(a) LiAlH4 (b) H3PO2 3
is
(c) H 3O+ (d) H2 / Pt
(a) 1  2  3 (b) 1  3  2
+
26. In the reaction benzene with an electrophile E , the structure (c) 3  2  1 (d) 3  1  2
of the intermediate  − complex can be represented as 31. The species that exhibits the highest Rf value in a thin layer
E
chromatogram using a nonpolar solvent on a silica gel plate is
H
(a) H (b) H E
H
E E
H H (a) (b)
(c) (d) +
H H N
27. The major product in the following reaction is
(c) (d)
H H
NaNH 2
⎯⎯ ⎯⎯→ N
H Br OH
H H 32. The major product of the following reaction
(a) H H (b) Cu, 
H NH2 ⎯⎯ ⎯→ is
I
I
H2C CH2
(c) (d) H3C NH2 (a) (b)
H2N NH2
28. The major product of the following reaction is
Conc. HBr
⎯⎯ ⎯⎯ ⎯→ I
HO
I I
Br Br (c) (d)
(a) (b)
HO
CH3
Br
I
(c) Br Br (d) Br 33. The major product of the reaction between CH 3 CH 2 ONa
H3C
and (CH 3 )3 CCl in ethanol is
29. The reaction that gives the following molecule as the major
product is (a) CH3CH2OC(CH3 )3 (b) CH2 = C(CH3 )2
CH3
H3C (c) CH3CH2C(CH3 )3 (d) CH3CH = CHCH3
CH3
O
H3C 34. The stability of carbocations
  
(CH3 )3 C (CH3 )2 C(OCH3 ) CH3CH2CH2 CH2
H3C H3C
H3C H3C I II III
(a) (b) ONa + CH3Br
Br + CH3ONa
H3C H3C 
CH3CHCH2CH3
H3C IV
H3C
H3C CH3 + CH3ONa
(c) OH + CH3ONa (d) follows the order
H3C H3C
(a) III  IV  II  I (b) III  IV  I  II
(c) IV  III  II  I (d) IV  III  I  II

35. In electrophilic aromatic substitution reactions of 10. How many structural isomers are possible for C4 H10 O
chlorobenzene, the ortho/para–directing ability of chlorine is
due to its (a) 3 (b) 4
(a) Positive inductive effects (+ I ) (c) 5 (d) 7
11. Which of the following does not exhibit tautomerism

(b) Negative inductive effect (− I )
(c) Positive resonance effect (+ R) O O

(a) O O (b)
(d) Negative resonance effect (− R)
Structural and Stereo Isomerism (c) O (d) O
O O
1. The isomerism exhibited by alkyl cyanide and alkyl isocyanide
is 12. Which of the following compounds will show geometrical
isomerism
(a) Functional (b) Positional
(a) Cyclohexene (b) 2-hexene
(c) Tautomerism (d) Metamerism
(c) 3-hexyne (d) 1, 1-diphenylethylene
2. The total number of possible isomeric trimethyl benzene is
13. Compound
(a) 2 (b) 3 Cl CH3
(c) 4 (d) 6 C=C

H C2H5
3. Dimethyl ether and ethyl alcohol are
has the following prefix
(a) Metamers (b) Homologues (a) E (b) Z
(c) Functional isomers (d) Position isomers (c) trans (d) Anti
4. Diethyl ether and methyl n-propyl ether are 14. The number of geometrical isomers in case of a compound
with the structure CH 3 − CH = CH − CH = CH − C 2 H 5 is
(a) Position isomers (b) Functional isomers
(c) Metamers (d) Chain isomers (a) 4 (b) 3
C7 H 9 N (c) 2 (d) 5
5. has how many isomeric forms that contain a
benzene ring 15. Which shows geometrical isomerism
(a) 4 (b) 5 H I H I
(a) C=C (b) C=C
H Br H 3C Br
(c) 6 (d) 7
CH3 Cl H Cl
6. Which isomer of hexane has only two different sets of (c) C=C (d) C=C
CH3 Br H 3C Cl
structurally equivalent hydrogen atoms
(a) 2, 2-dimethylbutane (b) 2-methyl pentane 16. Which pair show cis-trans isomerism
(c) 3-methylpentane (d) 2, 3-dimethylbutane (a) Maleic-fumaric acid (b) Lactic-tartaric acid
(c) Malonic-succinic acid (d) Crotonic-acrylic acid
7. Nitroethane can exhibit one of the following kind of isomerism
17. Stereoisomers which are not the mirror images of one another
(a) Metamerism (b) Optical activity
are called
(c) Tautomerism (d) Position isomerism (a) Enantiomers (b) Mesomers
8. Which of the following compounds will show metamerism (c) Tautomers (d) Diasteroisomers
(a) CH3COOC2H5 (b) C2H5 − S − C2H5 18. An organic compound
1
(c) CH3 − O − CH3 (d) CH3 − O − C2H5 CH3 − 2CH2 − 3 CH2 − 4 CH2 − 5 CH2 − 6 CH2 −7 CH3
9. How many primary amines are possible for the formula To make it chiral compound the attack should be on which
carbon atom
C 4 H 11 N
(a) 1 (b) 3
(a) 1 (b) 2
(c) 4 (d) 7
(c) 3 (d) 4

19. If the light waves pass through a nicol prism then all the 27. The configuration of the chiral centre and the geometry of the
oscillations occur only in one plane, such beam of light is double bond in the following molecule can be described by
called as
F
(a) Non-polarised light (b) Plane polarised light |
HOOC − C − OH
(c) Polarised light (d) Optical light |
C Me
20. Disymmetric object is one which is Me C
|
(a) Superimposable on its mirror image H
(b) Non-superimposable on its mirror image (a) R and E (b) S and E

(c) Optically inactive (c) R and Z (d) S and Z
(d) Achiral
28. Products of the reaction
21. What is the possible number of optical isomers for a
compound containing 2-dissimilar asymmetric carbon atom H 3C Br
H H Br2
C=C ⎯⎯⎯→ H C−C H
(a) 2 (b) 4 H 3C CH3
Br CH3
(c) 6 (d) 8
are
22. A compound whose molecules are superimposable on their
mirror images even though they contain an asymmetric (a) Meso-compounds
carbon atom is called
(b) Racemic mixtures
(a) A meso compound (b) An erythro isomer
(c) Mixtures of racemic and meso-compounds
(c) A threo isomer (d) A glycol
(d) None of the above
23. Which of the following compound is expected to be optically
active 29. Which compound is optically active
(a) (CH3 )2 CHCHO (b) CH3CH2CH2CHO (a) 4-chloro, 1-hydroxy butane
(c) CH3CH2CHBr CHO (d) CH3CH2CBr2CHO (b) 3 o -butyl alcohol

24. Which will show optical isomerism (c) Secondary butyl amine
(a) 3, 3-dichloropentane (b) 2-chloro-2-butanol (d) n-butyl alcohol
(c) 2-chloro-2-propanol (d) All of these
30. Which of the following statements is not true about
25. The optically active molecule is enantiomers
(a) They have same physical properties

COOMe COOMe
(b) They have different biological properties
HO H D OH
(a) (b)
HO H D OH (c) They have same chemical properties towards chiral
compounds
COOMe COOMe
(d) None of these
31. Consider the following representation

COOMe COOH
CH3 CH3
H OH H OH
(c) OH
(d) H Br F H
H H OH
F Br
COOH COOH
They are
26. Which among the following functional groups has been given (a) Enantiomers (b) Diastereomers
the highest priority while assigning R-S configuration
(c) Conformational isomers (d) Identical
(a) −C6 H 5 (b) −CN
(e) Cis–trans isomers
(c) −C2 H 5 (d) − CH 3

32. The number of racemic mixture obtained by optical isomers 38. Glucose has optical isomers
of 2, 3-dihydroxy butanal is/are
(a) 8 (b) 12
(a) Three (b) Two
(c) 16 (d) Cannot be predicted
(c) One (d) Zero
39. The optical rotation of an optically active compound is
33. The absolute configurations of the C 2 and C 3 atoms in the
molecule with the structure is (a) Directly proportional to length of the polarimeter tube only
1
(b) Directly proportional to the molar concentration of the
CH3
compound
Cl H (c) Independent of the length of the polarimeter tube and
2
concentration of the compound
3 OH
H
(d) Directly proportional to both the length of the polarimeter
tube and molar concentration of the compound
40. In a mixture, two enantiomers are found to be present in 85%
(a) 2S, 3S (b) 2R, 3S
and 15% respectively. The enantiomeric excess(e, e) is
(c) 2S, 3R (d) 2R, 3R
(a) 85% (b) 15%
34. While assigning R, S configuration the correct order of priority (c) 70% (d) 60%
of groups attached to chiral carbon atom is
41. When (–)-2-methylbutan-1-ol is heated with concentrated
(a) CONH2  COCH3  CH2OH  CHO hydrochloric acid, (+)1-chloro-2-methylbutane is obtained.
(b) CONH2  COCH3  CHO  CH2OH The reaction is an example of
(c) COCH3  CONH2  CHO  CH2OH (a) Retention (b) Inversion
(d) CHO  CH2OH  COCH3  CONH2 (c) Racemisation (d) Resolution
35. How many chiral isomers can be drawn from 2-bromo-3- (e) Mutarotation
chloro butane
42. The structure of 2R, 3S-dibromocinnamic acid is
(a) 2 (b) 3
CO2H CO2H
(c) 4 (d) 5 H Br Br H
(a) (b)
36. Which of the following is a chiral molecule H Br H Br
CH3 CH3
Ph Ph
CH3
(a) (b) CO2H
CO2H
CH3 Br H
H Br
CH3 CH3 (c) Br H (d) Br H
Ph Ph
(c) (d)
43. Least hindered rotation about carbon-carbon bond is
CH3 H3C observed in
37. Which of the following will not lose asymmetry on reduction (a) Ethane (b) Ethylene
with LiAlH 4
(c) Ethyne (d) Hexachloroethane
CHO
44. The maximum number of stereoisomers possible for 2-
(a) HOH 2C CH 2CH 3 hydroxy-2-methyl butanoic acid is
CH = CH 2
(a) 1 (b) 2
CH 3 (c) 3 (d) 4
(b) H 2C = HCO CHO 45. Among the following pairs, the pair that illustrates
CH 2CH 3 stereoisomerism is
CH 3 (a) 1-butanol and 2-butanol

(c) HOH 2C COOH (b) Cis-2-butene and trans-2-butene
C  CH
(c) Dimethyl ether and ethanol
CHO
(d) Acetone and propanal
(d) H 3C CN
(e) Ethanol and ethanal
CH 2 NH 2

46. On bromination, propionic acid yields two isomeric 2- 53. Identify the stereoisomer pair from the following choices
bromopropionic acids. This pair is an important example of
(a) CH3CH2CH2OH and CH3CH2OCH3
(a) Chain isomers (b) Optical isomers
(b) CH3CH2CH2Cl and CH3CHClCH3
(c) Cis-trans isomers (d) Position isomers
47. Which kind of isomerism is possible for 1-chloro-2-nitroethene H
(a) Functional group isomerism (c) CH3 C C CH3 and CH3 C C CH3
(b) Position isomerism H H H

CH3
(c) E / Z isomerism
(d) Optical isomerism (d) and

48. The correct relation between the following pair of compounds
is
54. Two possible stereoisomers for
H OH H COOH
are
*
HO HO HO H
OH H
(a) Enantiomers (b) Diastereomers
H H
(a) Constitutional isomers (b) Enantiomers (c) Conformers (d) Rotamers

55. The following two compounds are
(c) Diastereomers (d) None of these H
49. COOH COOH CH3 H3C H

H3C
H OH OH H (a) Geometrical isomers (b) Positional isomers

OH H H OH (c) Functional group isomers (d) Optical isomers
CH3 CH3 56. The compound that readily tautomerizes is

Pair is known as (a) CH3COCH2CO2C2H5 (b) CH3COCH2CHCH3
(a) Erythro stereoisomers (b) Threo stereoisomers
(c) CH3COCH2CH2CH3 (d) (CH3 )3 CCOC(CH3 )3
(c) Structure isomers (d) Geometrical isomers
50. Which of the following compounds can exhibit both 57. The number of isomers which are ethers and having the
geometrical isomerism and enantiomerism molecular formula C4 H10 O , is
(a) CH3 − CH = CH = CH3 (a) 2 (b) 3

CH3 (c) 4 (d) 5
|
(b) CH3CH2 − CH − C = CH − CH3 58. The number of stereoisomer possible for the following
CH3 compound is CH 3 − CH = CH − CH (Br) − CH 2 − CH 3
|
(c) CH3CH 2 − C = CH − COOH (a) 2 (b) 3
(d) CH3 − CHOH − COOH (c) 4 (d) 8
51. The total number of acylic isomers including the stereoisomers 59. The number of stereoisomers possible for the following
with the molecular formula C4 H7 Cl compound is CH 3 − CH = CH − CH (OH ) − CH 3
(a) 11 (b) 12 (a) 1 (b) 2

(c) 9 (d) 10
(c) 3 (d) 4
52. A compound is formed by substitution of two chlorine for two
hydrogens in propane. The number of possible isomeric 60. Which of the following molecules can exhibit optical activity
compounds is
(a) 1–bromopropane (b) 2–bromobutane
(a) 4 (b) 3
(c) 3–bromopentane (d) Bromocyclohexane
(c) 5 (d) 2

10. The enolic form of acetone contains [1990]
IIT-JEE/ AIEEE
(a) 8  -bonds, 2 -bonds and 1 lone pairs
1. The bond between carbon atom (1) and carbon atom (2) in
compound N  C − CH = CH 2 involves the hybridised (b) 9  -bonds, 1 -bond and 2 lone pairs
carbon as [1987] (c) 9  -bonds, 2 -bonds and 1 lone pairs

2 2 3
(a) sp and sp (b) sp and sp (d) 10  -bonds, 1  -bonds and 1 lone pairs
(c) sp and sp 2 (d) sp and sp 11. In allene (C3 H 4 ), the type(s) of hybridisation of the carbon
2. Number of  and  bonds present in 1- butene-3-yne atoms is (are) [2012]
respectively are [1989]
(a) sp and sp3 (b) sp and sp 2
(a) 7 , 3 (b) 5 , 2
(c) Only sp 2 (d) sp 2 and sp3
(c) 8 , 3 (d) 6 , 2
12. Which has zero dipole moment [1994; 1996]
3. In which of the following species is the underlined carbon
having sp 3 hybridisation [2002] (a) Cis-2-butene (b) Trans-2-butene
(a) CH3 COOH (b) CH3 CH2OH (c) 1-butene (d) 2-methyl-1-propene
(c) CH3 COCH3 (d) CH2 = CH − CH3 13. Among the following mixtures, dipole-dipole as the major
interaction, is present in [2006]
4. The hybridisation of carbons of C − C single bond of
(a) Benzene and ethanol
HC  C − CH = CH 2 is [199]
(b) Acetonitrile and acetone
(a) sp3 − sp3 (b) sp − sp2
(c) KCl and water
(c) sp3 − sp (d) sp2 − sp3
(d) Benzene and carbon tetrachloride
5. Maximum carbon-carbon bond distance is found in [1981]
14. For which of the following molecule, significant   0
(a) Ethyne (b) Ethene
Cl CN
(c) Ethane (d) Benzene
6. C-H bond length is greatest in [1989] (1) (2)
(a) C2H2 (b) C2H4 Cl CN
(c) C2H6 (d) C2H2Br2
7. Which of the following represents the given mode of OH SH

hybridisation sp2_ sp2_ sp-sp from left to right [2003]
(3) (4)
(a) H 2 C = CH − C  CH (b) HC  C − C  CH
CH 2 OH SH
(c) H 2 C = C = C = CH 2 (d) CH 2
(a) Only (1) (b) (1) and (2)

8. Number of  electrons in cyclobutadienyl anion (C4 H3 )− is
[1991] (c) Only (3) (d) (3) and (4)
(a) 2 (b) 4 15. Resonance structure of molecule does not have [1984]
(c) 6 (d) 8 (a) Identical arrangement of atoms
9. Which one of the following does not have sp 2 hybridised (b) Nearly the same energy content
carbon [2004]
(c) The same number of paired electrons
(a) Acetonitrile (b) Acetic acid
(d) Identical bonding
(c) Acetone (d) Acetamide

16. Arrangement of (CH 3 )3 − C, − (CH 3 )2 − CH , − CH 3 − CH 2 21. In the compound given below
when attached to benzyl or an unsaturated group in  
increasing order of inductive effect is [2002] H3N NH3
(Z)
(a) (CH3 )3 − C−  (CH3 )2 − CH−  CH3 − CH2 − (Y)
COOH
(b) CH3 − CH2 −  (CH3 )2 − CH −  (CH3 )3 − C −
(X)
(c) (CH3 )2 − CH−  (CH3 )3 − C−  CH3 − CH2 − The correct order of the acidity of the positions (X), (Y) and
(Z) is [2004]
(d) (CH2)3 − C−  CH3 − CH2 −  (CH3 )2 − CH −
(a) (Z) > (X) > (Y) (b) (X) > (Y) > (Z)
17. In CH 3 CH 2 OH , the bond that undergoes heterolytic
cleavage most readily is [1988] (c) (X) > (Z) > (Y) (d) (Y) > (X) > (Z)
(a) C – C (b) C – O
22. Arrange the carbanions, (CH3 )3 C, CCl3 , (CH3 )2 CH,
(c) C – H (d) O – H
18. Among the following, the least stable resonance structure is C6 H5 CH2 , in order of their decreasing stability [2009]
[ 2007]
(a) C6 H5 CH2  CCl3  (CH3 )3 C  (CH3 )2 CH
 O
(a)  (b) (CH3 )2 CH  CCl3  C6 H5 CH2  (CH3 )3 C
N
O (c) CCl3  C6 H5 CH2  (CH3 )2 CH  (CH3 )3 C
O (d) (CH3 )3 C  (CH3 )2 )CH  C6 H5 CH2  CCl3


N
(b)  23. The order of stability of the following carbocations
O ⊕
CH2
(c) O
  
 N CH2 = CH − CH2 ; CH3 − CH2 − CH2 ; is
I II III
O [2013]
(a) III > II > I (b) II > III > I

O

N (c) I > II > III (d) III > I > II
(d) 
24. Arrange the following compounds in order of decreasing
O
acidity
19. Hyperconjugation involves overlap of the following orbitals
OH OH OH OH
[2008]
(a)  −  (b)  − p
Cl ; CH3 ; NO2 ; OCH3;
(c) p − p (d)  − 
(I) (II) (III) (IV)
[2013]
20. The correct acidity order of the following is [2009]
(a) II > IV > I > III (b) I > II > III > IV
OH OH COOH COOH
(c) III > I > II > IV (d) IV > III > I > II
25. Which one of the following species is most stable [1995]
Cl CH3 + +
(I) (II) (III) (IV)

(a) p − O2 N − C6 H4 − C H2 (b) p − CH3O − C6 H4 − C H2
(a) (III) > (IV) > (II) > (I) (b) (IV)> (III) > (I) > (II) + +
(c) p − Cl − C6 H4 − C H2 (d) C6 H5 − C H2
(c) (III) > (II) > (I) > (IV) (d) (II)> (III) > (IV) > (I)
26. Which of the following resonating structures of 1-methoxy-1, 32. Which of the following has the highest nucleophilicity
3-butadiene is least stable [2005] [2000]
− 
(a) CH2 − CH = CH − CH = O− CH3 (a) F −
(b) OH −
− 
(b) CH2 = CH2 − CH − CH = O− CH3 (c) CH3− (d) NH 2−
− 
33. Which behaves both as a nucleophile and electrophile
(c) CH2 − CH − CH = CH − O − CH3
− 
[1991]
(d) CH2 = CH − CH − CH − O − CH3
(a) CH3 NH2 (b) CH3Cl
27. In the following carbocation, H / CH 3 that is most likely to
(c) CH3CN (d) CH3OH
migrate to the positively charged carbon is [2009]
34. In the following groups
H H
1 |2 + |4 5 −OAc −OMe −OSO2 Me −OSO2 CF3
H 3 C — C — C — C — CH 3
| 3| | I II III IV
HO H CH3
The order of leaving group ability is [1997]
(a) CH3 at C − 4 (b) H at C − 4 (a) I > II > III > IV (b) IV > III > I > II
(c) CH 3 at C − 2 (d) H at C − 2 (c) III > II > I > IV (d) II > III > IV > I
28. The correct stability order for the following species is 35. The reaction of propene with HOCl (Cl 2 + H 2 O) proceeds
through the intermediate [2016]
 
O (a) CH3 − CH + − CH2 − Cl (b) CH3 − CH(OH) − CH2+
(I) (II)
(c) CH3 − CHCl − CH2+ (d) CH3 − CH + − CH2 − OH
 36. The decreasing order of nucleophilicity among the

O 
nucleophiles
(III) (IV) (i) CH3 C − O − (ii) CH3O−
||
[2008] O
(a) (II)>(IV)>(I)>(III) (b) (I)>(II)>(III)>(IV) O
||
(c) (II)>(I)>(IV)>(III) (d) (I)>(III)>(II)>(IV) (iii) CN −
(iv) H3C − − S − O−
||
O
29. Due to the presence of an unpaired electron, free radicals are
[2005] is [2005]
(a) Chemically reactive (b) Chemically inactive (a) (i), (ii), (iii), (iv) (b) (iv), (iii), (ii), (i)
(c) Anions (d) Cations (c) (ii), (iii), (i), (iv) (d) (iii), (ii), (i), (iv)
30. Homolytic fission of C – C bond in ethane gives an 37. In SN 2 reactions, the correct order of reactivity for the
intermediate in which carbon is [1992]
following compounds: CH 3 Cl , CH 3 CH 2 Cl , (CH 3 )2 CHCl
(a) sp 3 hybridised (b) sp 2 hybridised and (CH 3 )3 CCl is [2014]
(c) sp hybridised (d) sp 3d hybridized
(a) CH3Cl  (CH3 )2 CHCl  CH3CH2Cl  (CH3 )3 CCl
31. Among the following compounds which can be dehydrated
very easily is [2004] (b) CH3Cl  CH3CH2Cl  (CH3 )2 CHCl  (CH3 )3 CCl
CH3 (c) CH3CH2Cl  CH3Cl  (CH3 )2 CHCl  (CH3 )3 CCl

|
(a) CH3 − CH 2 − C− CH 2 − CH3 (d) (CH3 )2 CHCl  CH3CH2Cl  CH3Cl  (CH3 )3 CCl
|
OH
OH 38. Tertiary alkyl halides are practically inert to substitution by
|
SN 2 mechanism because of [2005]
(b) CH3 − CH 2 − CH 2 − CH − CH3
(c) CH3 − CH2 − CH2 − CH2 − CH2 − OH (a) Insolubility (b) Instability
(d) CH3 − CH 2 − CH − CH 2 − CH 2 − OH
| (c) Inductive effect (d) Steric hindrance
CH3

39. The reaction 44. The major product obtained when Br2 / Fe is treated with
O
O − O − HN
R−C + Nu → R − C + X , is fastest when X
X Nu H3C CH3
is [2004]
is [2005]
O
(a) Cl (b) NH 2
HN
H3C CH3
(c) OC 2 H 5 (d) OCOR (a)
40. Elimination of bromine from 2-bromobutane results in the

Br
formation of [2004, 05]
(a) Equimolar mixture of 1 and 2-butene O

HN
(b) Predominantly 2-butene H3C CH3
(b)
(c) Predominantly 1-butene
(d) Predominantly 2-butyne Br

O
41. What is the decreasing order of reactivity amongst the HN
(c)
following compounds towards aromatic electrophilic H3C CH3
substitution
Br
I. Chlorobenzene II. Benzene
O
III. Anilinium chloride IV. Toluene HN
(d) H3C CH3
[1995]
(a) I  II  III  IV (b) IV  II  I  III Br
(c) II  I  III  IV (d) III  I  II  IV

45. CH3 Br + Nu− → CH3 − Nu + Br −
42. HBr reacts with CH 2 = CH − OCH 3 under anhydrous
The decreasing order of the rate of the above reaction with
conditions at room temperature to give [2006]
nucleophiles (Nu− ) A to D is
(a) CH3CHO and CH3Br
[ Nu− = ( A) PhO− ,(B)AcO− ,(C) HO− ,(D) CH3O− ] [2006]
(b) BrCH2CHO and CH3OH
(a) D  C  A  B (b) D  C  B  A
(c) BrCH2 − CH2 − OCH3 (c) A  B  C  D (d) B  D  C  A
(d) H3C − CHBr − OCH3

Me
43. Consider the following bromides 
46. +
Me
Me Me N
–
Me Me OH
Br n-Bu Et
Br Br
A B C The alkene formed as a major product in the above
elimination reaction is [2006]
The correct order of SN 1 reactivity is [2010] (a) Me (b) CH 2 = CH 2
(a) A > B > C (b) B > C > A Me Me
(c) B > A > C (d) C > B > A (c) (d)

47. OH 53. The number of structural isomers for C6 H 14 is [2007]
O– Na+
+ CHCl3 + NaOH → (a) 3 (b) 4
CHO
The electrophile involved in the above reaction is [2006] (c) 5 (d) 6
+
54. Which of the following compounds will exhibit geometrical
(a) Dichloromethyl cation (CHCl 2 )
isomerism [2000; 2015]
(b) Dichlorocarbene (: CCl 2 ) (a) 1-phenyl-2-butene (b) 3-phenyl-1-butene

–
(c) 2-phenyl-1-butene (d) 1, 1-diphenyl-1-propene
(c) Trichloromethyl anion (CCl 3 )
55. Which of the following does not show geometrical isomerism
(d) Formyl cation (CHO ) [2002]
(a) 1, 2-dichloro-1-pentene (b) 1, 3-dichloro-2-pentene

48. In the following reactions, the product S is
(c) 1, 1-dichloro-1-pentene (d) 1, 4-dichloro-2-pentene
H3C
i. O3
R
NH3
S
56. The correct statement(s) about the compound given below is
ii. Zn,H2O [2015]
(are) [ 2008]
H3C N H3C N H
(a) (b) Cl CH3
N
N
H3C
(c) (d)
H3C H3C H
49. The major product obtained in the following reaction is Cl
Br
H (a) The compound is optically active
C6H5
C6H5 (b) The compound possesses centre of symmetry
(+)
[2017]
(c) The compound possesses plane of symmetry
(a) C6 H5CH = CHC6 H5 (d) The compound possesses axis of symmetry
t
(b) (+)C6 H5CH(O Bu)CH2C6 H5 57. Racemic mixture is formed by mixing two [2002]
(c) (−)C6 H5CH(Ot Bu)CH2C6 H5
(a) Isomeric compounds (b) Chiral compounds
(d) ()C6 H5CH(Ot Bu)CH2C6 H5 (c) Meso compounds (d) Optical isomers
50. The increasing order of the reactivity of the following halides 58. Which of the following molecules is expected to rotate the
for the SN1 reaction is plane polarized light [2007]
CHO
(i) CH3 CHCH2CH3 (ii) CH 3 CH 2 CH 2 Cl
| HO H
(a) (b)
Cl SH
CH2OH
(iii) p − H 3 CO − C6 H 4 − CH 2 Cl [2017]
(a) (ii) < (i) < (iii) (b) (i) < (iii) < (ii) H2N NH2
COOH
(c) (ii) < (iii) < (i) (d) (iii) < (ii) < (i) (c) H H (d) H2N H
51. The compound C 4 H 10 O can show [1981] Ph Ph H
(a) Metamerism (b) Functional isomerism 59. The number of stereoisomers possible for a compound of the
(c) Positional isomerism (d) All types molecular formula CH 3 − CH = CH − CH (OH ) − Me is
[2009]
52. For which of the following parameters the structural isomers (a) 3 (b) 2
C2 H 5 OH and CH 3OCH 3 would be expected to have the
(c) 4 (d) 6
same values (Assume ideal behaviour) [2004]
(a) Boiling points 60. An enantiomerically pure acid is treated with racemic mixture
of an alcohol having one chiral carbon. The ester formed will
(b) Vapour pressure at the same temperature be [2003]
(c) Heat of vaporization (a) Optically active mixture (b) Pure enantiomer
(d) Gaseous densities at the same temperature and pressure (c) Meso compound (d) Racemic mixture
61. The correct statement about the compounds A and B is 68. A solution of D (+) - 2-chloro-2-phenylethane in toluene
racemises slowly in the presence of small amount of SbCl 5 ,
[1997]
due to the formation of [1999; 2013]
COOCH3 COOH
H OH H OH (a) Carbanion (b) Carbene
H OH H OH (c) Free radical (d) Carbocation
COOH COOCH3 CH3 Cl 2 / h
69. ⎯⎯ ⎯⎯→ N (isomeric product)
(A) (B)
(a) A and B are identical H3C

CH3
(b) A and B are diastereomers fractional distillation
C5 H11Cl ⎯⎯⎯⎯⎯⎯⎯→ M (isomeric product)
(c) A and B are enantiomers
What are N and M [2006]
(d) None of these
(a) 6, 6 (b) 6, 4
62. Which of the following will have a mesoisomer also
(c) 4, 4 (d) 3, 3
[2004]
70. The absolute configuration of
(a) 2, 3-dichloropentane (b) 2, 3-dichlorobutane
HO2C CO2H
(c) 2-chlorobutane (d) 2-hydroxypropanoic acid
63. Out of the following the alkene that exhibits optical isomerism
is [2010] OH is [2008]
HO H H
(a) 2-methyl-2-pentene (b) 3-methyl-2-pentene (a) R, R (b) R, S
(c) S, R (d) S, S
(c) 4-methyl-1-pentene (d) 3-methyl-1-pentene
71. Hydrogenation of the adjoining compound in the presence of
64. The absolute configuration of
CO2H poisoned palladium catalyst gives [2001]
H OH Me H Me
H Cl
Me H
CH3
[2016] (a) An optically active compound
(a) (2S, 3R) (b) (2S, 3S) (b) An optically inactive compound
(c) (2R, 3R) (d) (2R, 3S) (c) A racemic mixture
65. The optically active tartaric acid is named as D-(+)- tartaric (d) A diastereomeric mixture
acid because it has a positive [1999] CH 3
+ Br / CCl
H
(a) Optical rotation and is derived from D-glucose 72. ⎯⎯⎯→[F ] ⎯⎯⎯⎯⎯
2 4
→ C4 H8 Br2
− H2O
(b) pH in organic solvent H 3C OH 5 such products
are possible
(c) Optical rotation and is derived from D(+) glyceraldehyde

How many structures of F is possible [2003]
(d) Optical rotation only when substituted by deuterium
(a) 2 (b) 5
66. On monochlorination of 2-methyl butane, the total number of
chiral compounds is [2004; 2012] (c) 6 (d) 3
(a) 2 (b) 4 73. The number of stereoisomers obtained by bromination of
(c) 6 (d) 8 trans−2−butene is [2007]
67. Which of the following compounds is not chiral [2004] (a) 1 (b) 2
(a) 1-chloro-2-methyl pentane (c) 3 (d) 4
(b) 2-chloropentane
74.  − D-(+)-glucose and  -D-(+)-glucose are [2008]
(c) 1-chloropentane
(a) Epimers (b) Anomers
(d) 3-chloro-2-methyl pentane
(c) Enantiomers (d) Conformers

75. Name the compound, that is not isomer with diethyl ether 3. Only two isomeric monochloro derivatives are possible for
[1986]
[1981]
(a) n–butane (b) 2, 4-dimethyl pentane
(a) n-propylmethyl ether (b) Butane-1-ol (c) Benzene (d) 2-methyl propane
4. The compound in which C uses its sp3- hybrid orbitals for
(c) 2-methylpropane-2-ol (d) Butanone
bond formation is [1989]
76. A similarity between optical and geometrical isomerism is that (a) HCOOH (b) (H 2 N )2 CO
[2002] (c) (CH 3 )3 COH (d) CH 3CHO
(a) Each forms equal number of isomers for a given 5. Which of the following compounds will show geometrical
compound isomerism [1998]
(a) 2-butene (b) Propene
(b) If in a compound one is present then so is the other
(c) 1-phenyl propene (d) 2-methyl butene
(c) Both are included in stereoisomerism 6. Tautomerism is exhibited by [1998; 2013]
(d) They have no similarity (a) CH=CH–OH (b) O O
77. Which types of isomerism is shown by 2, 3-dichlorobutane

O O
[2005] (c) (d)
O O
(a) Distereo (b) Optical
(c) Geometric (d) Structural 7. Which one of following has the smallest heat of
hydrogenation per mole [1993]
78. The following compound can exhibits (a) 1-butene (b) Trans-2-butene
CH3 H (c) Cis-2-butene (d) 1, 3 butadiene
C=C H [1995]
CH3 C 8. Toluene, when treated with Br2 / Fe, gives p-bromotoluene
CH3 COOH
as the major product because the CH3 group [1999]
(a) Tautomerism (a) Is para-directing
(b) Is meta-directing
(b) Optical isomerism
(c) Activates the ring by hyperconjugation
(c) Geometrical isomerism (d) Deactivates the ring
(d) Geometrical and optical isomerisms 9. The correct statement(s) about the compound
H 3 C(HO)HC − CH = CH − CH (OH )CH 3 (X) is(are)
79. The number of isomers for the compound with molecular
[2009]
formula C 2 BrClFI is [2001]
(a) The total number of stereoisomers possible for X is 6
(a) 3 (b) 4 (b) The total number of diastereomers possible for X is 3
(c) If the stereochemistry about the double bond in X is
(c) 5 (d) 6
trans, the number of enantiomers possible for X is 4
JEE Advanced (d) If the stereochemistry about the double bond in X is cis,
the number of enantiomers possible for X is 2
10. The correct statement(s) concerning the structures E, F and
More than one correct answers
G is (are)
HC O H3C OH
1. Dipole moment is shown by [1986] 3
(a) 1, 4-dichloro benzene H3C CH3

H3C CH3 (F)
(b) Cis-1, 2-dichloro ethene (E)
H3C CH3
(c) Trans-1, 2-dichloro-2-pentene [2008]
(d) Trans-1, 2-dichloro ethane H3C OH
(G)
2. The molecules that will have dipole moment are [1992]
(a) 2, 2– dimethyl propane (a) E, F and G are resonance structures
(b) Trans-2- pentene (b) E, F and E, G are tautomers
(c) Cis-3- hexene (c) F and G are geometrical isomers
(d) 2, 2, 3, 3-tetramethyl butane (d) F and G are diastereomers

11. Keto-enol tautomerism is found in [1988] 17. Compound(s) that on hydrogenation produce(s) optically
O inactive compound(s) is (are) [2015]
|| H Br H Br
(a) H 5 C6 − C − H (a) (b)
H2C CH3
O H3C CH3
||
(b) H 5 C6 − C − C6 H 5
H Br
Br H
O (c) H2C (d)
|| H2C CH3
CH3
(c) H 5 C6 − C − CH 3
O O CH3
|| ||
(d) H 5 C6 − C − CH 2 − C − CH 3 18. Which of the following are not resolvable
(a) 2, 3 – Pentadiene
12. Which of the following act as nucleophiles [1999]
− CH3 CH3
(a) CH 3 NH 2 (b) RO
(b) C
(c) AlCl 3 (d) CH 3 MgBr
13. Amongst the given options, the compound(s) in which all H H

the atoms are in one plane in all the possible conformations CH3 CH3
(if any), is (are) [2011] (c)
H H H
H H
(a) C−C (b) H − C  C − C
H 2C CH2 CH 2 CH COOH
(d)
3
(c) H 2C = C = O (d) H 2C = C = CH 2
H H H H
14. The hyperconjugative stabilities of tert-butyl cation and 2-
butene, respectively, are due to [2013] COOH CH
3
(a)  → p (empty) and  →  * electron delocalisations 19. Which of the following can exist in diastereomeric pair
OH
(b)  →  * and  →  electron delocalisations (a) Cl Br (b)
(c)  → p (filled) and  →  electron delocalisations I
(d) p (filled) →  * and  →  * electron delocalisations

Br Me
15. The reactivity of compound Z with different halogens under Br H Br
appropriate conditions is given below (c) (d) H Br
mono halo substituted derivative when Me
OH
X2=I2 20. Which of the following compounds has one of the
streoisomer as a meso compound
X2
di halo substituted derivative when Cl Br
X2=Br2
Cl
Z C(CH3)
tri halo substituted derivative when (a) (b)
3
X2=Cl2 Br
The observed pattern of electrophilic substitution can be

explained by [2014]
(c) (d) 2, 3 − Dimethyl butane
(a) The steric effect of the halogen
(b) The steric effect of the tert-butyl group
21. Which of the following show stable or major form of
(c) The electronic effect of the phenolic group
tautomerism
(d) The electronic effect of the tert-butyl group
16. The correct combination of names for isomeric alcohols with O O O
(a) (b)
molecular formula C4 H10 O is/are [2014]
O
(a) tert-butanol and 2-methylpropan-2-ol
O O O
(b) tert-butanol and 1, 1-dimethylethan-1-ol
(c) n-butanol and butan-1-ol (c) (d)
(d) Isobutyl alcohol and 2-methylpropan-1-ol
O

22. Which of the following will not show geometrical isomerism 27. NH2
NH2
(a) Ph −− N == N −− Ph
N N NH
(b) 2,4 − Dinitro phenyl hydrazone of acetone H
(I ) (II) (III) (IV )
(c) Oxime of formaldeyde
Which of the following statements is/are correct
(d) Cyclohexan −1, 2 − diol (a) (I ) and (II ) are aromatic and have equal basic strength
23. Which of the following are resolvable (b) (I ) is aromatic and (II ) is anti – aromatic, but (II ) is
stronger base than (I )
CH3
(a) (c) The order of basicity of the above compounds is
H
(IV )  (III )  (II )  (I )
F (d) The conjugate acid of (IV ) is more stabilized than the

(b) conjugate acid of (II )
CH3
H 28. The decreasing order of pKa value of the following is
H CH3
I. CH  CH II. III.
CH3 CH3 H H
(c) (a) III  I  II (b) II  I  III
CH3
(c) I  III  II (d) I  II  III
H
29. b
4 3 N
OH
3
(d) CH (Me)
1
2 a
2 N N
N
OH H H
24. Which of the following will show geometrical isomerism Pyridine (I) Pyrrol (II) Imidazole (III)
C2 H5 Which one (s) is/are true
|
(a) CH3 −− C == CH2 (b) [ Pt( NH3 )2 Cl2 ] (a) ( I ) and (III ) are modest Bronsted bases whereas (II )
is not
(b) In (III) N a is more basic than N b
(c) (CrNH3 )4 Cl2 ] (d)
(c) When (II ) is protonated in the presence of a strong
acid, protonation occurs at C − 2
25. Which of the following compounds is chiral
(d) All the nitrogen present in (I ), (II ) and (III ) is sp 2
O
hybridised
NH 30. In which of the following reactions, rearrangement is
possible
(a) (b)
(a) E1 (b) SN1
(c) SN 2' (d) E1cB
CH3 31. Which of the following statements are correct about the
addition of HBr to buta –1, 3 – diene
Br Br
(c) (d) Br
Br
(a) 1, 2 – addition product Me 3 –Bromobut 1– ene
Br
is the major product at lower temperature (−80 C) and
26. Which of the following is diastereomer of meso –2, 3–
dibromo butane is a kinetic control or rate– controlled product.
CH3 CH3 3 1
(b) 1,4– addition 4 1–bromobut–2–ene
(a) H Br (b) Br H Me 2 Br
Br H H Br
CH3
product is the major product at high temperature
CH3
(40 C) and is a thermodynamic or equilibrium-
Br CH3
| controlled product.
Br Br
(c) CH 3 −− C −− Et (d) (c) In a non – polar solvent (e.g., hexane), 1, 2 – addition
| H H
Br CH3 product is predominantly favoured.
(d) In a polar solvent (e.g., acetic acid) 1, 4 – addition
product is predominantly favoured

Reasoning type questions 35. Which of the following is likely to be a solid
Br Br
Read the following statements carefully to mark the correct option (a) (b)
out of the options given below Br Br
(a) Statement 1 is true, statement 2 is true ; statement 2 is
a correct explanation for statement 1 (c) (d)
(b) Statement 1 is true, statement 2 is true ; statement 2 is 36. Which of the following is the most stable isomer of the
not a correct explanation for statement 1 hydrocarbon C10 H10
(c) Statement 1 is true, statement 2 is false H
H
(d) Statement 1 is false, statement 2 is true (a) (b)
32. Statement 1 : Molecules that are not superimposable
H
on their mirror images are chiral.
Statement 2 : All Chiral molecules have chiral centres.
(c) (d)
[2007] H
Passage- II
Comprehension type questions
P and Q are isomers of dicarboxylic acid C4 H 4 O4 . Both
Passage- I decolorize Br2 / H 2 O . On heating, P forms the cyclic
anhydride.
The word "aromatic" though started with benzene and its
Upon treatment with dilute alkaline KMnO4 , P as well as
derivatives only; now it signifies a large variety of organic
compounds. To examine the presence of aromaticity, the Q could produce one or more than one from S, T and U.
following tips are useful. Ensure that COOH COOH COOH
Your compound is cyclic. H OH H OH HO H
Each corner of the ring is either a double bonded atom, or H OH HO H H OH
must carry a negative charge or a positive charge or a hetero
COOH COOH COOH
atom with one or more lone pair of electron. S T U
Your compound must be planar. You may get deceived 37. Compounds formed from P and Q are, respectively [2013]
while examining this. On the plane of the paper everything (a) Optically active S and optically active pair (T, U)
appears planar unless specially specified. (b) Optically inactive S and optically inactive pair (T, U)
Your compound should have a closed shell of (4 n + 2) (c) Optically active pair (T, U) and optically active S
(d) Optically inactive pair (T, U) and optically inactive S
electrons. When the closed loop contains 4n electrons, the
system is rather less stable or antiaromatic. 38. In the following reaction sequences V and W are respectively
H / Ni
In fused ring system, some of the rings give up their aromatic Q ⎯⎯2⎯⎯→ V

nature to adjacent rings in a property known as
AlCl (anhydrous ) 1. Zn − Hg / HCl
"annellation". + V ⎯⎯⎯3⎯⎯⎯⎯⎯→ ⎯⎯⎯⎯⎯⎯⎯→W
2. H3 PO4
33. Which of the following is most acidic
H H O [2013]
H H
(a) (b) (a) O

and
H H H O O
H
V W
CH2OH
(c) (d)
(b) CH2OH and
V W
34. Which of the following has the highest value of dipole O
moment O
O O
(a) (b) (c) O and

V W
O HOH2C
(c) (d) CH2OH and

(d) CH2OH
V W

Passage - III 45. Refer to Q. No. 44 and find out which statement is correct
An organic compound ( A) (C10 H 20 ) on reductive (a) Both reactions proceed by E 2 mechanism
ozonolysis gives 2 – methyl butanal. Based on this (b) Both reactions proceed by E1 mechanism
information, answer the following questions (c) Formations of (B) and (C ) proceed by E1 and E 2
39. Compound (A) is Me mechanisms, respectively
Me (d) Formations of (B) and (C ) proceed by E 2 and E1
(a) Me mechanisms, respectively
Me
Me 46. Which statement is correct about the following reaction
Me Me
(b) Br CH 3OH Me Me Ph
Me Ph ⎯⎯⎯ ⎯→ +
Me Ph Me Me
Me Me Me
Me
(A) (I ) (II )
(c) Me
Me Me (a) The major product is (I ) by E1 mechanism
Me (b) The major product is (I ) by E 2 mechanism
(d) Me (c) The major product is (II ) by E1 mechanism
Me Me
(d) The major product is (II ) by E 2 mechanism
47. Which statement is wrong about the given reaction
40. If the stereochemistry about the double bond in (A) is cis ,
O
the total number of stereoisomers for (A) is || O
HO −− S
(a) 2 (b) 3 || Ph + OH
O Me
(c) 4 (d) 5
41. If the stereochemistry about the doubled bond in (A) is cis, H H H Me
+
the total number of enantiomers for (A) is HO3 S Me HO3 S H
(a) None (b) 2 (I) (II)
(Cis) (Trans)
(c) 4 (d) 6
42. If the stereochemistry about the double bond in (A) is (a) The reaction proceeds by E1cB mechanism
trans,the total number of stereoisomers for (A) is (b) EWG (−− SO 3 H ) stabilises the carbanion formed in
(a) 2 (b) 3 the first step

(c) The reaction is stereospecific but non – regioselective
(c) 4 (d) 5
43. If the stereochemistry about the double bond in (A) is trans, (d) PhO is a stronger base than OH ion
the total number of enantiomers for (A) is 48. Which statement is wrong about the given reaction
(a) None (b) 2
Ph Ph F3C − CO3 H Ph Ph 
(c) 4 (d) 6 ⎯⎯ ⎯ ⎯ ⎯⎯→
Me N Me N O
Passage - IV Me Me Me
Me
In elimination reaction, the major product is either Saytzeff
(more – substituted alkene) or Hofmann product (less – Ph Ph Me
+ HO N
substituted alkene) depending on the nature of the substrate Me H Me
and the nature of the base. (a) The reaction is called Cope reaction and proceeds by
44. Which statement is correct about the reactions E1cB mechanism
F (b) The reaction proceeds by syn – elimination
Me (c) The reaction is stereospecific and stereoselective
Me + OH ⎯⎯→(B)
(A) (d) The reaction is non – stereospecific and regioselective
Me 3 CO
⎯⎯⎯⎯→(C) Passage - V
(a) Both products (B) and (C ) are Hofmann product The leaving group is that functional group which is ejected
with electrons of the  − bond in a reaction. Better the
 
 Me
 leaving group, faster is the reaction. The relative leaving
  ability of the leaving group X in (R −− X ) is increased by
(b) Both products (B) and (C ) are Saytzeff product (i) The polarisability of (R −− X ) bond
 Me 
  (ii) The stability of X
 Me  (iii) The degree of stabilization through solvation of X
(c) Product (B) is Hofmann and (C ) is Saytzeff product (iv) The strength of (R −− X ) bond
(d) Product (B) is Saytzeff and (C ) is Hofmann product The leaving group tendency is also called fugacity

49. Which statement is wrong Integer type questions
(a) In polar aprotic solvents such as DMSO, DMF , and
This section contains some integer type questions. The answers
DMA , the fugacity order is I  Br  Cl  F
to each of the questions is a single-digit integer, ranging from
(b) Strong bases are good leaving groups
0 to 9.
(c) The leaving group order of the following is
55. The total number of cyclic structural as well as stereo isomers
OH  RO  CH  C  NH2 possible for a compound with the molecular formula
C 5 H 10 is [2009]
(d) Charged species are good leaving groups than neutral
species 56. The maximum number of isomers (including stereoisomers)
50. Which statement is correct that are possible on monochlorination of the following
compound, is CH3 [2011]
(a) Only SN1 reaction depends on the nature of leaving
group
C
(b) Only SN 2 reaction depends on the nature of leaving
group CH3CH2 CH2CH3
H
1 2
(c) Both SN and SN reactions depend on the nature 57. The total number of contributing structures showing
of leaving group hyperconjugation (involving C–H bonds) for the following
(d) All carbocation is [2011]
H3C  CH2CH3
51. Which one of the following has the highest fugacity
 
(a) Tosylate  OTs  (b) Mesylate
 
(c) Triflate (F3C −− SO3 ) (d) All are equal

52. Which one of the following undergoes SN reaction easily 58. The total number of basic groups in the following form of
(a) Vinyl bromide lysine is [2010]
(b) Bromobenzene 
H 3 N — CH 2 — CH 2 — CH 2 — CH 2 O
(c) p − Nitro bromobenzene
Me Me
CH — C
H2N O–
Br
(d) 59. The total number of cyclic isomers possible for a
hydrocarbon with the molecular formula C4 H 6 is [2010]
53. Which statement is correct
60. When the following aldohexose exists in its D-configuration,
(a) EtO is a strong base and therefore a good leaving
the total number of stereoisomers in its pyranose form is
group
[2012]
(b) The amine group in ArNH 2 is converted into a good
CHO
leaving group by reacting ArNH 2 with NaNO 2 + HCl |
CH 2
at 0 C |
(c) The (OH ) group is converted into a good leaving CHOH
group by reacting alcohols with TsCl ( p − toluene |
 O  CHOH
 ||  |
sulphonyl chloride)  Me S −− Cl  CHOH
 ||  |
 O 
 
CH 2OH
(d) The amine group in RNH 2 is converted into leaving 61. The total number(s) of stable conformers with non-zero
group by reacting RNH 2 with NaNO 2 + HCl at 0 C dipole moment for the following compound is (are)
Cl [2014]
54. Which of the following is the wrong order of fugacity
(a) SbH 3  AsH 3  PH 3  NH 3 Br CH3
(b) F  OH  NH2  CH3 Br Cl
(c) NH 3  NH 2 −− NH 2  MeNH −− NH −− Me  CH3

62. Consider all possible isomeric ketones, including
Me 2 N −− NMe 2 
stereoisomers of MW = 100. All these isomers are
(d) CN  OH  OMe  CH3 independently reacted with NaBH 4 (Note : stereoisomers
are also reacted separately). The total number of ketones
that give a racemic product(s) is/are [2014]

63. The total number of stereoisomers that can exist for M is 73. For the given compound X , the total number of optically
active stereoisomers is ….
HO
HO
M O [2015]
64. The number of resonance structures for N is HO
HO
OH X
This type of bond indicates that the configuration at the

[2015] specific carbon and the geometry of the double bond is fixed
65. In the following monobromination reaction, the number of This type of bond indicates that the configuration at the
possible chiral products is [2016] specific carbon and the geometry of the double bond is not
CH2CH2CH3 fixed [2018]
Br2(1.0 mole)
H Br 300º C
Matrix Match type questions
CH3
(1.0 mole)
In this section each question has some statements (A, B, C, D,...)
(enantiomerically pure)
given in Column-I and some statements (p, q, r, s, t,...) in
66. How many geometrical isomers are possible for the given Column-II. Any given statement in Column-I can have correct
compound matching with ONE OR MORE statement(s) in Column-II. For
example, if for a given question, statement B matches with the
statements given in q and r, then for that particular question against
67. Amongst the following the total number of compound will statement B, darken the bubbles corresponding to q and r in the
show geometrical isomerism ORS. i.e. answer will be q and r.
Br
Br ...
(a) (b)
Br
Br
C6H5 OH H3C NH2
(c) C N (d) C N
...
H H3C
74. Match the compounds/ions in Column I with their

properties/reactions in Column II. [2006]
68. (A) . Number of resonating structures of (A) is Column I Column II
(A) CH 3 − CHBr − CD 3 on (p) E1 reaction
69. Number of  − hydrogen in given compound is treatment with alc. KOH
gives CH 2 = CH − CD 3 as
a major product
(B) Ph − CHBr − CH 3 (q) E2 reaction
reacts faster than
70. How many total resonance structure can be drawn for the Ph − CHBr − CD 3
following carbocations
(C) Ph − CH 2 − CH 2 Br on (r) E1cb reaction
treatment with
O
−
71. Give total products (including stereoisomer) of SN1 and C2H5OD / C2H5O
E1 reaction Br
gives Ph − CD = CH 2
EtOH
as the major product
(D) PhCH 2CH 2 Br and (s) First order
72. Given total products (including stereoisomer) of SN1 and
reaction
E1 reactions PhCD 2CH 2 Br react with
EtOH
Cl same rate

75. Match the reactions in Column I with appropriate options
CH2
in Column II. [2010] (B) (q) A hydrocarbon
is the final
Column I Column II product
O
N2Cl OH (p)
(A) Racemic mixture (C) C (r) Aromaticity is
+ Cl destroyed
NaOH / H2O
⎯⎯ ⎯⎯⎯→
0C
N=N OH
(D) (s) Nucleophilic
substitution
OH OH
(B) | | (q) Addition reaction
H 3 C − C − C − CH 3
| | 77.
CH 3 CH 3
H SO
⎯⎯2⎯⎯
4
→ Column-I Column-II
O
||
C CH 3
H 3C C Compounds Characteristics
| CH3
CH 3
(A) O (p) Diastereomers
Me Et Reductive
(C) (r) Substitution
enzyme 
reaction
⎯⎯⎯⎯→
1. LiAlH4 OH
2. H3 O+
(+) Me Et
and
(B) COOH COOH (q) Conformation
H Br H Br
H Br Br H
COOH COOH
(D) HS Cl (s) Coupling reaction
and
(C) Me Me (r) Asymmetric
Base
⎯⎯⎯→ S H OH HO H
HO H H OH synthesis
Me Me
Me and Me
(t) Carbocation (D) (s) Enantiomers
Me H
intermediate
H H
H Me
Me and
(E)
76. Match the entries listed in Column I with appropriate
H Me
entries listed in Column II.
Me
H H H H
Column I Column II H
O
H H
C Electrophilic Me
(A) Cl (p) substitution

78. (F) E1cB (u) Bimolecular and second –
order kinetics
Column-I Column-II
(v) Unimolecular and second
order kinetics
Reaction Stereoisomers
81.
Column-I Column-II
(A) (p) 2
Reaction Mechanism
(B) CH3 (q) 4 (A) (p)
2 RBr + HCOOH + Solvent with E1
high dielectric constant
H3C CH3 (B) t − BuCl + MeCOOH (q) E2

(C) (r) 6 + MeCOO K

(Small)
(C) OH (r) SN1

(D) Ph (s) 8
+ SOCl2
Ph Me
79. O
(D) (s) SN 2
OH
Column-I Column-II
+ Cl C Cl
Compounds Characteristics Ph Me
(E) OH (t) SN i
(A) F Br (p) S
==
Cl I
Ph Me
(B) F I (q) Z + SOCl2
==
Cl Br + Pyridine
N
(C) H (r) E 82. Column – I contains reactions and Column – II contains
H3C OH major products
COOH Column – I Column – II
(D) COOH
(s) R
H2N H (A) + (p)
ONa Br OH
Me
80.
Column-I Column-II + HBr

(B) OMe (q) Br
Mechanism Stereochemistry
(A) SN1 (p) Stereospecific and

(C) + NaOMe (r)
stereoselective Br OMe
(B) SN 2 (q) Non – stereospecific and non

– stereoselective
(D) + MeBr (s)
ONa
(C) SN 2 (r) Non – stereospecific, but
stereoselective
O
(D) E1 (s) Stereospecific, but non – (t)
stereoselective
[2018]
(E) E2 (t) Unimolecular, and first –
order kinetics

14. General Organic Chemistry – Answers Keys
1. Bonding and Hybridisation in Organic 6 d 7 c 8 b 9 d 10 d
Compounds
11 a 12 b 13 a 14 a 15 b
1 b 2 c 3 c 4 c 5 a
16 a 17 d 18 b 19 b 20 b
6 c 7 b 8 a 9 a 10 c
21 b 22 a 23 c 24 b 25 c
11 c 12 c 13 d 14 c 15 d 26 b 27 c 28 b 29 c 30 a
16 b 17 b 31 d 32 b 33 d 34 b 35 c
36 b 37 b 38 c 39 c 40 c
2. Dipole Moment, Resonance and Reaction
Intermediates
41 a 42 d 43 a 44 b 45 b
1 a 2 d 3 e 4 d 5 a 46 b 47 c 48 c 49 b 50 b
6 a 7 b 8 a 9 b 10 b 51 b 52 c 53 c 54 a 55 b
11 a 12 d 13 d 14 d 15 b 56 a 57 b 58 c 59 d 60 b
16 a 17 a 18 b 19 c 20 c 5. IIT-JEE/ AIEEE
21 d 22 c 23 a 24 c 25 d 1 c 2 a 3 b 4 b 5 c
6 c 7 a 8 b 9 a 10 b
26 b 27 d 28 b 29 d 30 c
11 b 12 b 13 b 14 d 15 d
31 b 32 b 33 b 34 b
16 b 17 d 18 a 19 b 20 a
3. Organic Reactions and their Mechanism
21 c 22 c 23 d 24 c 25 b
1 c 2 b 3 a 4 d 5 b
26 c 27 d 28 d 29 a 30 b
6 c 7 d 8 c 9 a 10 c
31 a 32 c 33 c 34 b 35 a
11 d 12 d 13 a 14 c 15 c
36 c 37 b 38 d 39 a 40 b
16 b 17 a 18 d 19 d 20 d
41 b 42 d 43 b 44 a 45 a
21 a 22 b 23 c 24 c 25 b
46 d 47 b 48 a 49 a 50 a
26 d 27 a 28 b 29 b 30 c
51 d 52 d 53 c 54 a 55 c
31 a 32 a 33 b 34 b 35 c
56 a 57 d 58 a 59 c 60 a
4. Structural and Stereo Isomerism 61 c 62 b 63 d 64 a 65 c
1 a 2 b 3 c 4 c 5 b 66 b 67 c 68 d 69 b 70 a

71 b 72 d 73 a 74 b 75 d
76 c 77 b 78 b 79 d
6. JEE Advanced
1 bc 2 bc 3 ad 4 cd 5 ac
6 acd 7 d 8 ac 9 ad 10 bcd
11 cd 12 abd 13 bc 14 a 15 abc
16 acd 17 bd 18 cd 19 bcd 20 ab
21 bd 22 bc 23 bd 24 bcd 25 ab
26 ab 27 cd 28 b 29 acd 30 abc
31 abcd 32 c 33 a 34 b 35 c
36 c 37 b 38 a 39 a 40 b
41 b 42 b 43 b 44 a 45 a
46 a 47 d 48 d 49 b 50 c
51 c 52 c 53 c 54 d 55 7
56 8 57 6 58 2 59 5 60 8
61 3 62 5 63 2 64 9 65 5
66 2 67 3 68 3 69 6 70 3
71 3 72 6 73 7
74 A→ q; B→ q; C→ r, s; D→ p, s
75 A→ r, s; B→ t; C→ p, q; D→ r
76 A→ p, q; B→ q, r; C→ p, q, s; D→ s
77 A→ r; B→ p; C→ s; D→ p; E→ q
78 A→ q; B→ p; C→ r; D→ s
79 A→ q; B→ r; C→ s; D→ p
80 A→ p, t; B→ p, u; C→ p, u; D→ r, t; E→ p, u; F→ s, v
81 A→ r; B→ p, r; C→ t; D→ t; E→ s
82 A→ p, s; B→ q; C→ s; D→ r

15. Hydrocarbons
Introduction
Organic compounds composed of only carbon and hydrogen are called hydrocarbons.
Source
Mineral oil or crude oil, petroleum [Petra → rock; oleum → oil] is the dark colour oily liquid with offensive odour found at various
depths in many regions below the surface of the earth. It is generally found under the rocks of earth’s crust and often floats over
salted water.
Composition of Crude Oil
Alkanes
Found 30% to 70% contain upto 40 carbon atoms. Alkanes are mostly straight chain but some are branched chain isomers.
Cycloalkanes
Found 16% to 64% cycloalkanes present in petroleum are; cyclohexane, methyl cyclopentane etc. Cycloalkanes rich oil is called
asphaltic oil.
Aromatic Hydrocarbon
Found 8% to 15% compound present in petroleum are; Benzene, Toluene, Xylene, Naphthalene etc.
Sulphur, Nitrogen and Oxygen Compound
• Sulphur compound present to the extent of 6% include mercaptans [R–SH] and sulphides [R–S–R]. The unpleasant smell of
petroleum is due to sulphur compounds.
• Nitrogenous compounds are pyridines, quinolines and pyrroles.
• Oxygen compounds present in petroleum are alcohols, phenols and resins.
• Compounds like chlorophyll, haemin are also present in it.
Natural Gas
It is a mixture of Methane (80%), Ethane (13%), Propane (3%), Butane (1%), Vapours of low boiling pentanes and hexanes (0.5%)
and Nitrogen (1.3%).
LPG : Liquefied Petroleum Gas contains butane and propane and used as cooking gas. It is highly inflammable.
CNG : When natural gas is compressed to less than 1% of its volume, it is called compressed natural gas (CNG). Natural gas
has octane rating of 130. It consists, mainly of methane and may contain, small amount of ethane and propane.
Petroleum Refining
Separation of useful fractions by fractional distillation is called petroleum refining.
Table : 15.1 Fractions after Petrol Refining

Fraction Boiling range Approximate Uses
(oC) composition
Uncondensed gases Upto room C 1 – C4 Fuel gases: refrigerants; production of carbon black,
temperature hydrogen; synthesis of organic chemicals.
Crude naphtha on refractionation 30 – 150o C5 – C10
yields,
(i) Petroleum ether 30 – 70o C 5 – C6 Solvent.
o
(ii) Petrol or gasoline 70 – 120 C 6 – C8 Motor fuel; drycleaning; petrol gas.
(iii) Benzene derivatives 120 – 150o C8 – C10 Solvent; drycleaning.
Hydrocarbons | 80
Kerosene oil 150 – 250o C11 – C16 Fuel; illuminant; oil gas.
o
Heavy oil 250 – 400 C15 – C18 As fuel for diesel engines; converted to gasoline by
cracking.
Refractionation gives,
(i) Gas oil, (ii) Fuel oil,
(iii) Diesel oil
Residual oil on fractionation by Above 400o C17 – C40
vacuum distillation gives,
(i) Lubricating oil C17 – C20 Lubrication.
(ii) Paraffin wax C20 – C30 Candles; boot polish; wax paper; etc.
(iii) Vaseline C20 – C30 Toilets; ointments; lubrication.
(iv) Pitch C30 – C40 Paints, road surfacing.
Petroleum coke As fuel.
(on redistilling tar)
Petrochemicals
All such chemicals which are derived from petroleum or natural gas called petrochemicals. Some chemicals which are obtained from
petroleum are summarised in table :
Table : 15.2 Different Petrochemicals
Hydrocarbons Compounds Derived
Methane Methyl chloride, chloroform, methanol, formaldehyde, formic acid, freon, hydrogen for synthesis of ammonia.
Ethane Ethyl chloride, ethyl bromide, acetic acid, acetaldehyde, ethylene, ethyl acetate, nitroethane, acetic anhydride.
Ethylene Ethanol, ethylene oxide, glycol, vinyl chloride, glyoxal, polyethene, styrene, butadiene, acetic acid.
Propane Propanol, propionic acid, isopropyl ether, acetone, nitromethane, nitroethane, nitropropane.
Propylene Glycerol, allyl alcohol, isopropyl alcohol, acrolein, nitroglycerine, dodecylbenzene, cumene, bakelite.
Hexane Benzene, DDT, gammexane.
Heptane Toluene
Cycloalkanes Benzene, toluene, xylenes, adipic acid.
Benzene Ethyl benzene, styrene, phenol, BHC (insecticide), adipic acid, nylon, cyclohexane, ABS detergents.
Toluene Benzoic acid, TNT benzaldehyde, saccharin, chloramine-T, benzyl chloride, benzal chloride.
Characteristics of Hydrocarbons
Knocking
The metallic sound during working of an internal combustion engine is termed as knocking.
“The greater the compression greater will be efficiency of engine.” The fuel which has minimum knocking property is always
preferred.
The tendency to knock falls off in the following order : Straight chain alkanes > branched chain alkanes > olefins > cyclo
alkanes > aromatic hydrocarbons.
Octane Number
It is used for measuring the knocking character of fuel used in petrol engine. The higher the octane number, the more compression
the fuel can withstand before igniting. Fuels with a higher octane rating are used in high performance engines that require higher
compression ratios.
The octane number of a given sample may be defined as the percentage by volume of iso-octane present in a mixture of iso-octane
and n-heptane which has the same knocking performance as the fuel itself.
CH 3 − CH 2 − CH 2 − CH 2 − CH 2 − CH 2 − CH 3 ; n-heptane: octane no. = 0
Hydrocarbons | 81
CH3 CH3
| |
CH 3 − C − CH 2 − C − CH 3 ; 2, 2, 4-Trimethylpentane or iso-octane: Octane no. = 100
| |
CH3 H
Example: A given sample has the knocking performance equivalent to a mixture containing 60% iso-octane and 40% heptane. The
octane number of the gasoline is, therefore, 60.
Methods to Increase Octane Number
Presence of following types of compounds increases the octane number of gasoline.
• In case of straight chain hydrocarbons octane number decreases with increase in the length of the chain.
• Branching of chain increases the value of octane number
• Introduction of double bond or triple bond increases the value of octane number.
• Cyclic alkanes have relatively higher value of octane number.
• The octane number of aromatic hydrocarbons are exceptionally high.
• By adding gasoline additives (e.g., TEL).
Antiknock Compounds
To reduce the knocking property or to improve the octane number of a fuel, certain chemicals are added to it. These are called
antiknock compounds. One such compound, which is extensively used, is tetraethyl lead (TEL). TEL is used in the form of
following mixture,
TEL = 63%, Ethylene bromide = 26%, Ethylene chloride = 9% and a dye = 2%.
However, there is a disadvantage that the lead is deposited in the engine. To remove the free lead, the ethylene halides are
added which combine with lead to form volatile lead halides.
Pb + Br − CH2 − CH2 − Br → PbBr2 + CH2 = CH2
Ethylene bromide Volatile Ethylene
However, use of TEL in petrol is facing a serious problem of Lead pollution, to avoid this, a new compound cyclopenta dienyl
manganese carbonyl (called as AK-33-X) is used in developed countries as antiknocking compound.
Cetane Number
It is used for grading the diesel oils. CH3
CH 3 − (CH 2 )14 − CH 3 Cetane → cetane no. = 100

Cetane no. = 0
The cetane number of a diesel oil is the percentage of cetane (hexadecane) by
volume in a mixture of cetane and  -methyl naphthalene which has the same -Methyl naphthalene
ignition property as the fuel oil under consideration.
Classification
Hydrocarbons are classified into two types:
Acyclic or Aliphatic Hydrocarbons
These compounds contain open chains of carbon atoms in their molecule. These are further classified into following three categories:
(1) Alkanes (Paraffins), (2) Alkenes (Olefins) and (3) Alkynes
Cyclic Hydrocarbons
These compounds contain closed chains of carbon atoms. These are further classified into following two categories:
(1) Alicyclic and (2) Aromatic hydrocarbons (Arenes)
Alkanes [Paraffines]
“Alkanes are saturated hydrocarbon containing only carbon-carbon single bond in their molecules.”
Hydrocarbons | 82
Alkanes are less reactive so called paraffins; because under normal conditions alkanes do not react with acids, bases, oxidising agents and
reducing agent.
General Formula : C n H 2n+ 2 , Examples are CH 4 , C 2 H 6 , C3 H 8
Conformational Isomerism
Definition
The different arrangements of atoms in a molecule which can be obtained due to rotation about carbon-carbon single bond are
called conformational isomers (conformers) or rotational isomers (rotamers). This type of isomerism is found in alkanes and
cycloalkanes and their substituted derivatives.
Torsional Strain
Rotation around a C − C sigma bond is not completely free. It is in fact hindered by an energy barrier of 1 to 20 kJ mol–1 in
different bonds. There is a possibility of weak repulsive interactions between the bonds or electron pairs of the bonds on adjacent
carbon atoms. Such type of repulsive interaction is known as torsional strain.
Difference between Conformation and Configuration
The term conformation should not be confused with the configuration, which relates to those spatial arrangements of the atoms
of a molecule that can be changed only by the breaking and making of bonds whereas the spatial arrangements in conformation
are changed simply by rotation about a single bond.
Representation of Conformations H
Conformers can be represented in two simple ways. These are : (i) Saw horse Back
C carbon
representation and (ii) Newman projection
H H
• Sawhorse Representation
H H
In this projection, the molecule is viewed along the axis of the model from an C Front
carbon
oblique angle. The central carbon-carbon bond ( C − C ) is drawn as a straight line
slightly tilted to right for the sake of clarity. The front carbon is shown as the lower H
Fig. 15.1: Saw Horse Representation
left hand carbon and the rear carbon is shown as the upper right hand carbon. The
three bonds around each carbon atom (C − H in ethane or C − C in higher alkanes) are shown by three lines.
• Newmann Projection
H Back carbon
This is a simple method to represent the conformations. In this method, the molecule is H
H
viewed from the front along the carbon-carbon bond axis. The two carbon atoms forming
the -bond are represented by two circles; one behind the other so that only the front Front carbon
carbon is seen. The front carbon atom is shown by a point whereas the carbon further H H
from the eye is represented by the circle. Therefore, the C − H bonds of the front carbon
H
are depicted from the centre of the circle while C − H bonds of the back carbon are drawn Fig. 15.2: Newmann Projection
from the circumference of the circle at an angle of 120° to each other.
Conformation in Alkanes
• Conformations of Ethane H
H
When one of the carbon atom is kept fixed and other is rotated about H Eclipsed
H (less stable)
C − C bond an infinite numbers of isomers are possible. Out of all the H H
conformations for ethane, only two extreme conformations are important
and these are:
(a) Staggered conformation (b) Eclipsed conformation 12.5 kJ mol–1

Energy
60°
H H H H
H
H H 60° 60° H H Staggered H H
H H (stable)
H H H H H H H H
H H H
60° Eclipsed
Staggered conformation Fig. 15.3: The Variation of Energy versus
conformation Rotation about C–C Bond
Fig. 15.4: Staggered Conformation of Ethane is more Stable than Eclipsed.
Hydrocarbons | 83
Relative Stabilities of the Conformations of Ethane
The two conformations of ethane differ in their relative stabilities. The staggered conformation has minimum repulsions
between the H-atoms attached tetrahedrally to the two carbon atoms. On the other hand, the eclipsed conformation has
maximum force of repulsion between H-atoms. Therefore, the staggered conformation is more stable than the eclipsed
conformation. The difference in the energy contents of the staggered and eclipsed conformations is 12.5 kJ mol-1. This small
barrier to rotation is also called torsional barrier of the single bond.
However, this energy difference is not large enough to prevent rotation. Even at ordinary temperatures, the
molecules have thermal or kinetic energy to overcome this energy barrier. Therefore, the two conformations of ethane go on
changing from one form to another and consequently, it is not possible to isolate the different conformations of ethane.
• Conformations of Propane
The next higher member in alkane series, propane (CH 3 − CH 2 − CH 3 ) also has two extreme conformations, the energy
barrier in propane is 14kJmol–1, which is slightly higher than that in ethane.
CH3
CH3
H H H
H H H H
H H H
Staggered propane Eclipsed propane
Fig. 15.5 Newmann Projection of Propane
• Conformations of Butane
As the alkane molecule becomes larger, the conformation situation becomes more complex. In butane
(CH 3 − CH 2 − CH 2 − CH 3 ) , for example, the rotation about the single bond between two inner atoms ( C 2 and C3 ) is
considered. In this case, all the staggered as well as eclipsed conformations will not have same stability and energy because
of different types of interaction between C − C (of methyl) and C − H bonds.
The lowest energy conformation will be the one, in which the two methyl groups are as far apart as possible i.e., 180° away
form each other.
This conformation will be maximum staggered, most stable and is called anti or trans conformation (marked I). Other
conformations can be obtained by rotating one of the C 2 or C3 carbon atoms through an angle of 60° as shown ahead.
CH3 CH3 CH3
H H CH3
H H
H3C
H H H
H H
H H
CH3 H
I II III
Anti Eclipsed Skew or Gauche
CH3 CH3 CH3

CH3 CH3 H
H
H H H
H H H
H H H CH3
H
IV V VI
Fully eclipsed Skew or Gauche Eclipsed
(same as III) (same as II)
Hydrocarbons | 84
The order of stability of these conformations is, Anti > Skew or Gauche > Partially eclipsed > Fully eclipsed.
Fully eclipsed
Eclipsed IV Eclipsed
II VI
14.6 18.4 14.6

kJ/mol kJ/mol kJ/mol
Energy
Skew
III
3.8 kJ/mol Skew V
Anti
I
1 2 3 4
Fig. 15.6 : Energy Changes during Rotation about C2 – C3 Bond of n-butane C H3 − C H2 − C H2 − C H3
Conformations in Cycloalkanes
• Stability of Cycloalkanes
Compounds with three and four membered rings are not as stable as compounds with five or six membered rings.
a) Baeyer's-strain Theory
The German chemist Bayer's was the first to suggest that the instability 24.44°
of these small rings compounds was due to angle strain. deviation
Baeyer's strain theory was based upon the assumption that when an
open chain organic compound having the normal bond angle 109.5° is 109.5° 60°
convert into a cyclic compound, a definite distortion of this normal angle
109.5°
takes place leading to the development of a strain in the molecule.
24.44°
Baeyer assumed that cyclic rings are planar. Assuming that the rings are deviation
planar, the amount of strain in various cycloalkanes can be expressed in
terms of angle of deviation (d).
1 
d= [109.5 −  ] ; Where n = number of carbon-carbon  
2
bonds in cycloalkane ring;  = inner bond angle in the
cycloalkane ring. Cyclopropane Cyclobutane Cyclopentane
 = 60°  = 90°  = 108°
1 d = 22.44° d = 9.4° d = 0.44°
Angle strain  d  ;
inner angle
1  
Stability   inner angle( )
d 
Now let us take the case of three to eight membered cyclic Cyclohexane Cycloheptane Cyclooctane
compounds.  = 120°  = 128.6°  = 135°
d = –5.16° d = –9.33° d = –12.46°
The positive and negative values of (d) indicate whether the
inner angle is less than or more than the normal tetrahedral value.
Baeyer thus predicted that a five membered ring compound would be the most stable. He also predicted that six
membered ring compounds would be less stable and as the cyclic compounds become larger than five membered ring,
then they would become less and less stable.
Hydrocarbons | 85
b) Discrepancy in Baeyer’s Strain Theory
Contrary to what Baeyer predicted, however cyclohexane is more stable than cyclopentane. Furthermore, cyclic
compounds do not become less and less stable as the number of sides increase. Thus, Baeyer strain theory is applicable
only to cyclopropane, cyclobutane and cyclopentane.
The mistake that Baeyer made was to assume that all cyclic compounds are planar. But only cyclopropane is planar and
other cycloalkanes are not planar.
• Types of Strain
Cyclic compounds twist and bend in order to achieve structure that minimises the three different kinds of strain and that
can destabilise a cyclic compound.
a) Angle Strain is the strain that results when the bond angle is different from desired tetrahedral bond angle of 109.5°.
b) Torsional Strain is caused by repulsion of the bonding electrons of one substituent with bonding electrons of a nearby
substituent.
c) Steric Strain is caused by atoms or groups of atoms approaching each other too closely.
• Conformation of Cyclohexane
Six membered cyclic compounds are most stable because they can exist in a conformation that is almost completely free of
strain. This conformation is called the chair conformation. In a chair conformation of cyclohexane all bond angles are
109.38° which is very close to the 109.5° and all the adjacent carbon-hydrogen bonds are staggered.
a a
c H H
c c
H a a
a a CH2 H
1
c
6 5
H CH2 H
c c
H H a a
a a
Fig. 15.8: Newman Projection 2 3 4
Fig. 15.7: Chair Conformation of of the Chair Conformation
Cyclohexane a
a) Each carbon in chair conformation has an axial bond (a) and an equatorial bond (e).
b) Axial bonds are perpendicular to the plane of the ring and equatorial bonds are in the plane of the ring.
c) If axial bond on carbon-1 is above the plane of the ring then axial bond on carbon-2 will be below the plane of the ring.
Thus C − 1, C − 3 and C − 5 axial bonds are above the plane C − 2, C − 4 and

(a) Above
C − 6 axial bonds are below the plane.
(e) Below 1
C − 1 axial and C − 2 axial are trans to each other. Similarly, C − 1 and C − 5
(e) Above 2
axials are cis to each other.
(a) Below
d) If axial bond on carbon-1 will be above the plane then equatorial bond on this
carbon will be below the plane.
e) As a result of rotation about carbon-carbon single bonds

cyclohexane rapidly interconverts between two stable chair Flipping
conformations. This interconversion is known as ring –flip.
When the two chair forms interconvert, axial bonds
become equatorial and equatorial bonds become axial.
f) Cyclohexane can also exist in a boat conformation. Like the chair conformation, the boat conformation is free of angle
strain. However, the boat conformation is less stable than the chair conformation by 11 kcal/mole. Boat conformation
is less stable because some of the carbon-hydrogen bonds in boat conformation are eclipsed.
Hydrocarbons | 86
Flagpole
hydrogen
H CH2 H
H H
H H CH2
H H H H
Fig. 15.9: Boat Fig. 15.11: Half-Chair
Fig. 15.10: Newmann Fig. 15.12: Twist-
Conformation of
Projection of Boat Boat
Cyclohexane
Conformation
The boat conformations are further destabilised by the close proximity of the flag pole hydrogens. These hydrogens are 1.8 Å apart
but the vander Waal’s radii is 2.4 Å. The flag pole hydrogens are also known as trans nuclear hydrogens.
The relative stabilities of the four conformations of cyclohexane decrease in the order:
Chair > twist boat > boat > half chair.
Preparation of Alkanes
By Catalytic Hydrogenation of Alkenes and Alkynes (Sabatier and sendesen’s reaction)
Ni Ni
Cn H 2n + H 2 ⎯⎯
⎯→ Cn H 2n + 2 ; Cn H 2n − 2 + 2H 2 ⎯⎯→
⎯ Cn H 2n + 2
Alkene heat Alkane Alkyne heat Alkane
• Methane cannot be prepared by this method.
Birch Reduction
1. Na / NH
R − CH = CH 2 ⎯⎯⎯⎯⎯
⎯3
→ R − CH 2 − CH 3
2. CH3OH
From Alkyl Halides
Zn / HCl
• By reduction : RX + H 2 ⎯⎯⎯⎯
⎯→ RH + HX
Pd orPt.
• With hydrogen in presence of Pt/Pd : RX + H 2 ⎯⎯⎯⎯→ RH + HX
• With HI in presence of Red phosphorus : RBr + 2HI ⎯⎯→ RH + HBr + I 2

Purpose of Red P is to remove I in the form of PI
2 3
By Zn-Cu Couple
Cu
2CH3 CH2OH + Zn ⎯⎯→
⎯ (CH3 CH2O)2 Zn+ 2H ; RX + 2H ⎯⎯→ RH + HX
Zn- Cu couple Zinc ethoxide
Wurtz Reaction
Dry ether
RX + 2 Na + X R ⎯⎯ ⎯⎯→ R − R+ 2 NaX
Alkyl halide Alkyl halide Alkane
R − Br or RI preferred in this reaction. The net result in this reaction is the formation of even no. of carbon atoms in molecules.
Frankland’s Reaction
2RX + Zn ⎯⎯→ R − R + ZnX2
Corey-House Synthesis
1. Li CH 3 −CH 2 −Cl
2CH 3 − CH 2 − Cl ⎯⎯ ⎯→ (CH 3 − CH 2 )2 LiCu ⎯⎯ ⎯⎯⎯⎯→ CH 3 − CH 2 − CH 2 − CH 3
2. CuI Lithium dimethyl cuprate
• Reaction is suitable for odd number of Alkanes.
Hydrocarbons | 87
From Grignard Reagents
• By action of acidic ‘H’
RMgX + HOH ⎯⎯→ RH + Mg(OH ) X

Alkyl magnesium Water Alkane
halide
• By reaction with alkyl halide
R − X + RMgX ⎯⎯→ R − R + MgX 2
From Carboxylic Acids
• Laboratory Method [Decarboxylation Reaction or Duma reaction]
heat
RCOONa + NaOH ⎯⎯⎯→ R − H + Na2CO3
CaO Alkane
NaOH and CaO is in the ratio of 3 : 1 (Sodalime)
• Kolbe’s Synthesis
O
Electrolysis
||
R − C − O − Na+ R − C − O − + Na+
|| Ionization
O
a) At anode [Oxidation] :
• •
2R − C − O − − 2e − ⎯⎯→ 2R − C − O ⎯⎯→ 2 R+ 2CO2 
|| ||
O O
•
2 R ⎯⎯→ R − R (alkane)
b) At cathode [Reduction] :
2 H 2O
2Na+ + 2e − ⎯⎯→ 2Na ⎯⎯ ⎯⎯→ 2NaOH + H 2 (  )
c) Both ionic and free radical mechanism are involved in this reaction.
• Reduction of Carboxylic Acid

Reduction
CH3COOH + 6 HI ⎯⎯ ⎯⎯ ⎯→ CH3CH3 + 2H 2O + 3I 2
Acetic acid Red (200 o C) p Ethane
By Reduction of Alcohols, Aldehydes, Ketones or Acid Derivatives

Red P Red P
CH 3OH + 2HI ⎯⎯⎯→ CH 4 + H 2O + I 2 ; CH 3CHO + 4 HI ⎯⎯⎯→ C2 H 6 + H 2 O + 2 I 2
Methanol 150o C Methane Acetaldehyde 150o C Ethane
(Methyl alcohol) (Ethanal)
Red P
CH3COCH3 + 4 HI ⎯⎯ ⎯→ CH3CH2CH3 + H 2O + 2I 2
Acetone 150o C Propane
(Propanone)
O
||
Red P
CH3 − C − Cl + 6 HI ⎯⎯ ⎯→ CH3 − CH3 + H 2O + HCl + 3 I 2
Acetyl chloride 200o C Ethane
(Ethanoyl chloride)
O
||
Red P
CH3 − C − NH2 + 6 HI ⎯⎯ ⎯→ CH3 − CH3 + H 2O + NH3 + 3 I 2
Acetamide 200o C Ethane
(Ethanamide)
Aldehydes and ketones when reduced with amalgamated zinc and conc. HCl also yield alkanes.
Hydrocarbons | 88
Clemmensen Reduction
Zn − Hg Zn − Hg
CH3CHO+ 4 H ⎯⎯⎯⎯ → CH3 − CH3 + H 2O ; CH3COCH3 + 4 H ⎯⎯⎯⎯→ CH3CH2CH3 + H 2O
Acetaldehyde HCl Ethane Acetone Conc. HCl Propane
(Ethanal) (Propanone)
Wolff-Kishner Reduction
Aldehydes and ketones can be reduced to hydrocarbon in presence of excess of hydrazine and sodium alkoxide on heating.
R R R
H NNH C H ONa
C = O ⎯⎯2 ⎯⎯
⎯2
→ C = NNH2 ⎯⎯2 ⎯
5
⎯
⎯→ CH2
− H 2O 180o C,− N 2
R R R
Hydroboration of Alkenes
• Diborane (B2 H 6 ) adds to an olefinic bond forming trialkyl borane which on treatment with acetic acid yields corresponding
alkane.
B H CH COOH
R − CH = CH2 ⎯⎯2 ⎯
⎯6
→ (R − CH2 − CH2 )3 B ⎯⎯⎯
3
⎯⎯→ R − CH2 − CH3
+
Alkene Trialkyl borane [H ] Alkane
This method cannot be used to prepare methane.
• Coupling of alkyl boranes by means of silver nitrate

o
2 B2H6 AgNO3 25 C
6[R − CH = CH2 ] ⎯⎯ ⎯⎯→[2R − CH2 − CH2 −]3 B ⎯⎯ ⎯⎯⎯ ⎯→ 3[ RCH 2 CH 2 − CH 2 CH 2 R]
NaOH
By Desulfurization
Raney Ni
R − S − S − R ' + H2 ⎯⎯ ⎯⎯→ RH + R ' H.
Physical Properties
Physical State: Alkanes are colourless, odourless and tasteless.
Alkanes State
C1 − C4 Gaseous state
C5 − C17 Liquid state [Except neo pentane which is gas]
C18 and above Solid like waxes
Density: Alkanes are lighter than water.
1
Solubility: Insoluble in water, soluble in organic solvents, solubility 
Molecular mass
Boiling Points and Melting Points
Melting points and boiling points  Molecular mass Alkane : C3 H 8 C4 H10 C5 H12 C6 H14 C7 H16 C8 H18
1
Melting points and boiling points 
No. of branches M.P.(K) : 85.9 138 143.3 179 182.5 216.2
Exception : Few highly branched and symmetrical alkanes have higher melting point (but low boiling point) than their isomers.
E.g. M.P. of neo-pentane is higher than n-pentane.
Melting points of even > Odd no. of carbon atoms
This is because, the alkanes with even number of carbon atoms have more symmetrical structure and result in closer packing in
the crystal structure as compared to alkanes with odd number of carbon atoms.
Hydrocarbons | 89
C C C C C C
C C C C C
C C
Fig. 15.13: Odd no. of Carbons Fig. 15.14: Even no. of Carbons
Chemical Properties
• Halogenation : R − H + X − X ⎯⎯→ R − X + HX
The reactivity of halogen is : F2  Cl 2  Br2  I 2
a) Fluorine can react in dark Cl 2 , Br2 require light energy. I 2 does not show any reaction at room temperature, but on
heating it shows iodination.
b) Iodination of methane is done in presence of oxidising agent such as HNO 3 / HIO3 / HgO which neutralises HI .
• Chlorination of Methane
u v light u v light, Cl
− HCl
CH4 + Cl − Cl ⎯⎯ ⎯ ⎯→ CH2 − Cl2 ⎯⎯⎯⎯⎯
2
→ CHCl3 ⎯⎯ ⎯→ CCl4
− HCl − HCl Cl 2 hv
Thermal chlorination of alkane is known as Hare and McBee reaction.
High
• Nitration : R − H + HONO2 ⎯⎯ ⎯→ R − NO2 + H 2O (Free radical mechanism)
Alkane temp. Nitroalkane
Nitrating mixture : (Con. HNO 3 + Con. H 2 SO 4 ) at 250o C
SO
• Sulphonation : R − H + HOSO3 H ⎯⎯⎯3⎯⎯→ R − SO3 H + H 2O (Free radical mechanism)
Prolongedheating
Lower alkanes particularly methane, ethane, do not give this reaction.
Oxidation
• Complete Oxidation or Combustion
 3n + 1 
Cn H 2n + 2 +  O2 ⎯⎯→ nCO2 + (n + 1)H 2O + Q
 2 
• Incomplete Combustion or Oxidation
Burn
2CH4 + 3O2 ⎯⎯⎯ → 2CO + 4 H2O ; CH4 + O2 ⎯⎯→ C +2H2O
• Catalytic Oxidation
Cu − tube
CH4 + [O] ⎯⎯ ⎯⎯o→ CH3OH
100 atm / 200 C
This is the industrial method for the manufacture of methyl alcohol.
• Higher alkanes are oxidised to fatty acids in presence of manganese stearate

O2
CH3 (CH2 )n CH3 ⎯⎯
⎯→ o
CH3 (CH2 )n COOH
100 −160 C
• Chemical Oxidation
KMnO4
(CH3 )3 CH ⎯⎯ ⎯⎯→ (CH3 )3 .C.OH
Isobutane Tertiary butyl alcohol
Hydrocarbons | 90
Thermal Decomposition (Cracking or Pyrolysis or Fragmentation)
o o
1000 C 500 C
CH 4 ⎯⎯ ⎯⎯→ C + 2H 2 ; C 2 H 6 ⎯⎯ ⎯⎯→ CH 2 = CH 2 + H 2 ; C3 H 8 ⎯⎯→ C2 H 4 + CH4 or C 3 H 6 + H 2
Methane Ethane Cr2O3 + Al2O3 Ethylene Propane
This reaction is of great importance to petroleum industry.
Isomerisation
CH 3
|
AlCl3 + HCl 2-Methyl Pentane
CH 3CH 2CH 2CH 3 ⎯⎯⎯⎯⎯→ CH 3 CHCH 3 ;
n-Butane 200o C,35 atm Isobutane 2,3 Dimethyl
butane
Aromatisation
CH3
H2C CH3
+4H2
H2C CH2
CH2 Benzene
n-Hexane CH3 CH3
n-Heptane Methyl cyclo Toluene

Hexane
Step up Reaction (Insertion Reaction)
• Reaction with CH2 N2 (Diazo Methane)
hv
R − CH2 − H + CH2 N 2 ⎯⎯ → R − CH2 − CH2 − H
• Reaction with CHCl3 / NaOH

−
CHCl 3 / OH
R − CH2 − H ⎯⎯ ⎯⎯⎯ ⎯→ R − CH2 − CHCl2
: CCl 2
• Reaction with CH 2 = C = O
O
||
CH 2 = C / 
R − CH 2 − H ⎯⎯ ⎯ ⎯
⎯→ R − CH 2 − CH 3
:CH 2 / −CO
HCN Formation
N 2 / electricarc Al O
2CH4 ⎯⎯ ⎯⎯⎯⎯→ 2HCN + 3H 2 or CH4 + NH3 ⎯⎯2⎯
⎯
o
3
→ HCN + 3H 2
700 C
Chloro Sulphonation/ Reaction with SO2+Cl2

uv light
CH3 − CH2 − CH3 + SO2 + Cl2 ⎯⎯⎯ ⎯→ CH 3 − CH 2 − CH 2 SO 2 Cl + HCl
This reaction is known as Reed’s reaction. This is used in the commercial detergent formation.
Ni / Al O
Action of Steam CH4 + H2O ⎯⎯⎯⎯⎯
2 3
→ CO + 3H2
800o C
Pyrolysis
It is the process of heating a compound in absence of air when the compound decomposes. This process of pyrolysis of alkanes
is also called cracking.
• Alkane vapours when passed through red hot metal tube in absence of air decomposes to simpler hydrocarbons. The product
formed during cracking depends upon (i) Nature of alkane, (ii) Temperature and pressure, (iii) presence of catalyst.
• The case of cracking in alkanes increases with increase in molar mass and branching in alkane.
Hydrocarbons | 91
• C − H bond fission is catalysed by Cr2 O3 , V2 O5 , MoO3 whereas presence of SiO 2 , Al 2 O3 and ZnO catalyses C − C bond
fission.
• The products obtained during cracking increases with increase in molar mass of alkane.
CH3 CH = CH2 + H 2
CH3 − CH2 − CH3
CH2 = CH2 + CH4
• Cracking plays an important role in petroleum industry to convert higher alkanes to lower one (petrol C6 − C11 ).
Methane
It is also known as marsh gas or fire dump.
Preparation
Industrial Methods of Preparation
Methane gas is obtained on a large scale from natural gas by liquefaction.
From Carbon Monoxide
A mixture of carbon monoxide and hydrogen is passed over a catalyst containing nickel and carbon at 250o C when methane
is formed.
Ni + C
CO + 3H2 ⎯⎯ ⎯o
→ CH4 + H2O
250 C
Bacterial decomposition of cellulose material present in sewage water
(C6 H10O5 )n + nH2O ⎯⎯→ 3nCH4 + 3nCO2

Cellulose
By striking an electric arc between carbon electrodes in an atmosphere of hydrogen

o
1200 C
C + 2H 2 ⎯⎯ ⎯⎯→ CH4
By passing a mixture of hydrogen sulphide and carbon disulphide vapour through red hot copper tube
High temperature
CS2 + 2H2S + 8Cu ⎯⎯ ⎯⎯⎯⎯ ⎯→ CH4 + 4Cu2S
By the hydrolysis of Al or Be carbides

Heat Heat
Al4C3 + 12H2O ⎯⎯⎯ → 4 Al(OH)3 + 3CH4 ; Be2C + 4 H2O ⎯⎯⎯ → 2Be(OH)2 + CH4
Physical Properties
(1) It is a colourless, odourless, tasteless and non-poisonous gas.
(2) It is lighter than air. Its density at NTP is 0.71 g/l.
(3) It is slightly soluble in water but is fairly soluble in ether, alcohol and acetone.
(4) Its melting point is − 182.5 o C and boiling point is − 161.5 o C .
Uses
(1) In the manufacture of compounds like methyl alcohol, formaldehyde, chloroform, carbon tetrachloride, etc.
(2) In the preparation of carbon black which is used for making printing ink, black paints and as a filler in rubber vulcanisation.
(3) As a fuel and illuminant.
Ethane
Preparation
Laboratory Method of Preparation

Zn − Cu couple
C2 H 5 I + 2H ⎯⎯ ⎯⎯⎯ ⎯→ C2 H 6 + HI
Ethyl iodide C2H5OH Ethane
Hydrocarbons | 92
Industrial Method of Preparation
Ni
CH2 = CH2 + H 2 ⎯⎯→
⎯ CH3 − CH3
Ethylene 300 o C Ethane
(ethene)
Physical properties
(1) It is a colourless, odourless, tasteless and non-poisonous gas.
(2) It is very slightly soluble in water but fairly soluble in alcohol, acetone, ether, etc.
(3) Its density at NTP is 1.34 g/L
(4) It boils at – 89oC. Its melting point is –172oC.
Uses
(1) As a fuel
(2) For making hexachloroethane which is an artificial camphor.
(3) Interconversion of Alkanes
Alkenes (Olefins)
These are the acyclic hydrocarbons which contain carbon-carbon double bond. These are also known as olefins (oil forming), because
lower alkenes react with halogens to form oily substances. General formula is Cn H 2n . Examples, C 2 H 4 , C 3 H 6 , C 4 H 8 .
Preparation
From Alkynes
H
|
Lindlar's Catalyst
R − C  C − R + H 2 ⎯⎯⎯⎯⎯⎯ ⎯→ R − C = C − R
Pd . BaSO 4 |
H
Catalyst Poison such as BaSO 4 ,CaCO 3 are used to stop the reaction after the formation of alkene.
From Mono Halides
H H H
| | |
R − C − C − H + Alc. KOH ⎯⎯ ⎯→ R − C = C − H
− HX
| | |
H X H
Alkene
According to saytzeff's rule, when two alkenes may be formed, the alkene which is most substituted one predominates.
KOH (alc .)
CH 3 − CH 2 − CH − CH 3 ⎯⎯ ⎯⎯ ⎯→ CH3 − CH = CH − CH3 + CH3 − CH2 − CH = CH2
| 2- Butene(80%) 1- Butene(20%)
Cl
The ease of dehydrohalogenation for different halogens is in the order.
Tertiary alkyl halide > Secondary alkyl halide > Primary alkyl halide
From Dihalides
• From Gem Dihalides
X Zn X
R – CH + + CH – R R – CH = CH – R
X Zn X
Above reaction is used in the formation of symmetrical alkenes only.
Hydrocarbons | 93
• From Vicinal Dihalides
H H H H
| | | |
alcohol,
R − C − C − H + Zn (dust) ⎯⎯⎯o ⎯→ R − C = C − H + ZnX 2
| | 300 C
X X
• Alkene is not Formed from 1, 3 Dihalides
Cycloalkanes are formed by dehalogenation of it.

Zn dust
CH2 − CH2 − CH2 ⎯⎯ ⎯⎯→ CH2 + ZnX 2
| |
X X H 2C CH2
• By Action of NaI on Vicinal Dihalide
Br Br I I
| | | |
NaI
C− C ⎯⎯
⎯→ C− C ⎯⎯→ C=C
acetone −I2
From Alcohols [Laboratory Method]

H 2 SO 4 or H 3 PO4
CH3 CH2OH ⎯⎯ ⎯⎯⎯⎯⎯→ CH2 = CH2 + H 2O
Ethyl alcohol 443 K Ethene
| | | |
H − C − C − ⎯⎯⎯ →− C = C −+ H 2O
2 3 Al O
| 633 K
| alkene
H OH
• The Ease of Dehydration Follows
Tertiary (3o )  Secondary (2o )  Primary (1o )
Kolbe’s Reaction
CH 2COOK CH2
Electrolys is
| + 2H 2O ⎯⎯ ⎯⎯ ⎯→ || + 2CO2 + H 2 + 2KOH
CH 2COOK CH2
Potassium succinate Ethene
From Esters [Pyrolysis of Ester]
CH3 − CO − O H CH3 − COOH

Glass wool 450o
| | ⎯⎯ ⎯⎯⎯⎯→ +
liq. N 2
CH2 − CH2 CH2 = CH2
Pyrolysis of Quaternary Ammonium Compounds
+ −
heat
(C2 H5 )4 N OH ⎯⎯⎯→ (C2 H5 )3 N + C2 H4 + H 2O
Tetraethyl ammonium Triethylamine Ethene
hydroxide (Tert. amine)
Action of Copper Alkyl on Vinyl Chloride
CuR
H 2C = CHCl ⎯⎯⎯
2
→ H 2C = CHR
Vinyl chloride
By Grignard Reagents
R
Mg + X − CH = CH2 ⎯⎯→ MgX 2 + R − CH = CH2
X
Hydrocarbons | 94
Wittig Reaction
(Ph)3 P = CH2 + CH− R ⎯⎯→(Ph)3 P = O + R − CH

|| ||
O CH2
O
||
(Ph)3 P = CH − R + CH − R ⎯⎯→(Ph)3 P = O + R − CH = CH − R
From -bromo Ether [Boord Synthesis]
Br O − C2 H 5
| | Br
Zn
R − CH − CH ⎯⎯→⎯ R − CH = CH − R + Zn
C4 H9OH
| O − C2 H 5
R
Physical Properties
(1) Alkenes are colourless and odourless (except ethene).
(2) These are insoluble in water and soluble in organic solvents.
(3) Physical state: C1 − C4 ⎯⎯→ gas; C4 − C16 ⎯⎯→ liquid;  C17 ⎯⎯→ solid wax
(4) B.P. and M.P. decreases with increasing branches in alkene.
(5) The melting point of cis isomers are lower than trans isomers because cis isomer is less symmetrical than trans. Thus trans packs
more tightly in the crystal lattice and hence has a higher melting point.
(6) The boiling points of cis isomers are higher than trans isomers because cis-alkenes has greater polarity (dipole moment) than
trans one.
(7) These are lighter than water.
(8) Dipole moment: Alkenes are weakly polar. The -electrons of the double bond can be easily polarized. Therefore, their dipole
moments are higher than those of alkanes.
Chemical Properties
Francis Experiment
According to Francis, electrophile first attacks on olefinic bond.
CH2 = CH2 + Br – Br CH2 – CH2

| |
Br Br
CH2 – CH2 + CH2 – CH2

| | | |
Br Br Br Cl
Reaction with Hydrogen
H H H H
| | | |
Ni
R − C = C − R + H 2 ⎯⎯→
⎯ R − C − C− R
| |
H H
Reduction of Alkene via Hydroboration
Alkene can be converted into alkane by protolysis

H − BH +
H / H 2O
3RCH = CH2 ⎯⎯⎯⎯
2
→(R − CH2 − CH2 )3 B ⎯⎯ ⎯⎯ ⎯→ R − CH 2 − CH 3
Hydrocarbons | 95
Hydroboration
Alkene give addition reaction with diborane which is called hydroboration. In this reaction trialkylborane formed, which is very
important and used for synthesis of different organic compound
3R − CH = CH2 + BH3 ⎯⎯→ (R − CH 2 − CH 2 )3 B Trialkyl borane
CH3COOH/Zn NaOH/ H2O2 HI/H2O2
R – CH2 –CH3 R – CH2 –CH2OH R – CH2 –CH3
The overall result of the above reaction appears to be anti-Markownikoff’s addition of water to a double bond.
By Treatment with AgNO3 + NaOH
This is a coupling reaction:
CH 3 CH3
| |
B2 H 6 AgNO / NaOH
6CH 3 − CH 2 − CH 2 − C = CH 2 ⎯⎯ ⎯→ 2[CH3 − (CH2 )2 − C − CH2 ]3 B ⎯⎯⎯3⎯⎯⎯→
⎯
|
H
CH3 CH3
| |
CH3 − CH2 − CH2 − C − CH2 − CH2 − C − CH2 − CH2 − CH3
| |
H H
Birch Reduction
This reaction is believed to proceed via anionic free radical mechanism.
− −
Na Et .− O − H
Na
R − CH = CH2 ⎯⎯ ⎯⎯→ R − CH − CH 3 ⎯⎯
Et − O − H
⎯→ R − CH − CH 2 ⎯⎯ ⎯→ R − CH− CH3 ⎯⎯
−
⎯⎯ ⎯→ R − CH2 − CH3
+e − +e
Halogenation
o
500 C
CH3 CH = CH2 + Cl2 ⎯⎯ ⎯⎯→ ClCH2 − CH = CH2 + HCl
Propene Allylchloride
or 3-Chloro-1- propene
• NBS [N-bromo succinimide] reagent is used for the specific purpose of brominating alkenes at the allylic position.
CH2 – CO CH2 – CO
CH3 CH=CH2 + | N – Br CH2 – CH = CH2+ | N–H
CH2 – CO | CH2 – CO
NBS Br
Propene
Allyl bromide Succinimide
• In presence of polar medium, alkene form vicinal dihalide with halogen.
H H H H
| | | |
CCl 4
R − C = C− H + X − X ⎯⎯ ⎯→ R − C − C− H ; Reactivity of halogen is F2  Cl 2  Br2  I 2
| |
X X
Vicinal dihalide
CCl 4
Br2 + CH 2 = CH 2 ⎯⎯ ⎯→ CH 2 Br − CH 2 Br
(Brown) (inert solvent) Ethylene bromide
(colourless)
a) The reaction with fluorine is explosive whereas iodine reacts very slowly.
b) The reaction is stereospecific, anti-addition is observed.
c) In general for symmetrical alkenes and symmetrical reagents, the addition takes place as :
Hydrocarbons | 96
Cis – alkene + syn-addition → meso
Trans–alkene + syn – addition → racemic
Cis–alkene + anti – addition → racemic
Trans– alkene + anti – addition → meso
Reaction with HX [Hydrohalogenation]
H
|
C=C + HX ⎯⎯→ C− C
|
alkene
X
Alkyl halide
• Markownikoff’s Rule
This rule states that: The addition of unsymmetrical reagents to unsymmetrical alkenes occurs in such a way that the negative
part of the reagent goes to that carbon atom of the double bond which carries lesser number of hydrogen atoms.
H H
| |
CH3 − CH = CH2 + HBr ⎯⎯→ CH3 − C − C− H
| |
Br H
This rule can be used only in those alkenes which fulfil the following conditions:
a) Alkene should be unsymmetrical.
b) Substituent / substituents present on doubly bonded carbon/(s) should only be +I group.
c) If phenyl group is present on doubly bonded carbon, then both doubly bonded carbons should be substituted by phenyl
groups.
• Mechanism of Markownikoff’s Rule is as follows:

 + |
Slow
C=C + E ⎯⎯ ⎯→ C− C − E
Olefin Electrophile |
Carbonium ion
 | − |
Fast
C− C− E + X ⎯⎯⎯ → C − C− E
| Nucleophile | |
X
Addition product
• Anti-Markownikoff’s Rule (Peroxide effect or Kharasch effect)
In the presence of some peroxides, the addition of HBr to unsymmetrical alkenes takes place contrary to Markownikoff’s rule
i.e. negative part of the reagent goes to the carbon atom of the double bond which carries higher number of hydrogen atoms.
H H H H
| | | |
Peroxide
CH3 − CH = CH2 + HBr ⎯⎯ ⎯⎯→ CH 3 − C − C − H + CH 3 − C − C − H
| | | |
Br H H Br
(minor) (major)
Peroxide effect is effective only in case of HBr and not effective in the case of HCl and HI due to following reasons :
a) H − Cl bond (103 Kcal/mol) is stronger than H − Br bond (87 kcal/mol) H − Cl is not decomposed by peroxide-free
radical.
b) Iodine free radical formed as H − I bond is weaker but iodine free radicals readily combine with each other to form
iodine molecules rather than to attack the double bond.
c) In H − Br both the chain propagation steps 3 and 4 are exothermic while in HCl and HI one of the step is
endothermic.
Hydrocarbons | 97
• Mechanism of Anti-Markownikoff’s Rule is as follows:
a) Step I : Chain-initiating step : (O − O) bond in peroxide is weak and is easily broken homolytically in presence of
. .
light or heat to form a radical (R O) which in turn removes a hydrogen atom from HBr giving Br radical.
. .
Homolytic
RO : OR
. ⎯⎯ ⎯ ⎯⎯ → 2 RO
UV Free radical
. .
RO + H : Br ⎯⎯→ ROH + Br
Free radical
. .
H : Br ⎯⎯→ H + Br
b) Step II : Chain Propagating Step : Br radical completes its octet by combining with one of the electrons in the 
-bond of the alkene to form a bromine-carbon bond. Bromine radical can join to any of the sp 2 -hybridised carbons of
the alkene to form primary or secondary free radicals.
. .
Br + CH2 = CHCH3 ⎯⎯→ BrCH2 CH CH3
(2o Free radical more stable than 1o )
.
Br + CH2 = CHCH3 ⎯⎯→ .CH2CHCH3
|
Br
(1o Free radical)
Since stability of 2o free radical is greater than 1o free radical, hence this radical formed predominantly and addition
of HBr in presence of peroxide is regioselective.
c) Step III : Chain-Terminating Step : Alkyl radical that is formed removes a hydrogen atom from another molecule of
HBr to produce alkyl halide and bromine radical.
. .
BrCH2 CHCH3 + H : Br ⎯⎯→ BrCH2 CH2 CH3 + Br
Since the first species that adds to the alkene is a radical, the addition of HBr in the presence of peroxides is called a
radical addition reaction.
Reaction with Hypohalous Acids

− +
Cl , H O
CH2 = CH2 + H O Cl ⎯⎯2⎯2⎯
⎯→ CH2OH.CH2Cl
Ethylene Ethylenechlorohydrin
In case of unsymmetrical alkenes Markownikoff rule is followed.
Reaction with Sulphuric Acid
CH2 = CH2 + H + HSO4− ⎯⎯→ CH3 CH2 HSO4

Ethylene Ethyl hydrogen sulphate
CH3CH2 HSO4 ⎯⎯→ CH2 = CH2 + H2SO4
a) This reaction is used in the separation of alkene from a gaseous mixture of alkanes and alkenes.
b) In case of unsymmetrical alkenes Markownikoff rule is followed.
Reaction with Nitrosyl Chloride
NO
|
C=C + NOCl ⎯⎯→ C − C ( NOCl is called Tilden's reagent)
|
Cl
If hydrogen is attached to the carbon atom of product, the product changes to more stable oxime.
Hydrocarbons | 98
NO
| H
C− C C − C = NOH
| | |
Cl Cl
Oxime
Oxidation
• With Alkaline KMnO4 [Baeyer’s reagent]
H H H H
| | | |
Alk. KMnO4
R − C = C − H + [O] + H − OH ⎯⎯⎯⎯⎯ → R − C − C− H (also with neutral KMnO4 )
− OH | |
HO OH
glycol
• With Acidic KMnO4
H H O
| | ||
acidic
R − C = C − H + [O] ⎯⎯ ⎯→ R − C − O − H + CO2 + H 2 O
KMnO4
This reaction is used as a test of unsaturation.

Hydroxylation
• Using Peroxy Acid
CH3 CH3
| |
H O , HCOOH
H −C ⎯⎯2⎯2 ⎯⎯⎯→ H − C − OH
|| or HCO 3 H
|
C−H HO − C − H
| |
CH3 CH3
trans 2 - Butene (racemic)
While cis gives a meso-compound

• Hydroxylation by OsO4
R H
R
H OH
HO H
R
H R ()
Trans
If perbenzoic acid or peroxy acetic acid is used then oxirane are formed.
C6 H 5 CO3 H − H 2O
R − CH = CH − R ⎯⎯ ⎯⎯⎯→ R − CH − CH − R ⎯⎯ ⎯⎯→ R − CH − CH − R
or CH 3CO3 H | |
OH OH O
[Oxirane]
Combustion
3n
Cn H 2n + O2 ⎯⎯→ nCO2 + nH 2O
2
They burn with luminous flame and form explosive mixture with air or oxygen.
Ozonolysis
O O O
C C C +C
O O [Aldehydes, or ketones
Ozonide or mixture]
Hydrocarbons | 99
This process is quite useful to locate the position of double bond in an alkene molecule. The double bond is obtained by
joining the carbon atoms of the two carbonyl compounds.
Oxy – Mercuration Demercuration
With mercuric acetate (in tetrahydrofuran- THF), followed by reduction with NaBH 4 / NaOH is also an example of hydration
of alkene according to Markownikoff’s rule.
(CH3 )3 C − CH = CH2 + (CH3 COO)2 Hg ⎯⎯→ (CH3 )3 C − CH − CH2 HgOOCCH3 ⎯⎯ ⎯⎯⎯⎯→ (CH 3 ) 3 C − CH − CH 3
NaBH 4 / NaOH
3,3-dimethyl -1- butene Mercuric acetate
|
THF |
OCOCH3 OH
3, 3 − Dimethyl − 2− butanol
Epoxidation
• By O2 / Ag
O
1 Ag
CH 2 = CH 2 + O2 ⎯⎯
⎯→ CH 2 − CH 2
2
• Epoxidation by performic acid or perbenzoic acid
O
||
C–O–O–H
|
O
CH 2 = CH 2 ⎯⎯⎯⎯⎯⎯→ CH 2 − CH 2
O
O
||
H − C −O −O − H
CH3 − CH = CH2 ⎯⎯ ⎯⎯⎯⎯→ CH3 − CH − CH2
Hydroboration
−
H O / OH
3R − CH = CH2 + BH3 ⎯⎯→(R − CH2 − CH2 )3 B ⎯⎯2⎯2 ⎯⎯⎯→ R − CH 2 − CH 2 − OH + B(OH ) 3
Trialkyl borane
(Anti Markownikoff’s rule)

Hydroformylation
H H
| |
CoH (CO)4
R − CH = CH 2 + CO + H 2 ⎯⎯ ⎯⎯⎯→ R − C − C − H
| |
H C=O
|
H
If CO + H 2 O is taken then respective acid is formed.

CoH (CO)4
R − CH = CH 2 + CO + H 2 O ⎯⎯ ⎯⎯⎯→ R − CH 2 − CH 2
|
COOH
Addition of Formaldehyde
    HOH
R − CH = CH 2
H 2 C = O + H ⎯⎯→[H 2 C = O H ⎯→ H 2 C− OH] ⎯⎯ ⎯ ⎯ ⎯ → R − C H − CH 2 − CH 2 − OH +
−H
H2
C

R – CH CH2 HCHO / H
⎯ ⎯⎯ ⎯⎯ R − CH − CH 2 − CH 2
| |
O O
OH OH
C
1, 3−diol
H2
Cyclic acetal
Hydrocarbons | 100
Polymerisation
H H  H H H H
 
| |  | | | |
Trace O2 + Catalyst
C = C ⎯⎯ ⎯ ⎯ ⎯ ⎯⎯→− C − C − C − C 
1500o / high pressure  
| |  | | | |
H H  H H H H
 n
Isomerisation
CH 3 − CH 2 − CH 2 − CH = CH 2 AlCl3 CH 3 − CH 2 − CH = CH − CH 3
The mechanism proceeds via carbocation.
Alkenylation of Alkenes (Dimerisation)
CH3 CH3
| |
H+
⎯→ H 2C = C− CH2 − C− CH3 + CH3 − C = CH − C − CH3
2CH3 − C = CH2 ⎯⎯
| o | | | |
80
CH3 CH3 CH3 CH3 CH3
2 − Methylpropene ( A) Major C8 H16 ( B) minor C8 H16
(Isobutene)
Addition of HNO3
CH2 = CH2 + HO − NO2 ⎯⎯→ CH2OH.CH2 NO2

Ethene 2-Nitroethanol
Addition of Acetyl Chloride
CH2 = CH2 + CH3 COCl ⎯⎯→ CH2ClCH2COCH3

Ethene 4-Chlorobutanone- 2
Uses
(1) For the manufacture of polythene – a plastic material
(2) For artificial ripening of fruits
(3) As a general anaesthetic
(4) As a starting material for a large number of compounds such as glycol, ethyl halides, ethyl alcohol, ethylene oxide, etc
(5) For making poisonous mustard gas (War gas)
(6) For making ethylene-oxygen flame.
Alkynes
These are the acyclic hydrocarbons which contain carbon-carbon triple bond are called alkynes. General formula is Cn H 2n− 2 .
Example: Ethyne CH  CH ; Propyne CH 3 − C  CH
Preparation
Preparation of Acetylene
• Copper and silver acetylides are very sensitive to shock when dry and may explode violently. However these can be
decomposed by acids to regenerate acetylene.
HNO3
AgC  C − Ag ⎯⎯ ⎯
⎯→ HC  CH + 2 AgNO3
dil.
Hydrocarbons | 101
alc KOH or NaNH2
CH2Br – CH2Br
alc KOH, NaNH2
CH3 – CHBr2
Ag dust(Powder)
CHCl3

Zn dust
CHBr2 – CHBr2

CHBr
Zn
CHBr
alc KOH, NaNH2
CH2 = CH – Cl
C2H2
[Acetylene]
HC – COONa
Kolbe’s electrolytic synthesis
HC – COONa
H2O (Laboratory method)
CaC2
Electric arc, 1200oC
2C+ H2
Bertholot’s process
(i) Na (ii) R-X

CH3 – C CH
(i) CH3MgI (ii) R-X
CH3 – C CH
Preparation of Higher Alkynes
• Acetylene gives salt with NaNH 2 or AgNO 3 (ammonical) which react with alkyl halide to give higher alkyne.
NaNH 2 2CH 3 I
2CH  CH ⎯⎯⎯⎯ → Na − C  C − Na ⎯⎯⎯ ⎯→ CH3 − C  C − CH3
disodium acetylide Butyne
• By Grignard reagent
R− X
CH3 − C  CH + CH3 − Mg − X ⎯⎯→ CH 3 − C  C − Mg − X + CH 4 ⎯⎯ ⎯→ CH 3 − C  C − R+ MgX 2
Alkyne
Physical Properties
(1) Physical State: The first three members of this family are colourless gases, the next eight are liquids while the higher ones are
solid.
(2) Smell: All the alkynes are odourless. However acetylene has garlic odour due to presence of impurities of phosphorous and
hydrogen sulphide. It is somewhat poisonous in nature.
(3) Solubility: These are insoluble in water but highly soluble in acetone and alcohol. Acetylene is transported under high pressure
in acetone soaked on porous material packed in steel cylinders.
(4) Melting and Boiling point: The m.p. and b.p of alkynes are slightly higher than those of the corresponding alkenes and
alkanes because of linear structure and close packing in crystal lattice.
(5) Density: Densities of alkynes increases as the molecular size increases. However, these are lighter than water. Acetylene is
lighter than air.
(6) Burning: It burns with luminous flame and forms explosive mixture with air.
Hydrocarbons | 102
Chemical Reactivity of Alkynes
Electrophilic Addition Reaction
C  C is less reactive than the carbon-carbon double bond towards electrophilic addition reaction. This is because in alkyne,
carbon has more s-character so more strongly will be the attraction for  electrons.
Nucleophilic Addition Reaction
Alkyne also undergo nucleophilic addition with electron rich reagents. e.g. Addition of water, cyanide, carboxylic acid, alcohols.
Nucleophilic addition can be explained on the basis that alkynes form vinylic carbanion which is more stable than alkyl
carbanion formed by alkene.
Nu Nu
| − | −
− −
−C  C − + Nu ⎯⎯→ − C = C− −C = C − + Nu ⎯⎯→ − C − C−
(vinylic carbanion- more stable) (alkyl carbanion- less stable)
Acidity of Alkynes Red hot

tube
Acetylene and other terminal alkynes (1- alkynes) are weakly NH3
acidic in character. 
S/H2S
1
Example: CH  CH + NaNH 2 ⎯⎯→ H − C  C Na + + H2 
2 40%
H2SO480
/1%HgSO
o
C 4
(Monosodium
with
acetylide) CH2+3COOH
Hg , 80oC
The acetylenic hydrogen of alkynes can be replaced by copper (I)
and silver (I) ions. They react with ammonical solutions of cuprous Cl2 CHCl2 Alc. CHCl
| ||
chloride and silver nitrate to form the corresponding copper and CHCl2 KOH
CCl2
silver alkynides. (Westron) (Westroso
l)
ClAsCl2 CHCl (Cadet and Busen
CH  CH + 2[Cu(NH3 )2 ]Cl ⎯⎯→ Cu − C  C − Cu + 2NH4 Cl + 2NH3 |
AlCl3 reaction)
CHAsCl
| 2
Dicopper acetylide (red ppt) Lewisite
CH3COO
CH  CH + 2[ Ag(NH3 )2 ]NO3 ⎯⎯→ AgC  C − Ag + 2NH4 NO3 + 2NH3
HgH
+2
Disilver acetylide (white ppt)

Hg2+/HCl
This reaction can be used to distinguish between 2-alkynes and 60oC
1-alkynes. 1-alkynes will give this test while 2-alkynes will not give
HCN
this test. Ba(CN)
CH3 − C  CH + 2[ Ag( NH3 )2 ] NO3 ⎯⎯→ CH3 − C  C − Ag Cu2Cl2,

Chloroprene
1- propyne NHHCl
4Cl
Cu2O
Cuprene
CH3 − C  C − CH3 + 2[ Ag(NH3 )2 ]NO3 ⎯⎯→ No reaction.
alk. COO
• Explanation for the Acidic Character: It is explained by KMnO4
Oxidation |H
COOH
sp hybridisation. We know that an electron in s − orbital is Oxalic
Lindlar’s acid
more tightly held than in a p -orbital. In sp hybridisation, s -
Catalyst
character is more (50%) as compared to sp 2 (33%) or sp 3
Ni
(25%), due to large s -character the carbon atom is quite
300°C
electronegative.
Na
Chemical Properties of Acetylene

O3/SeO2 CHO
|
CHO
Glyoxal
Hydrocarbons | 103
Chemical Properties of other Alkynes
Oxidation
Alkynes react with BH 3 (in THF) and finally converted into carbonyl compounds.
Tautomerises
⎯→ CH3 − CH = CHOH ⎯⎯⎯⎯⎯
⎯→ CH3CH2CHO
BH3 / THF H O2
3CH3 − C  CH ⎯⎯⎯ ⎯⎯→(CH3 − CH = CH)3 B ⎯⎯2⎯
Propyne OH − (Propanal)
O
||
H 2 SO4
or ⎯⎯⎯⎯
→ CH3 − C − CH 3 (Acetone)
HgSO4
Thus it is useful for preparing aldehyde from terminal alkyne.
Reduction
• Terminal Alkyne
Ni Ni
CH  CH + H 2 ⎯⎯→
⎯ CH2 = CH2 ⎯⎯→
⎯ CH3 − CH3
H2
• Non-terminal Alkyne
If the triple bond is not present at the end of the carbon chain of the molecule, the alkene formed may be cis and trans
depending upon the choice of reducing agents.
With Na / NH 3 or Li / NH 3 (in liquid ammonia) trans alkene is almost an exclusive product while catalytic reduction at
alkyne affords mainly cis alkenes.
R R R H
H2 Li / NH 3
C=C ⎯⎯⎯⎯⎯⎯ R − C  C − R ⎯⎯⎯⎯→ C=C
Pd . / BaSO 4 / quinoline
H H (Lindlarcatalyst) H R
Cis Trans
CC–CC
Trans
Cis
Self Addition or Polymerisation of Alkyne
• Cyclic Polymerisation
Heat
3HC  CH ⎯⎯ ⎯→
Acetylene 600o C
Benzene
CH3
Cu tube
3CH3 − C  CH ⎯⎯ ⎯⎯→
Propyne Heat CH3 CH3
Mesitylene
CH = CH
Anhydrous Ni(CN )2
HC CH
4 CH  CH ⎯⎯ ⎯ ⎯⎯ ⎯⎯→ || ||
Acetylene Tetrahydro furan (solvent)
High pressure
HC CH
CH = CH
Cyclo- octatetraene
• Linear Polymerisation
Cu2Cl2 CH  CH
a) HC  CH + HC  CH ⎯⎯ ⎯ ⎯→ CH2 = CH − C  CH ⎯⎯ ⎯⎯→ CH2 = CH − C  C − CH = CH2
NH4Cl Monovinyl acetylene Divinylacetylene
Cu Cl2
b) HC  CH + HC  CH ⎯⎯2⎯ ⎯→ HC  C − C  CH + H2
NH4Cl , air
Hydrocarbons | 104
Reaction with Formaldehyde
Li / NH 3
HC  CH + 2CH 2 O ⎯⎯→ CH 2 − C  C − CH 2 ⎯⎯ ⎯⎯→ CH − CH = CH − CH OH
2 2
| | |
OH OH OH [Trans-product]
Uses of Acetylene
(1) Acetylene is used as an illuminant.
(2) It is used for the production of oxy-acetylene flame. The temperature of the flame is above 3000o C . It is employed for cutting
and welding of metals.
(3) Acetylene is used for artificial ripening of fruits.
(4) It is used as a general anaesthetic under the name Naracylene.
(5) Acetylene has synthetic applications. It serves as a starting material for the manufacture of a large variety of substances.
(6) On electrical decomposition acetylene produces finely divided carbon and hydrogen. Hydrogen is used in airships.
Degree and Test of Unsaturation
Degree of Unsaturation
2n1 + 2 − n2
The number of degree of unsaturation in a hydrocarbon is given by , Where n1 is the number of carbon atoms; n2 is
2
the number of hydrogen atoms.
2  6 + 2 − 12
For example in C 6 H 12 , the degree of unsaturation is = =1
2
Tests of Unsaturation
Baeyer’s Reagent
It is 1% KMnO 4 solution containing sodium carbonate. It has pink colour.
In aqueous solution of the compound, a few drops of Baeyer’s reagent are added, the pink colour of the solution disappears.
The decolourisation of pink colour indicates the presence of unsaturation in the compound.
R R
Alkene without any hydrogen atom on the carbon forming the double bond C=C don't show this test.
R R
Bromine- Carbon Tetrachloride Test
The compound is dissolved in carbon tetrachloride or chloroform and then a few drops of 5% bromine solution in carbon
tetrachloride are added to it, the colour of bromine disappears. It indicates the presence of unsaturation in the compound.
This test also fails in the case of alkene without any hydrogen atom on the carbon forming the double bond.
Interconversion between Aliphatic Hydrobarbon
Conversion of Ethane into Ethene : (Alkane into alkene)

Br2 Alc.
CH3 − CH3 ⎯⎯⎯→ C2 H 5 Br ⎯⎯⎯→ CH2 = CH2
Ethane hv Ethyl bromide KOH Ethene
Ethene into Ethane : (Alkene into Alkane)

H2
CH2 = CH2 ⎯⎯
⎯o→ CH3 − CH3
Ethene Ni, 300 C Ethane
Hydrocarbons | 105
Ethane into Ethyne (Acetylene) : i.e., Alkane into Alkyne
Br2 Alc. Br2 Alc. KOH
CH3 − CH3 ⎯⎯⎯→ CH3 CH2 Br ⎯⎯⎯→ CH2 = CH2 ⎯⎯⎯→ CH 2 Br − CH 2 Br ⎯⎯⎯⎯→ CH  CH
Ethane hv KOH Ethene CCl 4 1, 2- Dibromoethane or NaNH 2 Ethyne
Ethyne into Ethane : (Alkyne into Alkane)

H2 H2
CH  CH ⎯⎯
⎯o→ CH2 = CH2 ⎯⎯
⎯o→ CH3 − CH3
Ethyne Ni, 300 C Ethene Ni, 300 C Ethane
Ethene into Propene : Ascending in Alkene Series

HI KCN [H] HNO 2
CH 2 = CH 2 ⎯⎯
⎯→ CH 3 CH 2 I ⎯⎯ ⎯→ CH 3 CH 2 CN ⎯⎯⎯→ CH 3 CH 2 CH 2 NH 2 ⎯⎯⎯⎯→ CH3 CH 2 CH 2 OH
Ethene Iodoethane Propane nitrile Reduction 1- Aminopropane 1−Propanol
(Ethyl cyanide)
Alc. PBr3
CH3 CH = CH2 ⎯
⎯⎯ CH3 CH2CH2 Br ⎯⎯⎯
Propene KOH 1 − Bromopropane
HI Li (CH ) Cu Cl 2 Alc.
⎯ CH3CH2 I ⎯⎯⎯3⎯2 ⎯→ CH3CH2CH3 ⎯⎯
or CH2 = CH2 ⎯⎯→ ⎯→ CH3CH2CH2Cl ⎯⎯⎯→ CH3CH = CH2
Ethene Iodoethane Propane hv 1- Chloro propane KOH Propene
HI CH 3 I / Na Cl 2 Alc.
or CH2 = CH2 ⎯⎯→
⎯ CH3CH2 I ⎯⎯⎯ ⎯⎯→ CH3CH2CH3 ⎯⎯⎯→ CH3CH2CH2Cl ⎯⎯⎯→ CH3CH = CH2
Propane hv 1- Chloro propane KOH Propene
Propene into Ethene : Descending an Alkene Series

O /H O
[H] H2SO4
CH3 − CH = CH2 ⎯⎯3 ⎯2⎯→ CH3CHO ⎯⎯⎯→ CH3CH2OH ⎯⎯ ⎯ ⎯→ CH2 = CH2
o LiAlH4
Propene Ethanal Ethanol 170 C Ethene
Acetylene into Propyne (Methyl Acetylene) : (Ascent)

Na CH 3 I
CH  CH ⎯⎯
⎯→ CH  CNa ⎯⎯ ⎯→ CH  C − CH3
Acetylene Monosodium Propyne
acetylide
Propyne into Acetylene : (Descent)

Lindlar's catalyst O3 / H 2O PCl 5 Alc.
CH3C  CH ⎯⎯ ⎯⎯⎯⎯→ CH3CH = CH2 ⎯⎯ ⎯⎯→ CH3CHO ⎯⎯⎯ → CH3CHCl2 ⎯⎯⎯→ CH  CH
Propyne Propylene Acetaldehyde Ethylidene KOH Acetylene
chloride
1-Butyne into 2-Pentyne : (Ascent)

NaNH 2 CH 3 I
CH3CH2C  CH ⎯⎯⎯⎯ → CH3CH2C  C − Na ⎯⎯⎯ → CH3CH2 − C  CCH3
1− Butyne 2 − Pentyne
1-Butyne into 2-Pentanone :
O
||
H O, H 2SO4
NaNH 2
CH3 CH2C  CH ⎯⎯ ⎯→ CH3 CH2C  CCH3 ⎯⎯2 ⎯⎯
CH 3 I
⎯⎯→ CH3 CH2C  CNa ⎯⎯ ⎯→ CH3 CH2CH2 C CH3
1- Butyne ( Liq. NH 3 ) 2 − Pentyne HgSO 4 2 − Pentanone
Separation of Aliphatic Hydrocarbon
The gaseous mixture is passed through ammonical cuprous chloride solution. The terminal alkyne (acetylene) reacts with Cu 2Cl 2 and
forms a red precipitate. It is filtered. The alkyne or acetylene is recovered by decomposition of the precipitate with an acid.
C2 H2 + Cu2Cl2 + 2NH4 OH → C2Cu2 + 2NH4 Cl + 2H2O

(red ppt.)
C2Cu 2 + 2 HNO 3 → C2 H 2 + Cu 2 ( NO 3 )2
The remaining gaseous mixture is passed through concentrated H 2 SO 4 . Alkene is absorbed. The Hydrogen sulphate derivative is heated
at 170oC to regenerate ethene.

C2 H4 + H2SO4 ⎯⎯→ C2 H5 HSO4 ⎯⎯→ C2 H4 + H2SO4
170o C
The methane or ethane is left behind unreacted.
Hydrocarbons | 106
Distinction between Alkanes, Alkenes and Alkynes
Table : 15.3 Distinction between Alkanes, Alkenes and Alkynes
Property Alkane (Ethane) Alkene (Ethene) Alkyne (Ethyne)
Molecular CnH2n+2(C2H6) CnH2n(C2H4) CnH2n–2(C2H2)

formula
Nature Saturated Unsaturated Unsaturated
Single bond between Double bond between two carbon Triple bond between two carbon atoms both
carbon atoms. Each carbon atoms. Both carbon atoms are sp2- carbon atoms are sp-hybridized
atom is sp3-hybridized hybridized –CC–
C–C C=C 1.20 Å
Bond length 1.54 Å 1.34 Å 200 Kcal mol–1
–1
Bond energy : 83 Kcal 144 Kcal mol
mol–1
Burning Burns with nonluminous Burns with luminous flame Burns with smoky flame
flame C2H4+3O2 → 2CO2+2H2O C2H2+5/2O2 → 2CO2+H2O
C2H6+7/2O2→
2CO2+3H2O
Reaction with H2 – CnH2n + H2 ⎯⎯→

Ni
CnH2n+2 CnH2n + H2 ⎯⎯→
Ni
CnH2n+2
300o C 300o C
C2H4 + H2 → C2H6 CnH2n–2 + H2 ⎯⎯→

Ni
CnH2n
300o C
Reaction with – Addition Addition

conc. H2SO4 and C2H4+H2SO4 → C2H5HSO4 C2H2→ CH3CH(HSO4)2 ⎯⎯⎯
H 2O
→
hydrolysis H O
⎯⎯⎯
2
→ C2H5OH CH3CHO
Br2/CCl4 – Decolourises Decolourises

Dibromo derivatives, Tetrabromo derivatives,
C2H4 + Br2 → C2H4Br2 C2H2Br4
Baeyer’s reagent – Decolourises Decolourises

(Alk. KMnO4) Glycol is formed Oxalic acid is formed
CH 2 CH 2OH CH COOH
|| + H 2O + O → | ||| + 4O → |
CH 2 CH 2OH CH COOH
Ammonical – – Red precipitate

Cu2Cl2 CH CCu
||| + Cu2Cl2 + 2 NH 4OH → |||
CH CCu
(Red)
+ 2NH4Cl + 2H2O
Ammonical silver – – White precipitate

nitrate CH C − Ag
||| + 2 AgNO3 + 2 NH 4OH → |||
CH C − Ag
(White)
+ NH4NO3 + 2H2O
Hydrocarbons | 107
Cycloalkanes
Preparation
From Dihalogen Compounds (Freund Reaction)

Freund reaction for the production of cycloalkane is useful in preparation of 3 to 6 membered ring. It is also known as
intramolecular wurtz reaction.
CH2Cl CH2
CH2 +2Na heat +2NaCl
CH2Cl H2C CH2
1,3 Dichloropropane Cyclopropane
From Alkenes
Zn− Cu alloy
CH 3 − CH = CH 2 + CH 2 I 2 ⎯⎯ ⎯⎯⎯→ CH 3 − CH − CH 2
Propene
CH 2
Methyl cyclopropane
From Aromatic Compounds
+ 3H2
Benzene Cyclohexane
From Calcium Salts of Dicarboxylic Acids

Clemmensen reduction of cycloketones results cycloalkanes
O
||
CH2CH2 C O− CH2CH2 CH2CH2
heat Zn / Hg
|
−
Ca2 + ⎯⎯ ⎯→| C = O ⎯⎯ ⎯ ⎯→| CH2
CH2CH2 C O − CaCO 3 CH CH
2 2
HCl CH2CH2
|| Cyclopentanone Cyclopentane
O
Calciumadipate
Dickmann Cyclisation
Esters of dicarboxylic acids undergo intramolecular claisen condensation in presence of sodium or sodium ethoxide yielding
cyclic -ketoesters.
COOC2H5 COOH
| |
CH2 CH CH
CH2 COOC2 H 5 CH2 heat CH
C2 H5ONa
| ⎯⎯ ⎯⎯ ⎯→ | C = O ⎯⎯⎯→ | 2 C=O
CH2 COOC2 H 5 − C2 H5OH
CH2 CH 2
CH2 CH2 CH 2
 − ketoester
Physical Properties
(1) First two members are gases, next three members are liquids and higher ones are solids.
(2) They are insoluble in water but soluble in alcohol and ether.
(3) Their boiling points show a gradual increase with increase of molecular mass. Their boiling points are higher than those of
isomeric alkenes or corresponding alkanes.
(4) Their density increases gradually with increase of molecular mass.
Chemical Properties
Cycloalkanes behave both like alkenes and alkanes in their chemical properties.
(1) All cycloalkanes undergo substitution reaction with halogen in the presence of light (like alkane).
Hydrocarbons | 108
(2) Lower members undergo addition reaction (e.g. Addition of H 2 , HX , X 2 ). Further the tendency of forming addition
compounds decreases with increase in size of ring Cyclopropane > Cyclobutane > Cyclopentane.
(3) Addition in Spiro Cycloalkane
If two cycloalkane fused with one another then addition take place in small ring, because small ring is more unstable than large
ring
+ H2
Spiro compound
Higher cycloalkanes do not give addition due to more stability.
Free Radical Substitution with Cl2

hv
CH2 − CH2 + Cl2 ⎯⎯→
⎯ CH2 − CH Cl + HCl
CH2 CH2
Cyclopropane Chlorocyclopropane
Addition Reactions
Br2
BrH2C – CH2 – CH2Br
(CCl4) dark 1, 3-Dibromopropane
HBr
H2C – CH2 CH3 – CH2 – CH2Br
1-Bromopropane
CH2
(i) Conc. H2SO4
Cyclopropane CH3 – CH2 – CH2OH
(ii) H2O 1-Propanol
H2, Ni CH3 – CH2 – CH3

80oC Propane
Oxidation
CH2
H2C CH2 CH2CH2COOH

+ 5[O]
H2C CH2 CH2CH2COOH
Adipic acid
CH2
Cyclohexane
Cycloalkene
Definition
Carbocyclic compounds with double bonds in the ring are called cycloalkenes. Some of the common cycloalkenes are
6
5 1
4 2
3
Cyclobutene Cyclopentene Cyclohexene 1, 4-Cyclohexadiene
Preparation
(1) Cycloalkenes can be easily obtained by Diels-Alder reaction.
(2) Cycloaddition: Diels – Alder reaction
Hydrocarbons | 109
CH2 CH2 CH 2
CH CH2 CH2 CH2 CH CH 2
200o C
| + || ⎯⎯ ⎯⎯→ | | ⎯⎯→ || |
CH CH2 or hv CH2 CH2 CH CH 2
CH2 CH2 CH 2
Cyclic transition state Cyclohexene
Chemical Properties
(1) These compounds undergo the electrophilic addition reactions which are characteristic of alkenes, while the ring remains intact.
(2) Cycloalkenes decolourise the purple colour of dilute cold KMnO4 or red colour of bromine in carbon tetrachloride.
+ Br2
Br
Cyclopentene
Br
1, 2-Dibromo
cyclopentane
KMnO4(aq.)
+O + H2O
OH
Cyclopent-1-ene
OH
Cyclopentane 1,2-diol
(3) Ozonolysis
CH2
O H2O
+ O3 O CH2 CHO
O
CHO
Cyclohexene CH2
CH2
Dienes
These are hydrocarbon with two carbon-carbon double bonds.
Types
Dienes are of three types.

Conjugated dienes : Double bonds are separated by one single bond.
Ex : CH 2 = CH − CH = CH 2 (1, 3-butadiene)
Cumulative dienes : Double bonds are adjacent to each other.
Ex : CH 2 = C = CH 2 Propadiene [allene]
Isolated or Non-conjugated : Double bonds are separated by more than one single bond.
Ex : CH 2 = CH − CH 2 − CH = CH 2 (1, 4 pentadiene)
(4) The general formula is Cn H 2n− 2 . The predominant member of this class is 1, 3-butadiene.
Preparation of 1, 3-butadiene
(1) From Acetylene

Cu2Cl 2 H2
2HC  CH ⎯⎯ ⎯→ CH2 = CH − CH = CH2
⎯⎯→ HC  C − CH = CH 2 ⎯⎯
NH 4 Cl Vinyl acetylene Pd / BaSO 4 1, 3-Butadiene
Hydrocarbons | 110
(2) From 1, 4-dichlorobutane
Cl Cl
| |
Alc. KOH
CH 2 CH 2 CH 2 CH 2 ⎯⎯ ⎯⎯ ⎯→ CH 2 = CH − CH = CH 2
1,4-Dichlorobutane 1, 3-Butadiene
(3) From 1,4-butanediol
OH OH
| |
H 2SO4
CH 2 CH 2 CH 2 CH 2 ⎯⎯ ⎯⎯→ CH 2 = CH − CH = CH 2
1, 4 -Butanediol heat 1, 3-Butadiene
(4) From butane

Catalyst
CH3 CH 2 CH 2 CH3 ⎯⎯ ⎯ o
⎯→ CH 2 = CH − CH = CH 2 (Cr2O3 used as catalyst on an alumina support)
n-Butane 600 C 1, 3-Butadiene
(5) From cyclohexene
→ CH2 = CH − CH = CH2 + CH2 = CH2

1, 3-Butadiene Ethene
Chemical Properties of 1, 3-butadiene
Addition of Halogens
CH2BrCHBrCH=CH2
3,4-Dibromo-1-butene (1, 2-Addition)
predominates (62%) in non-ionising solvent
CH2 = CHCH = CH2 + Br2 (hexane)
CCl4
1, 3-Butadiene
CH2BrCH=CH.CH2Br
1,4-Dibromo-2-butene (1, 4-Addition)
predominates (70%) in an ionising solvent
(acetic acid)
Addition of Halogen Acids
CH3CHBrCH=CH2
(1, 2-Addition)
3-Bromo-1-butene
CH2 =CH–CH=CH2 +HBr
(Major yield at low temp.)
[Buta 1, 3-diene]
CH3–CH=CH–CH2Br
(1, 4-Addition)
1-Bromo-2-butene
(Major yield at high temp.)
Addition of Water
CH3CHOHCH=CH2
But-3-en-2-ol
CH2 =CH–CH=CH2 +H2O
[Buta 1, 3-diene]
CH3CH=CHCH2OH
But –2-en-1-ol
Polymerisation
Peroxide
nCH2 = CHCH = CH2 ⎯⎯ ⎯⎯→[− CH2 CH = CHCH2 −]n
1, 3-Butadiene Buna rubber
Hydrocarbons | 111
Diels-alder reaction
CH2 CH2
H–C CH2 HC CH2

+
H–C CH2 HC CH2
CH2 Ethene CH2
(Dienophile) Cyclohexene
1, 3-Butadiene
(Adduct)
Ozonolysis
CH 2 = CHCH = CH 2 + 2O3 ⎯⎯⎯⎯ → 2HCHO + OHC − CHO

2 Zn / H O
O3
H2O
CH2–O–CH – CH–O–CH2
O O O O
(Diozonide)
Stability of Conjugated Dienes
It is explained on the basis of delocalisation of electron cloud between carbon atoms.
The four  electrons of 1, 3-butadiene are delocalised over all the four atoms. This delocalisation of the  electrons makes the
molecule more stable.
Partial Double Bond Character
H H
C C C C
H H
C C C C–
Delocalised
 -electrons
Aromatic Hydrocarbon or Arenes
Definition
Hydrocarbons and their alkyl, alkenyl and alkynyl derivatives which contain one or more benzene rings are called aromatic
hydrocarbons or arenes (aromatic alkenes).
All arenes have general formula [Cn H2n−6 y ] . Where y is number of benzene rings and n is not less than 6.
Source of Arenes
Sources of arenes are coal and petroleum. It contains benzene, xylene, naphthalene etc. Arenes are obtained by destructive
distillation of coal.
Distillation of Coal
Coal tar is a mixture of large numbers of arenes.
Hydrocarbons | 112
COAL
Heated to 1273-1373 K
(Destructive distillation)
COKE HOT VAPOURS AND GASES

(Solid residue nearly 70%).
It is used as a fuel and as Cooled and
reducing agent in metallurgy. passed through
water
CONDENSED COAL GAS

LIQUID (Mixture of uncondensed gases
nearly 17%).
Allowed to settle, It is used as a fuel.
two layers are
separated
Upper layer Lower layer
AMMONICAL LIQUOR COAL TAR

(nearly 8-10%) (nearly 4-5%)
It is used for the preparation of Black, viscous liquid having
(NH4)2SO4 to be used as a unpleasant odour
fertilizer.
Distillation of Coal Tar
Arenes are isolated by fractional distillation of coal tar,
Table : 15.4 Fractions of Coal Tar
Name of the fraction Temperature range (K) Main constituents

Light oil (or crude oil) fraction Upto 443 Benzene, toluene, xylene etc
Middle oil fraction (Carbolic oil) 443-503 Phenol, naphthalene, pyridine
Heavy oil fraction (Creosote oil) 503-543 Naphthalene, naphthol and cresol
Green oil (Anthracene oil) 543-633 Anthracene, phenanthracene
Pitch (left as residue) Non-volatile Carbon
Isolation of Benzene
distillation
cold H2SO4
Light oil ⎯⎯ ⎯→ Phenols removed ⎯⎯⎯⎯
NaOH
⎯⎯⎯→ Basic impurities removed ⎯⎯ ⎯ ⎯→ Benzene (255 - 257K)
[Like pyridine] [Acidic impurities] Toluene (383 K)
Aromaticity or aromatic character
Aromatic compound undergo substitution rather than addition reactions, this characteristic behaviour of aromatic compounds is
called aromaticity. Aromaticity is due to extensive delocalisation of -electrons in planar ring system. Huckel (1931) explained
aromaticity on the basis of following rule.
Huckel Rule
For aromaticity, the molecule must be planar, cyclic system having delocalised (4 n + 2) electrons where n is an integer equal
to 0, 1, 2, 3,------ and possesses unusual stability due to complete delocalisation.
Thus, the aromatic compounds have delocalised electron cloud of 2,6,10 or 14  electrons.
Hydrocarbons | 113
• Examples of Aromatic Compounds
4
4n + 2 = 6 ; 4n = 4 ; n = =1
4
Benzene 6 electrons
n=1
Naphthalene 10 electrons Anthracene 14 electrons

n=2 n=3
Similarly, cyclolpentadienyl anion or tropylium ion are also aromatic because of containing 6  electrons (n=1).
H H H
H H 
.. 
H
H H H

H H
H
Cyclopentadienyl anion 6 Tropylium ion 6  electrons Cyclopropenyl cation
electrons (n=1) (n=1) (n = 0)
• Examples of Non-aromatic Compounds
Molecules do not satisfy huckel rule are not aromatic.
H ..
H 
Cyclopentadiene Cyclopentadienyl cation
4 electrons 4 electrons Cyclooctatetraene Cyclopropenyl anion
8 electrons 4 electrons
• Aromaticity of Heterocyclic compounds
Following heterocyclic compounds also have 6 electrons (n = 1).
..
.. ..
N O S N
H Pyridine
Furan Thiophene
Pyrrole
Antiaromaticity
• Planar cyclic conjugated species, less stable than the corresponding acyclic unsaturated species are called antiaromatic.
• Molecular orbital calculations have shown that such compounds have 4n electrons. In fact such cyclic compounds
which have 4n electrons are called antiaromatic compounds and this characteristic is called antiaromaticity.
• Example: 1,3-Cyclobutadiene.
It is extremely unstable antiaromatic compound because it has 4n electrons (n = 1) and it is less stable than 1,3 butadiene
by about 83.6 kJ mol–1.
4
4n = 4 ; n = =1
4
Hydrocarbons | 114
• Other Examples
 

Cyclopropenyl anion Cycloheptatrienyl anion Cycloctatetraene

4 electrons Cyclopentadienyl 8 electrons 8 electrons
4 electrons
Benzene (C6H6)
Benzene is the first member of arenes. Hofmann (1845) obtained it from coal tar, which is still a commercial source of benzene.
Structure of Benzene
Benzene has a special structure, which is although unsaturated, behaves as a saturated compound.
Kekule's Structure
According to Kekule, in benzene, 6-carbon atoms placed at corner of hexagon and bonded with hydrogen and double bonds
are present at alternate position.
• Evidences in Favour of Kekule's Structure
Benzene combines with 3 molecules of hydrogen or three molecules of chlorine. It also combines with 3 molecules of ozone
to form triozonide. These reactions confirm the presence of three double bonds.
Cyclohexane
Studies on magnetic rotation and molecular refraction show the presence of three double bonds and a closed conjugated
system.
The synthesis of benzene from three molecule of acetylene also favours Kekule's structure.
• Objections against Kekule's Formula
a) C − C bond length in benzene are equal, (although it contains 3 double bonds and 3 single bonds) and are 1.39 Å.
b) Unusual stability of benzene towards strong oxidizing agents and undergoes substitution reactions even though it
contains 3 double bonds.
c) According to Kekule, two ortho disubstituted products are possible. In one of

the structure there is a double bond between the two carbon atoms carrying
bromine atoms, but in other structure there is a single bond. If Kekule structures
were correct, both these isomers should exist and should have different
properties.
But in practice only one o-dibromobenzene is known. To account for this, Kekule proposed a dynamic equilibrium between
the two structures.
Hydrocarbons | 115
Some other Structures of Benzene
Ladenberg’s prism Claus-diagonal Dewar’s parallel Armstrong and Baeyer’s

Formula formula formula centric formula
These structures were rejected due to asymmetry or non-planar structure. Also these could not explain the reduction and
addition products.
Modern Theory for Benzene Structure
Modern theory proposed that double bonds in benzene ring were continuously oscillating between two adjacent positions. In
the resonance structure all π- electrons are delocalized.
The resonance structure was further supported by the fact that, heat of hydrogenation of benzene is 49.8 kcal/mole, whereas
theoretical value of heat of hydrogenation of benzene is 85.8 kcal/mole. It means resonance energy is 36 kcal/mole.
• Summary of Benzene Structure
a) Benzene has a cyclic, planar hexagonal structure.
b) All the six carbon atoms in benzene are equally reactive and so, all the hydrogen atoms in benzene are equivalent.
c) All carbon atom in benzene are sp 2 -hybridized.

d) All carbon-carbon bond lengths in benzene are equal (139 pm), all carbon-hydrogen bond lengths are equal (110 pm)
and its dipole moment is zero.
Methods of Preparation of Benzene
Laboratory Method
COONa
+ NaOH CaO
heat + Na2CO3
Sodium benzoate Benzene
From Benzene Derivatives
• From Phenol
OH
distill + ZnO
+ Zn
(dust)
Benzene
Phenol
• From Chlorobenzene
Cl
Ni-Al alloy
+ 2H + HCl
NaOH
Chlorobenzene Benzene
Hydrocarbons | 116
• By First Preparing Grignard Reagent of Chlorobenzene and then Hydrolysed
Mg H 2O OH
C6 H 5 Cl ⎯⎯
⎯→ C6 H 5 MgCl ⎯⎯ ⎯→ C6 H 6 + Mg
Chlorobenzene dry ether Phenyl magnesium Benzene Cl
chloride
• From Benzene Sulphonic Acid
SO3H
150°-200°C
+ HOH +H2SO4
Steam
Benzene sulphonic acid HCl,pres Benzene
• From Benzene Diazonium Chloride
N2Cl
SnCl2
+ 2H +N2+HCl
NaOH
Benzene
• Aromatisation
Cr2O3 / Al2O3
C6 H14 ⎯⎯ ⎯⎯⎯ ⎯→ C6 H6 + 4 H 2
n − Hexane 500C Benzene
at high pressure
Physical Properties
(1) Benzene is a colourless and volatile liquid. Its boiling point is 80°C and freezing point is 5.5°C. It has characteristic odour.
(2) It is highly inflammable and burns with sooty flame.
(3) It is lighter than water. Its specific gravity at 20°C is 0.8788.
(4) It is immiscible with water but miscible with organic solvents such as alcohol and ether.
(5) Benzene itself is a good solvent. Fats, resins, rubber, etc. dissolve in it.
(6) It is an extremely poisonous substance. Inhalation of vapours or absorption through skin has a toxic effect.
Chemical Reactivity
Due to the presence of  electron clouds above and below the plane benzene ring, the ring serves as a source of electrons and is
easily attacked by electrophiles (Electron loving reagents). Hence electrophilic substitution reactions are the characteristic reactions
of aromatic compounds.
Substitution reactions in benzene are preferred rather than addition are due to the fact that in the former reactions resonance
stabilised benzene ring system is retained while the addition reactions lead to the destruction of benzene ring.
Chemical Reactions
Principal reactions of benzene can be studied under three heads:
Addition Reactions
In these reactions, benzene behaves like unsaturated hydrocarbons.
• Addition of Hydrogen
Benzene reacts with hydrogen in the presence of nickel (or platinum) as catalyst at 150°C under pressure to form
cyclohexane.
Ni
+ 3H2 or C6H12
150°C, pressure
Benzene Cyclohexane
Hydrocarbons | 117
Hydrogenation of substituted aromatic compounds :
CH3 R
Ni / liq. NH − C H OH
+ 2H 2 ⎯⎯⎯⎯⎯
3
⎯ ⎯⎯→
2 5
(Birch reduction)
Alkyl cyclohexene
• Addition of Halogen
Cl H
H
C C
H Cl
HC CH C C
hv Cl H
+ 3Cl2 H Cl
HC CH C C
Cl H
C
C
H
H Cl
Benzene
Hexachlorocyclohexane
• Addition of Ozone
O O
H
C O CH
HC CH O CHO
H C CH 3H2O
+3O3 → O 3 + 3H2O2
Zn
H C CH CHO
HC CH O Glyoxal
C O C
H
H O O
Benzene triozonide
Benzene
• Nucleophilic Substitution
a) Unimolecular: Mostly uncommon in aromatic substitution, there is only one example which is benzene diazonium
dichloride.
HOH ArOH
(Slow)
Ar − N 2+ ⎯⎯ ⎯⎯→ N 2 + Ar + (Fast) Phenol
X–
Arenediazonium
cation
ArX
Aryl halide
b) Bimolecular:
Y Z Y Z Y Z Y Z Y
Z Z
- - -
-. -  (Fast)
- - . or +Z 
Y attaches to the positively

Y + Y +

 
charged carbon atom (slow)

-
(Resonating structures of the
hexadienyl anion)
Example: Cl OH Cl OH
(Slow) (Fast)
OH +  + Cl 
Phenol
Hydrocarbons | 118
• Electrophilic Substitution
Mechanism
 H  H H H
E ; E E E
+ (Slow)
E
 
Carbonium ion
( - complex) Resonance forms of carbonium ion (Arenium ion)
H
 E
E
 (Fast) + H – Nu
+ Nu:
Substitution product
Table : 15.5 Different Electrophiles
Electrophile (E) Name Source Name of substitution reaction

Cl + Chloronium Cl2 + AlCl3 or FeCl3 Chlorination
Br + Bromonium Br2 + AlBr3 or FeBr3 Bromination
NO2+ Nitronium HNO3 + H 2 SO4 Nitration
SO3 Sulphur trioxide Conc. H 2 SO4 , Fuming sulphuric acid Sulphonation
R+ Alkyl carbonium RX + AlX3 (X = Cl or Br), ROH + H + Friedel-Craft's (Alkylation)

+ Acyl carbonium RCOCl + AlCl3 Friedel-Craft's (Acylation)
R −C =O
• Free Radical Aromatic Substitution
The aromatic substitution reactions which follow free radical mechanisms are very few and have limited synthetic value. But
some typical example of these reactions are:
 
(a) (CH 3 )3 COOC − (CH 3 )3 ⎯⎯⎯
heat
→ 2(CH 3 )3 CO ⎯⎯
→ 2CH 3 + 2CH 3 COCH 3
Methyl free radical Acetone
X X X X
. H
+ CH3 . CH3+ . + . H
CH3
(X = Cl, OCH3, NO2, CH3 etc.) H CH3
(ortho, para and meta derivatives)
X X
X
CH3 .
+ + + H
CH3
o m
CH3
p
(b) The mechanism of chlorination of benzene at high temperature is similar to that of the free radical aliphatic substitution
. .
Cl2 ⎯⎯→ Cl + Cl (Chain initiation)
. .
C6 H 6 + Cl ⎯⎯→ C6 H 5 + HCl (H- abstraction)
. .
C6 H 5 + Cl2 ⎯⎯→ C6 H 5 Cl + Cl (Chain propagation)
Hydrocarbons | 119
Oxidation Reactions
→12CO2 + 6H 2O ; H = 6530 kJ/mole

• 2C6 H6 + 15O2 ⎯⎯
• When vapours of benzene and air are passed over vanadium pentoxide at 450 – 500°C, maleic anhydride is obtained.
V2O5
CHCO
C6 H6 + 9[O] ⎯⎯ ⎯→|| O+ 2CO2 + 2H 2O
450 − 500C CHCO
Maleicanhydride
• Strong oxidising agents converts benzene slowly into CO 2 and water on heating.
Reduction Reaction
CH3
2 +12HI + +6I2
Benzene Cyclohexane Methylcyclopentane
Uses
(1) In dry cleaning
(2) As a solvent
(3) In the manufacture of gammexane (As insecticide)
(4) In the preparation of nitrobenzene, chlorobenzene, benzene sulphonic acid, aniline, styrene, etc. Many of these are employed
for making dyes, drugs, plastics, insecticides, etc.
Directive Effect in Substituted Benzene Derivatives
Directive Effect in Mono-Substituted Benzene Derivatives
Activity Effect
The substituent already present can increase or decrease the rate of further substitution, i.e., it either activates or deactivates
the benzene ring towards further substitution. These effects are called activity effects.
Directive or the Orientation Effect
The substituent already present on the benzene ring directs the incoming substituent to occupy ortho (2 or 6), meta (3 or 5) or
para (4) position. This direction depends on the nature of the first substituent and is called directive or the orientation effect.
There are two types of substituents which produce directive effect:
• Those which direct the incoming group to ortho- and para-positions simultaneously (Neglecting meta all together).
• Those which direct the incoming group to meta-position only (Neglecting ortho- and para-positions all together).
Table 15.6 Directive Effect of Substituent
Ortho-para Directors Meta directors
.. .. .. .. ..– Moderately deactivating

Strongly activating − NH 2 , − NHR, − NR2 , – .OH,
. – .O:
.
−C  N , − SO3 H , −COOH , −COOR, −CHO, COR
.. .. .. .. Strongly deactivating − NO2 , − NR3 , −CF3 , −CCl3

Moderately activating − NHCOCH 3 , − NHCOR, . 3, – .OR
– .OCH .
Weakly activating −CH 3 , −C2 H 5 , − R, −C6 H 5

.. .. .. ..
Weakly deactivating – .F:. , – Cl:
. . , – Br:
. . , –. I. :
Hydrocarbons | 120
• Theory of Ortho–para Directing Group
S S S
:S :S
.. ..
,i.e.,

..
 S Ortho attack S S
Ortho
E
 
 

+ E +
 
Ortho product
E
Para attack Para product
CH3 CH3 CH3 CH3
.. ..
..
The above mechanism is followed when S is −OH , − NH 2 ,−Cl , − Br,− I ,−OR,− NR 2 ,− NHCOR etc.
In methyl or alkyl group, the +I effect of the methyl group or alkyl group initiates the resonance effect.
Thus, methyl or alkyl group directs all electrophiles to ortho and para positions.
• Theory of Meta Directing Group
The substituent, S withdraws electrons from ortho and para positions. Thus, m-position becomes a point of relatively high
electron density and further substitution by electrophile occurs at meta position. For example, − NO 2 group is a meta
directing (Electron withdrawing). Its mechanism can be explained as:
O 
 O O 
 O 
O 
 O 
O 
 O 
O 
 O 
N N N N N
 ..


All meta-directing groups have either a partial positive charge or a full positive charge on the atom directly attached to the
ring.
Directive Effect in Di-substituted Benzene
Case- 1: When the directive effects of two substituents reinforce each other
A single product will be formed.
Example :
CH3 CH3 CH3

NO2
; Nitration
+NO2
NO2 (m) NO2 NO2
Thus, both (CH 3 , NO 2 ) direct further substitution to the same position (Ortho with respect to CH3).
Hydrocarbons | 121
Case- 2: If the directing effect of two substituents oppose each other
Strongly activating groups win over deactivating or weakly activating group. The sequence of directing power is
− NH 2  −OH  −OCH 3 −  NHCOCH 3  −C6 H 5  CH 3  meta directors

Example :
OH OH OH OH OH
(Powerful
Directs activator)
Br
Br2
FeBr3
CH3 CH3 CH3 CH3 CH3

Directs Directs
Case- 3: When the two groups are meta to each other CH3
Too hindered position
There is normally little substitution when the two groups are meta to each other. Aromatic
rings with three adjacent substituents are generally prepared by some other routes.
Cl
Toluene
Toluene is the simplest homologue of benzene. It was first obtained by dry distillation of tolubalsam and hence named toluene. It is
commercially known as toluol.
Methods of Preparation
From Benzene [Friedel-craft's reaction]
CH3
AlCl3 + HCl
+CH3Cl
Benzene Toluene
• Alkyl Halide Employed May Undergo an Isomeric Change
AlCl CH3
C6 H 6 + ClCH2CH2CH3 ⎯⎯⎯
3
→ C6 H 5 CH + HCl
n − Propyl chloride CH3
Isopropyl benzene (65 − 70%)
(Cumene)
• The Reactivity of Catalysts which can be used in place of Anhydrous AlCl 3 are:
AlCl 3  SbCl 3  SnCl 4  BF3  ZnCl 2  HgCl 2
Wurtz Fittig Reaction
Ether
Br+2Na+BrCH3 CH3+2NaBr
Bromobenzene Methyl bromide Toluene
Decarboxylation
CH3 Soda lime

C6 H 4 + NaOH ⎯⎯ ⎯⎯ ⎯→ C6 H 5 CH3 + Na2CO3
COONa Toluene
(o-,m- or p-)
Sodium toluate
Hydrocarbons | 122
From Cresol
CH3
CH3
OH
heat
+Zn + ZnO
o-Cresol Toluene
From Toluene Sulphonic Acid
CH3 CH3
+HOH Boil +H2SO4

steam
SO3H Toluene
p-Toluene sulphonic acid
From Toluidine
CH3 CH3
CH3
NaNO2 C2H5OH
HCl
+N2+CH3CHO+HCl
NH2 N2Cl Toluene

p-Toluidine p-Toluene diazonium chloride
From Grignard Reagent
MgBr CH3
+CH3Br +MgBr2
Phenyl magnesium bromide Toluene
Commercial Preparation
The main source of commercial production of toluene is the light oil fraction of coal-tar.
From n- Heptane and Methyl Cyclohexane
CH3
|
CH2
CH3
H2C CH3
Cr2O3 / Al2O3
500-550°C
H2C CH2 150 atms
Toluene
CH2
n-Heptane
Physical Properties
It is a colourless liquid having characteristic aromatic odour.
It is lighter than water (sp. gr. 0.867 at 20°C).
It is insoluble in water but miscible with alcohol and ether in all proportions.
Its vapours are inflammable. It boils at 110°C and freezes at –96°C.
It is a good solvent for many organic compounds.
It is a weak polar compound having dipole moment 0.4D.
Chemical Properties
Toluene shows the behaviour of both an aliphatic and an aromatic compound.
Hydrocarbons | 123
CH3
Side chain (Aliphatic)
Benzene ring (Aromatic)
Electrophilic Substitution Reactions
Aromatic character (more reactive than benzene) due to electron releasing nature of methyl group.
CH3 CH3 CH3

E

+ E +
Electrophile + + +
E+ may be Cl, NO2 , SO3 H etc.
o-Derivative
E
p-Derivative
Reactions of Side Chain
• Side Chain Halogenation
CH3 CH2Cl CHCl2 CCl3

Cl2
Cl2 Cl2
UV
UV UV
Toluene Benzyl chloride Benzal chloride Benzo trichloride
• Benzyl Chloride on Hydrolysis with Aqueous Caustic Soda Forms Benzyl Alcohol.
C6 H5CH2Cl + NaOH ⎯⎯→ C6 H5CH2OH + NaCl

(Benzyl chloride)
• Benzal Chloride on Hydrolysis Forms Benzaldehyde.
C6 H5CHCl2 + 2 NaOH ⎯⎯→ C6 H5CH(OH)2 + 2 NaCl

(Benzal chloride) 
C6 H5CHO+ H2O
• Benzotrichloride on Hydrolysis Forms Benzoic Acid.
C6 H5 CCl3 + 3 NaOH ⎯⎯→ C6 H5 C(OH)3 + 3 NaCl

(Benzotrichloride) 
C6 H5 COOH + H 2O
Oxidation
• With hot Acidic KMnO4
CH3 COOH
KMnO4 / H+
+ H2O
3[O]
Toluene Benzoic acid
• With Acidic Manganese Dioxide or Chromyl Chloride (Etards Reaction)
CH3 CHO
CrO2Cl2
+ 2[O] +H2O
Toluene Benzaldehyde
Hydrocarbons | 124
• All alkyl benzenes on oxidation with hot acidic KMnO4 or Na 2Cr2O7 form benzoic acid. The length of the side chain
does not matter.
Hydrogenation
R R
+ 2H2 Na / liquid NH3 – C2H5OH

(Birch reduction)
Alkyl benzene Alkyl cyclohexene
Combustion
C6 H5CH3 + 9O2 ⎯⎯→7CO2 + 4 H2O
Ozonolysis
O O
H
C O CH CH3 –C=O CHO
CH3C CH O +2 + 3H2O2
CH3 C CH Zn
+3O3 → O H – C=O CHO
H HOH
C CH Methyl glyoxal Glyoxal
HC CH O
C O C
H
H O O
Triozonide
Toluene
Uses
(1) In the manufacture of benzyl chloride, benzal chloride, benzyl alcohol, benzaldehyde, benzoic acid, saccharin, etc.
(2) In the manufacture of trinitrotoluene (TNT), a highly explosive substance.
(3) As an industrial solvent and in drycleaning.
(4) As a petrol substitute.
(5) In the manufacture of certain dyes and drugs.
T.N.T. (Tri-Nitro Toluene)
Preparation
CH3
CH3
O2N NO2
H2SO4 + 3H2O
+ 3HNO3
Fuming
Toluene NO2
Properties
It is pale yellow crystalline solid (M.P. = 81°C).
Uses
(1) It is used as an explosive in shells, bombs and torpedoes under the name trotyl.
(2) When mixed with 80% ammonium nitrate it forms the explosive amatol.
(3) TNT is also used with a mixture of aluminium nitrate, alumina and charcoal under the name ammonal.
Hydrocarbons | 125
T.N.B. (Tri-Nitro Benzene)
Preparation
CH3 CH3 COOH

O2N NO2 O2N NO2
O2N NO2
H2SO4 K2Cr2O7 Soda
HNO3 H2SO4 lime
Toluene NO2 NO2

NO2
T.N.B.
Properties and Uses
It is colourless solid (M.P. = 122°C). It is more explosive than T.N.T. and used for making explosive.
Xylenes (Dimethyl Benzene)
The molecular formula, C8 H 10 represents four isomers.

CH3 CH3 CH3 C2H5
CH3
CH3
o-Xylene m-Xylene CH3 Ethyl benzene
p-Xylene
Preparation
These are produced along with benzene, toluene and ethylbenzene when aromatisation of C 6 − C 8 fraction of petroleum naphtha
is done. The xylenes are isolated from the resulting mixture by fractional distillation.
Wurtz–Fittig Reaction
A mixture of bromotoluene and methylbromide is treated with sodium in dry ethereal solution to form the desired xylene.
CH3
CH3
Br
CH3
+ 2Na + BrCH3 + 2NaBr
o-Bromotoluene
o-Xylene
CH3 CH3
Br CH3
m-Bromotoluene m-Xylene
CH3 CH3
Br CH3
p-Bromotoluene p-Xylene
(2) These can also be obtained by Friedel – Craft's synthesis.
(3) m-Xylene can be obtained from mesitylene.
Hydrocarbons | 126
Physical Properties
(1) Xylenes are colourless liquids having characteristic odour.
(2) The boiling points of three isomers are: o-Xylene=144°C; m-Xylene=139°C; p-Xylene=138°C.
Chemical Properties
Xylenes undergo electrophilic substitution reactions in the same manner as toluene. Upon oxidation with KMnO 4 or K 2 Cr 2 O7 ,
Xylenes form corresponding dicarboxylic acids.
COOH COOH
COOH
, ,
COOH COOH
Phthalic acid Isophthalic acid
COOH
Terephthalic acid
Uses
(1) Xylenes are used in the manufacture of lacquers and as solvent for rubber.
(2) o-Xylene is used for the manufacture of phthalic nhydride.
Ethyl Benzene (C6H5C2H5)
Preparation
By Wurtz-Fittig Reaction
C6 H 5 Br + 2Na + BrC2 H 5 ⎯⎯→ C6 H 5 C2 H 5 + 2NaBr
By Friedel-Craft's Reaction
AlCl3
C6 H 5 H + BrC2 H 5 ⎯⎯ ⎯⎯→ C6 H 5 C2 H 5 + HBr
By Catalytic Reduction of Styrene
Ni
C6 H5CH = CH2 + H 2 ⎯⎯→
⎯ C6 H5CH2CH3
20 o , 3atm
By Alkyl Benzene Synthesis
AlCl3 , HCl
C6 H 5 H + H 2 C = CH2 ⎯⎯ ⎯⎯ ⎯→ C6 H 5 CH2 CH3
95C,Pressure
Chemical Properties
(1) It undergoes electrophilic substitution reactions in the same way as toluene.
(2) When oxidised with dil. HNO 3 or alkaline KMnO 4 or chromic acid it forms benzoic acid.
[O]
C6 H 5 C2 H 5 ⎯⎯⎯→ C6 H 5 COOH
Styrene (C6H5CH=CH2)
It is present in storax balsam and coal-tar in traces.
Hydrocarbons | 127
Preparation
Dehydrogenation of Side Chain of Ethylbenzene
CH2CH3 CH = CH2
AlCl3 600°C
+ CH2 = CH2 Cr2O3 / Al2O3
Benzene Ethylbenzene Styrene
Decarboxylation of Cinnamic Acid
This is the laboratory preparation and involves heating of cinnamic acid with a small amount of quinol.
Quinol
C6 H 5 CH = CHCOOH ⎯⎯ ⎯ ⎯→ C6 H 5 CH = CH2 + CO2
Dehydration of 1-phenyl Ethanol with H2SO4

H2SO4
C6 H 5 CHOHCH3 ⎯⎯ ⎯⎯→ C6 H 5 CH = CH2
− H2O
Dehydration of 2-phenyl Ethanol with ZnCl2

ZnCl2 , heat
C6 H 5 CH2 CH2 OH ⎯⎯ ⎯⎯⎯→ C6 H 5 CH = CH2
− H2O
Dehydrohalogenation of 1-phenyl-1-chloro Ethane
On heating with alcoholic potassium hydroxide, a molecule of hydrogen chloride is eliminated by the chloroderivative.
Alc.KOH
C6 H5 CHClCH3 ⎯⎯ ⎯⎯→ C6 H5 CH = CH2
Heat
Physical Properties
(1) It is a colourless liquid, boiling point 145°C.
(2) On keeping, it gradually changes into a solid polymer called metastyrene. The polymerisation is rapid in sunlight or when
treated with sodium.
Chemical Reactivity
It shows properties of benzene ring (Electrophilic substitution) and unsaturated side chain (Electrophilic addition). However, the
side chain double bond is more susceptible to electrophilic attack as compared to benzene ring.
Chemical Properties
At lower temperature and pressure, it reacts with hydrogen to produce ethylbenzene and at higher temperature and pressure,
it is converted into ethyl cyclohexane.
CH = CH2 CH2CH3 CH2CH3
H2 / Ni H2 / Ni
20°C, 3 atm 125°C, 110 atm
Styrene Ethyl benzene Ethyl cyclohexane
With Bromine, it gives the Dibromide.
CH = CH2 CHBr.CH2Br
+ Br2
Styrene Styrene dibromide
Halogen Acids Add to the Side Chain.
C6 H 5 CH = CH2 + HX ⎯⎯→ C6 H 5 CHXCH3
Hydrocarbons | 128
Preparation of Ring Substituted Styrenes is not done by direct halogenation but through indirect route.
CH2CH3 CH2CH3
CHClCH3 CH = CH2
FeCl3 Cl2
+ Cl2 Alc.. KOH
hv
Heat
Cl Cl Cl
When oxidised under drastic conditions, the side chain is completely oxidised to a carboxyl group.
CH = CH2 COOH
[O]
KMnO4
Styrene Benzoic acid
In presence of peroxides, styrene undergoes free radical polymerisation resulting in the formation of
polystyrene – an industrially important plastic.
 
 
Peroxide
nC6 H 5 CH = CH 2 ⎯⎯ ⎯⎯→ − CH − CH 2 −
 | 
 C6 H5 
 n
Bi-phenyl (C6H5 – C6H5)
It occurs in coal-tar. It is the simplest example of an aromatic hydrocarbon in which two benzene rings are directly linked to each other.
Preparation
Fittig Reaction
It consists heating of an ethereal solution of bromobenzene with metallic sodium.
Br +2Na + Br + 2NaBr
Ullmann Biaryl Synthesis
Iodobenzene, on heating with copper in a sealed tube, forms biphenyl. The reaction is facilitated if a strong electron withdrawing
group is present in ortho or para position.
I+ 2Cu + I + 2CuI
Grignard Reaction
Phenyl magnesium bromide reacts with bromo benzene in presence of CoCl 2 .
CoCl2
MgBr + Br + MgBr2
Physical Properties
It is a colourless solid, melting point 71°C.
Chemical Reactivity
It undergoes usual electrophilic substitution reactions.
Since aryl groups are electron withdrawing, they should have deactivating and m-orientating effect. But, it has been experimentally
shown that presence of one benzene ring activates the other for electrophilic substitution and directs the incoming group to o- and
p- positions.
Hydrocarbons | 129
It has been shown that mono-substitution in the bi-phenyl results in the formation of para isomer as the major product.
Another special feature of the biphenyl is the behaviour towards second substitution in a monosubstituted biphenyl. The second
substituent invariably enters the unsubstituted ring in the ortho and para position no matter what is the nature of substituent already
present.
HNO3 / H2SO4
NO2 HNO3 / H2SO4
O2N NO2
Polynuclear Aromatic Hydrocarbons- Carcinogenicity and Toxicity
Hydrocarbons containing two or more fused or isolated benzene rings are called polynuclear aromatic hydrocarbons.
Naphthalene Anthracene
Pyrene
Most of the polynuclear aromatic hydrocarbons (PNH) are cancer-producing, i.e., carcinogenic. Notable among these are 1,2-
benzanthracene, 20-methylcholanthrene, 1, 2-benzpyrene,
It is believed that when these polynuclear hydrocarbons enter to the body of a human being, they are first converted into their oxides
called epoxides and then into dihydroxy epoxides. The dihydroxy epoxides thus produced react with purine bases present in DNA and
RNA of human cell.
O2 DNA or RNA
PNH ⎯⎯
⎯→ PNH epoxide ⎯⎯→ PNH dihydroxy epoxide ⎯⎯ ⎯ ⎯ ⎯→ Mutations ⎯⎯→ cancer.
Hydrocarbons | 130
15. Hydrocarbons – Multiple Choice Questions
10. Which of the following is obtained at lowest temperature by
Alkane
fractional distillation of petroleum
1. Which of the following has highest octane number (a) Kerosene (b) Diesel oil
(a) n-hexane (b) n-heptane (c) Gasoline (d) Heavy oil
(c) n-pentane (d) 2, 2, 4-trimethyl pentane 11. The poisonous gas that comes out with petrol burning in a car
is
2. The chemical added to leaded petrol to prevent the deposition
of lead in the combustion chamber is (a) CH4 (b) C2H6
(a) Iso-octane (b) Ethylene dibromide (c) CO2 (d) CO
(c) Tetraethyl lead (d) Mercaptan 12. The marsh gas detector used by miners works on the principle
(e) n-heptane of
3. Petroleum consists mainly of (a) Difference in the rates of diffusion of gases

(b) Avogadro's hypothesis
(a) Aliphatic hydrocarbons (b) Aromatic hydrocarbons
(c) Gay-Lussac's law of gaseous volumes
(c) Aliphatic alcohols (d) None of these
(d) Berzelius hypothesis
4. Tetraethyl lead is used as
13. The purest form of coal is
(a) Fire extinguisher (b) Pain reliever
(a) Peat (b) Anthracite
(c) Petroleum additive (d) Mosquito repellent (c) Bituminous (d) Lignite
5. LPG is a mixture of 14. The most volatile compound is
(a) 2, 2-dimethyl propane (b) 2-methyl butane
(a) C6 H12 + C6 H6 (b) C4 H10 + C3H8
(c) Isobutane (d) n-pentane
(c) C2H4 + C2H2 (d) C2H4 + CH4 15. In Wurtz reaction, the reagent used is
6. In the process of cracking (a) Na (b) Na liquid NH 3
(a) Organic compounds decompose into their constituent (c) Na/dry ether (d) Na dry alcohol
elements
16. In catalytic reduction of hydrocarbons which catalyst is mostly
(b) Hydrocarbons decompose into carbon and hydrogen used
(c) High molecular weight organic compounds decompose to (a) Pt / Ni (b) Pd

give low molecular weight organic compounds (c) SiO 2 (d) Misch metal
(d) Hydrocarbons yield alkyl radicals and hydrogen 17. Which of the following does not give alkane
7. Octane number has 0 value for
(a) Reaction of CH 3 I with Na in ether
(a) Iso-octane (b) n-hexane
(b) Reaction of sodium acetate with sodalime
(c) n-heptane (d) Iso-heptane
(c) Electrolysis of concentrated sodium acetate solution
8. Natural gas is a mixture of
(d) Reaction of ethyl chloride with alco. KOH
(a) CO + CO2 (b) CO + N2
18. The reagent used in Wolff-Kishner reduction is
(c) CO + H2 + CH4 (d) CH4 + C2H6 + C3H8
(a) NH 2 − NH 2 and KOH in ethylene glycol
9. Gasoline has composition
(b) Zn − Hg / conc. HCl
(a) C8 − C12 (b) C2 − C5
(c) NaBH4
(c) C6 − C8 (d) None of these
(d) Na − Hg / H 2 O
Hydrocarbons | 131
19. To prepare a pure sample of n-hexane using sodium metal as 26. Propane cannot be prepared from which reaction
one reactant, the other reactant will be
B H
(a) CH3 − CH = CH2 ⎯⎯⎯→
2 6
(a) n-propyl bromide OH −
HI
(b) Ethyl bromide and n-butyl bromide (b) CH3CH2CH2I ⎯⎯ ⎯→
P
(c) Ethyl chloride and n-butyl chloride

Na
(c) CH3CH2CH2Cl ⎯⎯⎯
→
(d) Methyl bromide and n -pentyl chloride
(d) None of these
20. Which of the following reactions will not give propane
27. The best method for the preparation of 2,2-dimethylbutane is
Mg /ether
(a) CH3CH2CH2Cl ⎯⎯⎯⎯→ via the reaction of
H2O
CH MgX
(a) Me 3 CBr and MeCH 2 Br in Na/ether
(b) CH3COCl ⎯⎯⎯⎯→
3
H2O
(b) (Me 3 C)2 CuLi and MeCH 2 Br
B2 H6
(c) CH3CH = CH2 ⎯⎯⎯→
CH3 COOH (c) (MeCH 2 )2 CuLi and Me 3 CBr
P / HI (d) Me 3 CMgl and MeCH 2l

(d) CH3CH − CH3 ⎯⎯⎯→
|
OH 28. The decreasing order of boiling points is
21. A reaction between methyl magnesium bromide and ethyl (a) n-pentane > iso-pentane > neo-pentane
alcohol gives
(b) Iso-pentane > n-pentane > neo-pentane
(a) Methane (b) Ethane
(c) Neo-pentane > iso-pentane > n-pentane
(c) Propane (d) Butane
(d) n-pentane > neo-pentane > iso-pentane
22. Methane and ethane both can be obtained in a single step
29. Halogenation of alkanes is an example of
from
(a) Electrophilic substitution
(a) CH3I (b) C2H5 I
(b) Nucleophilic substitution
(c) CH3OH (d) C2H5OH (c) Free-radical substitution
23. Propionic acid is subjected to reduction with hydroiodic acid (d) Oxidation
in the presence of a little P, the product formed is
30. Carbon black, which is used in making printer's ink, is
(a) Ethane (b) Propane obtained by decomposition of
(c) Butane (d) None of these (a) Acetylene (b) Benzene
24. In which case butane is formed (c) Carbon tetrachloride (d) Methane
(a) 2C2H5 − Cl + Na 31. In the dichlorination reaction of propane, mixture of products

are obtained. How many isomers, the mixture contains
(b) C2H5COOH + Na2CO3 (a) 2 (b) 3
(c) CH2 = CH − CH3 + H2SO4 (c) 4 (d) 5
32. Which hydrocarbon will be most stable

(d) None of these
(a) Methane (b) Ethane
25. Grignard reagent is not prepared in aqueous medium but
prepared in ether medium because the reagent (c) Propane (d) Butane
(a) Reacts with water 33. n-pentane and isopentane can be distinguished by
(b) Is insoluble in water
(a) Br2 (b) O3
(c) Is highly reactive in ether
(c) Conc. H2SO4 (d) KMnO4
(d) Becomes inactive in water
Hydrocarbons | 132
34. Arrange the following in decreasing order of their boiling 40. Dry distillation of sodium propanoate with sodalime gives
points
(a) Propane (b) Propene
A. n-butane (c) Ethane (d) Ethene
B. 2-methylbutane 41. The major product of the reaction of 2 – butene with alkaline
C. n-pentane KMnO 4 solution is
D. 2, 2-dimethylpropane
(a) (b)
(a) A  B  C  D (b) B  C  D  A OH
O
(c) D  C  B  A (d) C  B  D  A
35. The correct IUPAC name of the following alkane is

O OH
H 3 C − CH2 − CH − CH2 − CH2 − CH − CH2 − CH3
| | (c) (d)
CH CH2 OH
|
CH3
42. Which of the following hydride is capable of showing
(a) 3, 6-diethyl-2-methyloctane conformations
(b) 5-isopropyl -3-ethyloctane (a) NH2 − NH2 (b) B2H6
(c) 3-ethyl-5-isopropyloctane (c) CH4 (d) None of these

(d) 3-isopropyl-6-ethyloctane 43. Which are the staggered forms of ethane
36. Arrange the following alkyl halides in decreasing order of the
rate of  − elimination reaction with alcoholic KOH H H
HH
H C
H
|
A. CH3 − C − CH2 Br B. CH 3 − CH 2 − Br H H C H
| H H
CH3 1 H H 2
C. CH 3 − CH 2 − CH 2 − Br
H
H
(a) A  B  C (b) C  B  A
H H C H H
(c) B  C  A (d) A  C  B H
C H H
37. Which of the following reactions of methane is incomplete 3 4 H
H H
combustion
Cu /523 K /100atm
(a) 2CH4 + O2 ⎯⎯⎯⎯⎯⎯⎯
→ 2CH3OH (a) 1 and 4 (b) 3 and 4
Mo O (c) 2 and 4 (d) 1 and 3

(b) CH4 + O2 ⎯⎯⎯⎯
2 3
→ HCHO + H2O
44. Which statement is true for cyclohexane
(c) CH4 + O2 ⎯⎯→ C(s) + 2H2O(l)
(a) It has two possible isomers
(d) CH2 + 2O2 ⎯⎯→ CO2(g) + 2H2O(l) (b) It has three conformations
38. Water gas is (c) Boat conformation is most stable
(d) Chair and boat conformations differ in energy by 30

(a) CO + CO2 (b) CO + N2
kJ/mol
(c) CO + H2 (d) CO + N2 + H2 45. The aromatic carbocation among the following is
39. Producer gas is a mixture of

(a) (b)
(a) CO and N2 (b) CO2 and H 2
(c) N 2 and O2 (d) CH4 and N 2 (c) (d)
Hydrocarbons | 133
46. Among 51. In the following, the most stable conformation of n − butane
is
H
N O CH3 CH3
H
N H CH3
H
(i) (ii) (iii) (iv) (a) (b) H
H H3C H H
H
The compound which is not aromatic is
(a) (i) (b) (ii) CH3 CH3

CH3
(c) (iii) (d) (iv) H H
47. Among the following

(c) H (d) H
H H H
H
CH3
N 52. The correct statement regarding the comparison of staggered

O and eclipsed conformation of ethane, is
(I) (II) (III) (IV) (V)
(a) The staggered conformation of ethane is less stable than
The antiaromatic compounds are eclipsed conformation, because staggered conformation
(a) (I) and (IV) (b) (III) and (V) has torsional strain
(b) The eclipsed conformation of ethane is more stable than

(c) (II) and (V) (d) (I) and (III)
staggered conformation, because eclipsed conformation
48. The most stable conformation of 2, 3 − dibromobutane is has no torsional strain
Br Br (c) The eclipsed conformation of ethane is more stable than

staggered conformation even through the eclipsed
H Br B
(a) (b)
r H conformation has torsional strain
H H H H (d) The staggered conformation of ethane is more stable than

H
H eclipsed conformation, because staggered conformation
has not torsional strain
Br Br
53. Given
H H H
(c) (d)
Br
Br
H H H CH3 H Br H Br
H
Br H H
49. Which one of the following conformation of cyclohexane is H CH3 CH3

Br CH3
chiral
(a) Twist boat (b) Rigid I II
(c) Chair (d) Boat I and II are
50. Increasing order of stability among the three main (a) Identical
conformation (i.e. Eclipse, Anti, Gauche) of 2-fluoroethanol is
(b) A pair of conformers
(a) Eclipse, Gauche, Anti (b) Gauche, Eclipse, Anti (c) A pair of geometrical isomers
(c) Eclipse, Anti, Gauche (d) Anti, Gauche, Eclipse (d) A pair of optical isomers
Hydrocarbons | 134
54. Which of the following conformers for ethylene glycol is most 4. Which of the following yield both alkane and alkene
stable
(a) Kolbe’s reaction (b) Williamson’s synthesis
OH OH
OH (c) Wurtz reaction (d) Sandmeyer reaction
H H
5. Cyclopentene on treatment with alkaline KMnO4 gives
H H
(a) H H (b) H (a) Cyclopentanol
H
OH (b) Trans 1, 2-cyclopentanediol

OH (c) Cis 1, 2-cyclopentanediol
OH
H H OH
(d) 1 : 1 mixture of cis and trans 1, 2-cyclopentanediol
(c) (d)
6. 2-chlorobutane is heated with alcoholic NaOH, the product
H H H H
H OH formed in larger amount is
H
(a) 1-butene (b) 1-butyne
55. The isomers which can be converted into another forms by
(c) 2-butene (d) All of these
rotation of the molecules around single bond are
(a) Geometrical isomers (b) Conformers 7. What is obtained, when propene is treated with N-bromo
succinimide
(c) Enantiomers (d) Diastereomers
(a) CH3 − C = CH2 (b) BrCH 2 − CH = CH 2
56. In the given conformation C2 is rotated about C2 − C3 bond |
anticlockwise by an angle of 120° then the conformation Br

obtained is
(c) BrCH 2 − CH = CHBr (d) BrCH2 − CH − CH2 Br
C4 |
CH3 Br
H H
C3 H 3C CH3 CH3 CH3
C2 X
H H 8. C=C ⎯⎯→ C =O+O=C
KOH (heat)
CH3 H 3C CH3 CH3 CH3
C1
(a) Fully eclipsed conformation X in the above reaction is

(b) Partially eclipsed conformation (a) HNO 3 (b) O 2
(c) Gauche conformation
(c) O 3 (d) KMnO 4
(d) Staggered conformation
9. How many gram of bromine will react with 21g C 3 H 6
Alkene
(a) 80 (b) 160
1. The final product formed when ethyl bromide is treated with
excess of alcoholic KOH is (c) 240 (d) 320
(a) Ethylene (b) Ethane 10. The molecular formula of Wilkinson catalyst, used in
hydrogenation of alkenes is
(c) Ethyne (d) Vinyl bromide
(a) Co (CO )8 (b) (Ph3 P )3 RhCl
2. When alcoholic solution of ethylene dibromide is heated with
granulated zinc, the compound formed is (c) [ Pt ( NH 3 )2 Cl 2 ] (d) K [ Ag (CN )2 ]
(a) Ethylene (b) Ethyne
11. Arrange the following hydrogen halides in order of their
(c) Cyclobutane (d) Butane
decreasing reactivity with propene
3. A reagent used to test for unsaturation of alkene is
(a) HCl  HBr  HI (b) HBr  HI  HCl
(a) Conc. H 2 SO 4 (b) Ammoniacal Cu 2 Cl 2
(c) Ammoniacal AgNO 3 (d) Solution of Br2 in CCl 4 (c) HI  HBr  HCl (d) HCl  HI  HBr
Hydrocarbons | 135
12. A hydrocarbon X adds on one mole of hydrogen to give 18. The product of following reaction is
another hydrocarbon and decolourises bromine water. X
CH3
reacts with KMnO 4 in presence of acid to give two moles of |
(i) Hg (OAc)2 ; H 2O
CH 3 − C − CH = CH 2 ⎯⎯ ⎯⎯⎯⎯⎯→
the same carboxylic acid. The structure of X is | (ii) NaBH4
CH3
(a) CH 2 = CH − CH 2 CH 2 CH 3 CH3
|
(a) CH3 − C − CH − CH3
(b) CH 3 CH 2 CH 2 − CH = CHCH 3 | |
CH3 OH
(c) CH 3 CH 2 CH = CHCH 2 CH 3 CH3
|
(b) CH 3 − C − CH 2 − CH 2 OH
(d) CH 3 CH = CHCH 2 CH 2 CH 3 |
CH3
13. Which of the following are formed on addition reaction of DCl OH CH3
| |
with 3-methyl-1-butene (c) CH 3 − C − CH − CH 3
|
(a) CH 2 DCHClCH (CH 3 )2 (b) CH 2 DCH 2 CCl (CH 3 ) 2 CH3

CH3
|
(c) CH 3 CDClCH (CH 3 ) 2 (d) ClCH 2 CHDCH (CH 3 ) 2 (d) HOCH2 − C − CH2 − CH2
|
14. The olefin which on ozonolysis gives CH 3 CH 2 CHO and

CH3
CH 3 CHO is 19. Position of double bond in an organic compound is

determined by
(a) 1-butene (b) 2-butene (a) Ozonolysis (b) Oxidation
(c) 1-pentene (d) 2-pentene (c) Reduction (d) Hydrogenation

20. The major products obtained during ozonolysis of 2, 3–
15. Addition of HCl does not obey anti-Markownikov’s rule
dimethyl–1–butene and subsequent reductions with Zn and
because H 2 O are
(a) It is a strong acid (b) It is a gas (a) Methanoic acid and 2-methyl-2-butanone
(c) Its bond energy is high (d) Its bond energy is less (b) Methanal and 3-methyl-2-butanone
(c) Methanol and 2, 2-dimethyl-3-butanone
16. In the following reaction, RCH 2 CH == CH 2 + ICl → [ A]
(d) Methanoic acid and 2-methyl-3-butanone
Markownikoff's product [A] is 21. The addition of HBr is easiest with
(a) RCH 2 C H — CH 2 I (a) Cl 2 C = CHCl (b) ClCH = CHCl

|
Cl (c) CH 3 − CH = CH 2 (d) (CH 3 ) 2 C = CH 2
(b) RCH 2 — C H — CH 2 Cl 22. The addition of HBr to 1-butene gives a mixture of products
|
I A, B and C
(c) RCH − CH = CH2

| (A) C (B) H
C
I
H
(d) RCH = CH − CH 2 I (C) CH 3 − CH 2 − CH 2 − CH 2 − Br
17. Presence of peroxides affects the addition of The mixture consists of
(a) A and B as major and C as minor products

(a) HBr (b) HCl
(b) B as major, A and C as minor products
(c) HI (d) All of these
(c) B as minor, A and C as major products
(d) A and B as minor and C as major products
Hydrocarbons | 136
(d) Diels–Alder reaction
23. Which of the following will not show geometrical isomerism 31. An alkene given two moles of HCHO, one mole of CO 2 and
F H F F one mole of CH 3 COCHO on ozonolysis. What is its structure

(a) C=C (b) C=C
Cl D Cl Cl (a) CH 2 = C = CH − CH 2 − CH 3
H 3C C2 H 5 CH3 CH3 CH 3
(c) C=C (d) C=C
H 3 C2 CH3 CH3 C2 H5 |
(b) CH 2 = CH − CH − CH = CH 2
24. One mole of each of the following alkenes is catalytically
(c) CH2 = C = C − CH3
hydrogenated. The quantity of heat evolved will be the lowest |
in the case of CH3
(a) 1-butene (b) trans-2-butene CH3

|
(c) cis-2-butene (d) 1, 3-butadiene (d) CH2 = C = C − CH = CH2
25. The order of reactivity of alkenes,
32. Cyclohexene is reacted with bromine in CCl 4 in the dark.
(CH 3 ) 2 C = CH 2 , CH 3 CH = CH 2 , CH 2 = CH 2 The product of the reaction is Br
(I) (II) (III) (a) Br (b)
when subjected to acid catalyzed hydration is Br
Br
(a) I > II > III (b) I > III > II Br
(c) III > II > I (d) II > I > III Br

(c) (d)
26. Which of the following compounds represents acrylonitrile
(a) Vinyl cyanide (b) Cyanoethene
33. The major product of the reaction
(c) Prop-2-ene nitrile (d) All of them
27. The following is a conjugated diene H+
Products
H2O
(a) CH 3 − CH = C = CH − CH 3
(b) CH 2 = CH − CH 2 − CH = CH 2 OH HO
(c) CH 2 = CH − CH 2 − CH 2 − CH = CH 2
OH
(d) CH2 = C− CH = CH2 OH
|
(I) (II) (III) (IV)
CH3
28. Addition of bromine to 1, 3-butadiene gives

(a) (I) (b) (II)
(a) 1, 2 addition product only
(c) (III) (d) (IV)
(b) 1, 4 addition product only
(c) Both 1, 2 and 1, 4 addition products 34. The major product formed when 2–butene is reacted with O3
followed by treatment with Zn / H 2 O is
(d) No reaction
29. Which of the following order of reagent is chosen to prepare (a) CH 3 COOH (b) CH 3 CHO
1, 3-butadiene from C 2 H 2
(c) CH 3 CH 2 OH (d) CH 2 = CH 2
(a) Cu 2 Cl 2 / NH 4 Cl and H 2 / Pd (BaSO 4 )
(b) NH 4 Cl / CuCl and H 2 / Pd (BaSO 4 ) Alkyne

+
(c) H 2 / Pd (BaSO 4 ) and CuCl / NH 4 Cl O3 / H 2O / OH
1. CaC2 + H 2O ⎯⎯→ X ⎯⎯ ⎯⎯⎯⎯→ HCOOH + HCOOH ,
(d) H 2 / Pd (BaSO 4 ) and NH 4 Cl / CuCl X is
(a) C 2 H 4 (b) C2 H 2
30. An alkyne combines with a conjugated diene to give an
unconjugated cycloalkadiene. The most likely title of this
(c) C2 H 6 (d) Ca (OH )2
reaction is
(a) Schotten–Baumann reaction 2. What is formed when calcium carbide react with heavy water
(b) Hofmann–Bromasmide reaction (a) C2 D2 (b) CaD 2

(c) Pinacol– Pinacolone rearrangement
Hydrocarbons | 137
(c) CaD 2 O (d) CD 2 9. What is the major product of the following reaction
1 mole of Cl2
3. Which of the following gases is used for welding CH3 C  C − CH2 − CH3 ⎯⎯⎯⎯⎯⎯⎯ →
(a) Methane (b) Ethane Cl Cl

(a) C=C
CH3 CH2CH3
(c) Acetylene (d) Ethene
Cl
4. Identify the alkyne in the following sequence of reactions |
(b) CH 3 − CH 2 − C − CH 2 CH 3
|
H Ozonolysis B Wacker Cl
Alkyne ⎯⎯ ⎯⎯2⎯⎯⎯→ A ⎯⎯⎯⎯⎯→ only
Lindlar's catalyst
⎯ ⎯⎯⎯
Process
Cl CH2CH3
(c) C=C
CH 2 = CH 2 CH3 Cl
(a) H 3 C − C  C − CH 3 Cl Cl
| |
(d) CH 3 − C − C − CH 2 CH 3
|
(b) H 3 C − CH 2 − C  CH |
Cl Cl
(c) H 2 C = CH − C  CH
10. A compound C 5 H 8 which give white ppt. with ammonical
(d) HC  C − CH 2 − C  CH AgNO 3 . A give (CH 3 ) 2 CHCOOH with hot alcoholic
KMnO 4 then compound is

5. (i) X
CH3 C  CCH3 ⎯⎯ ⎯→ CH3 − C − C − CH3
(ii) H2O / Zn || ||
O O
(a) CH 3 CH 2 − CH 2 − CH = CH 2
(b) CH 3 − CH 2 − C  CH
X in the above reaction is
(c) (CH 3 ) 2 CH − C  CH
(a) HNO 3 (b) O 2
(d) CH 2 = CH − CH 2 − CH = CH 2
(c) O3 (d) KMnO 4
11. Identify X in the following sequence of reactions
lindlar's
6. [ A] ⎯ ⎯⎯⎯ CH 3 − C  C − CH 3 ⎯⎯⎯→[B] Na in
1. NaNH
catalyst liq. NH 3 CH3 − C H − CH − CH2 − CH2 − CH3 ⎯⎯ ⎯⎯⎯2⎯⎯→ X
2. Na in liquid NH3
| |
[A] and [B] are respectively Br Br
(a) Cis, trans-2-butene (b) Both trans-2-butene (a) CH3 − CH − CH − CH2CH2CH3

| |
Br NH2
(c) Trans, cis-2-butene (d) Both cis-2-butene
7. When 2-butyne is treated with Pd − BaSO 4 ; the product

(b)
formed will be
(a) Cis − 2 − butene (b) Trans − 2 − butene

(c)
(c) 1− butene (d)
8. Arrange the following carbanions in order of their decreasing

stability (d) CH3 − CH − CH − CH2CH2CH3
| |
− − NH2 NH2
A. H3C − C  C B. H − C  C
12. A compound is treated with NaNH 2 to give sodium salt.
C. H3C − CH2 Identify the compound
(a) A  B  C (b) B  A  C (a) C2H2 (b) C6 H6
(c) C  B  A (d) C  A  B (c) C2H6 (d) C2H4
Hydrocarbons | 138
13. If acetylene is passed through an electric arc in the atmosphere 21. CH  CH ⎯⎯⎯
⎯4 HgSO
→ ⎯⎯⎯
3
⎯
⎯→ ⎯⎯⎯
⎯2
→ CH MgBr P / Br
of nitrogen, the compound formed is H2SO4 H2O
(a) HCN (b) Pyrrole (a) CH 3 CH (Br )CH 3 (b) CH 3 CH 2 CH 2 Br

(c) Pyrazole (d) Pyridine
(c) CH 2 = CH − Br (d) BrCH = CH − CH 3
14. Acetylene adds on to HCN gives
(a) Acetylene cyanide (b) Cyano acetylene 22. Which pair does not represent the cyclic compound of the
(c) Vinyl ethene (d) Acrylonitrile molecular formula C 4 H 6
15. Catalyst used in dimerisation of acetylene to prepare

chloroprene is
(a) (b)
(a) HgSO 4 + H 2 SO 4 (b) Cu 2 Cl 2
(c) Cu 2 Cl 2 + NH 4 Cl (d) Cu 2 Cl 2 + NH 4 OH
2+
H 2O / Hg LiAlH4 P4 / Br2
16. CH  CH ⎯⎯ ⎯⎯⎯→ X ⎯⎯ ⎯⎯→ Y ⎯⎯ ⎯ ⎯→ Z Here Z is (c) (d)
H 2SO4
(a) Ethylene bromide (b) Ethanol 23. Hydrocarbon C 6 H 6 decolourise Br2 water and gives ppt.
(c) Ethyl bromide (d) Ethylidene bromide with ammoniacal AgNO 3 . Hydrocarbon can be
Ni(CN )
17. CH  CH ⎯⎯⎯⎯
2
→ X . Here X in the reaction (a) 1, 3, 5-cyclohexatriene (b) 1, 5-hexadiyne
Pressure
(c) 2, 4-hexadiyne (d) None
(a) Benzene (b) Ethane
24. A dibromo derivative of an alkane reacts with sodium metal
(c) Cyclooctatetraene (d) Cyclohexane
to form an alicyclic hydrocarbon. The derivative is
CH
18. ||| reacts with acetic acid in presence of Hg2+ to give (a) 1,1-dibromopropane (b) 2,2-dibromobutane
CH
(c) 1,2-dibromoethane (d) 1,4-dibromobutane
CH3 CH(CH3COO)2
(a) | (b) | 25. The alkene C 6 H 10 producing OHC − (CH 2 )4 − CHO on
CH(CH3COO)2 CH(CH3COO)2
ozonolysis is
CH3
(c) | (d) None of these (a) Hexene-1 (b) Hexene-3
CH2(CH3COO)
(c) Cyclohexene (d) 1-methylcyclohexene-1
H2SO4
19. In the following reaction HC  CH ⎯⎯⎯⎯
⎯→ ' P ' 26. The final product in the given reaction is
Hg 2 +
Product 'P' will not give

KMnO4
⎯⎯ ⎯⎯→
(a) Tollen's reagent test (b) Brady's reagent test H2SO4 , 
(c) Victor Meyer test (d) Iodoform test OH

CHO
20. The structure of the product(Z) in the reactions given below (a) (b) CHO
NaNH 2 ,CH 3COCH 3 Hg , H 3O 2+ + OH
HC  CH ⎯⎯ ⎯⎯⎯ +
⎯⎯⎯→ X ⎯⎯ ⎯⎯⎯→ Z is
H H 2O
O COOH
O
||
(c) (d) COOH
(a) CH3 − CH 2 − CH 2 − C − CH 2 OH
27. In the following reaction,
CH 3
|
(b) CH 3 − C − CH − CH 2 OH
||
O the major product obtained is
CH 3
|
(c) CH 3 − C − C − CH 3 (a) (b)
|| |
O OH
CH3
| (c) (d)
(d) CH3 − CHOH − CH − CHO
Hydrocarbons | 139
28. Which of the following compounds is the most-stable 34. Which one of the following on ozonolysis followed by
oxidation will give adipic acid
CH3
(a) (b)
(a) (b)
CH3
(c) (d) (c) (d)
29. Identify the compound X in the following reaction 35. The major product in the following reaction is
H3C − C  C − H + HBr (excess)

CHC6H5 O Br
CH2
⎯⎯(⎯
i) O3
⎯ ⎯→ +X (a) (b) H3C C CH3
(ii) Zn / H2O
H3C Br
Br
CHO CHO H
H3C C CH2 H2 Br
(a) (b) (c) (d) H3C C CH
Br Br Br
Aromatic Hydrocarbon
OH
COOH 1. Which compound is aromatic
(c) (d)
[[[[
(a) (b)
30. The angle strain in cyclobutane is O C6H5
(c) (d)
(a) 19º 22 (b) 9º 44 C
(c) 24º 44 (d) 29º16 HC=CC6H5

2. Most common reactions of benzene (aromatic hydrocarbon)
31. Which cycloalkane has the lowest heat of combustion per and its derivatives are
CH 2 group
(a) Electrophilic addition reactions
(b) Electrophilic substitution reactions
(a) (b) (c) Nucleophilic addition reactions
(d) Nucleophilic substitution reactions
(c) (d)
3. Aromatic compounds burn with sooty flame because
32. Cyclohexene on reaction with OsO 4 followed by reaction (a) They have a ring structure of carbon atoms
with NaHSO 3 gives (b) They have a relatively high percentage of hydrogen
(c) They have a relatively high percentage of carbon
(a) Cis-diol (b) Trans-diol
(d) They resist reaction with oxygen of air
(c) Epoxy (d) Alcohol
4. Three fused benzene rings are found in
33. Ozonolysis of an alkene produces only one dicarbonyl (a) Naphthalene (b) Anthracene
compound. The structure of the alkene is
(c) Phenanthroline (d) Triphenyl methane
H 3 C − CH = CH − CH 3
(a) 5. Which of the following is aromatic
(a) (b)
(b)
(c) + –
(c) (d)
(d) CH3 − CH = CH − CH = CH2
Hydrocarbons | 140
6. Which of the following species is aromatic 13. Acylation of benzene to produce aliphatic aromatic ketones is
known as
(a) (b)

(a) Benzoin condensation (b) Hydroformylation

(c) Clemmensen reduction (d) Friedel-Craft’s reaction

(c) (d)

14. Which of the following group activates the benzene ring most
7. Which is a non-aromatic compound towards electrophilic substitution
CH3
(a) −CHO (b) − NR 2
(a) .O. (b) (c) − NHCOCH 3 (d) − NO 2

N
H
(c) (d) 15. The compound ‘A’ when treated with HNO 3 (in presence of
H 2 SO 4 ) gives compound ‘B’ which is then reduced with Sn
and HCl to aniline. The compound ‘A’ is
8. In the following reaction, the product 'R' is
(a) Toluene (b) Benzene
H 2O hot iron CH 3Cl
CaC2 ⎯⎯ ⎯→ P ⎯⎯ ⎯ ⎯→ Q ⎯⎯ ⎯ ⎯→ R
tube AlCl3
(c) Ethane (d) Acetamide
(a) Benzene (b) Ethylbenzene 16. Chlorobenzene is o,p-directing in electrophilic substitution

reaction. The directing influence is explained by
(c) Toluene (d) n-propylbenzene
(a) +M of Ph (b) +I of Cl
9. Nitration of benzene by nitric acid and sulphuric acid is
(c) +M of Cl (d) +I of Ph
(a) Electrophilic substitution (b) Electrophilic addition
(c) Nucleophilic substitution (d) Free radical substitution HNO Br2

17. ⎯⎯⎯⎯
3
→ A ⎯⎯⎯→ B, The compound B is
H 2SO4 FeBr3
10. Benzene can be obtained by heating either benzoic acid with
X or phenol with Y. X and Y are respectively
NO2 NO2
(a) Zinc dust and soda lime Br
(a) (b)
(b) Soda lime and zinc dust
Br
(c) Zinc dust and sodium hydroxide NO2 NO2
(d) Soda lime and copper
(c) (d)
11. Find the major product in the following reaction
Br Br
CCl3
Br
18. Friedel – Craft reaction is not related with

CCl3 CCl3
(a) Sulphonation (b) Nitration
(a) (b)
Cl (c) Acylation (d) Reduction
CCl3 Cl
19. Which one of the following reactions is most suitable for the
(c) Cl (d) preparation of n-propyl benzene
12. Which of the following compounds reacts slower than (a) Friedel-Craft's reaction (b) Wurtz reaction
benzene in electrophilic substitution
(c) Wurtz-Fittig reaction (d) Grignard reaction
CH3 NH2
20. Which of the following does not respond to Friedel Craft
reaction
(a) (b)
(a) (b)
NO2 OH
S
CH3 NH2
(c) (d)
(c) (d)
Hydrocarbons | 141
21. Propyne on polymerisation gives O
||
(a) Mesitylene (b) Benzene 29. Reaction of benzene with Me3 C C − Cl in the presence of
anhydrous AlCl 3 gives
(c) Ethyl benzene (d) Propyl benzene
Me3C O
22. Xylenes on oxidation with acidic KMnO 4 gives C CMe3
(a) (b)
(a) Terphthalic acid (b) Phthalic acid
(c) Isophthalic acid (d) All of these AlCl3

CMe3 Me3C O
23. The product formed when toluene is heated in light with Cl 2 C
(c) (d)
and in absence of halogen carrier is
(a) Benzotrichloride (b) Gammexane

C
Me3C O
(c) Chlorobenzene (d) None of these
24. What is the end product which is obtained on the nitration of 30. Identify the product (E) in the following sequence of reactions
toluene CH3
FeCl3
Br2 Sn / HCl NaNO2 / HCl
(a) o-nitrotoluene (b) p-nitrotoluene ⎯⎯⎯→ A ⎯⎯ ⎯⎯→ B ⎯⎯ ⎯⎯⎯ ⎯→ C 273− 278K
(c) 2, 4-dinitrotoluene (d) 2, 4, 6-trinitrotoluene H2O/H3PO2

NO2
25. An equimolar mixture of toluene and chlorobenzene is treated E ⎯⎯⎯
KMnO
− ⎯ D
4
OH
with a mixture of conc. H 2 SO 4 and conc. HNO 3 . Indicate COOH COOH
the correct statement from the following Br
(a) p − nitrotoluene is formed in excess (a) (b)

CH3 CH3
(b) Equimolar amounts of p − nitrotoluene and p−
nitrochlorobenzene are formed (c) Br (d) O2N Br
(c) p − nitrochlorobenzene is formed in excess 31. Friedel– Crafts acylation is

(a)  – acylation of a carbonyl compound
(d) m − nitrochlorobenzene is formed in excess
(b) Acylation of phenols to generate esters
26. Catalytic dehydrogenation of n-heptane in presence of
Cr 2 O3 / Al 2 O3 at 750 K gives (c) Acylation of aliphatic olefins
(d) Acylation of aromatic nucleus
(a) Iso-heptane (b) 1-heptene
32. In the following set of aromatic compounds
(c) Toluene (d) 2, 3-dimethylpentene-1
NO2 COOCH3 OCH3
27. The final product formed in this reaction is
KMnO4 / KOH H3O + (i) (ii) (iii ) (iv )

⎯⎯ ⎯⎯⎯ ⎯→ A ⎯⎯ ⎯
⎯→ B
The correct order of reactivity toward Friedel–Crafts alkylation
is
(a) (b)
(a) i  ii  iii  iv (b) ii  iv  iii  i
(c) iv  ii  iii  i (d) iii  i  iv  ii

(c) (d)
33. The major product obtained in the reaction of toluene with 1–
bromo–2–methyl propane in the presence of anhydrous
AlCl 3 is CH3
28. Acylation process is preferred than direct alkylation because
H3C
(by the Friedel-Craft's reaction) (a) (b)
(a) In alkylation, a poisonous gas is evolved

(b) In alkylation, large amount of heat is evolved H3C
H3C
(c) In alkylation, polyalkylated product is formed (c) (d)
(d) Alkylation is very costly
Hydrocarbons | 142
IIT-JEE/ AIEEE (a) CH3 − CH2 − CH − Br
|
CH3
1. A mixture of ethyl iodide and n-propyl iodide is subjected to
Wurtz reaction. The hydrocarbon that will not be formed is (b) CH3 − CH − CH2 − Br
|
[1990] CH3
(a) n-butane (b) n-propane CH3

|
(c) CH3 − C − Br
(c) n-pentane (d) n-hexane |
CH3
2. 1-Butene may be converted to butane by reaction with
(d) CH 3 − CH 2 − CH 2 − CH 2 − Br
[2003]
8. Of the five isomeric hexanes, the isomer which can give two
(a) Zn-HCl (b) Sn-HCl
monochlorinated compounds is [2005]
(c) Zn-Hg (d) Pd/ H 2 (a) n-hexane (b) 2, 3-dimethylbutane
3. When isobutyl magnesium bromide in dry ether is treated with (c) 2, 2-dimethylbutane (d) 2-methylpentane
absolute ethyl alcohol, the products formed are [1995] 9. Which one of the following has the minimum boiling point
(a) CH 3 − CH − CH 2 OH and CH 3 CH 2 MgBr [2004]
|
CH 3 (a) 1-butene (b) 1-butyne
(c) n-butane (d) Isobutane

(b) CH 3 − CH − CH 2 − CH 2 − CH 3 and Mg(OH )Br
|
CH 3 10. Main constituent of marsh gas is [1980]
(a) C2H2 (b) CH4

(c) CH 3 − CH − CH 3 and CH 3 − CH 2 OMgBr
|
CH 3 (c) H2S (d) CO
(d) CH 3 − CH − CH 3 , CH 2 = CH 2 and Mg(OH )Br 11. Which one of the following compounds gives methane on
| treatment with water [1990]
CH 3
(a) Al4 C3 (b) CaC2
4. The highest boiling point is expected for [1986]
(c) VC (d) SiC
(a) n − butane
(e) B4C
(b) Iso-octane
12. The major organic compound formed by the reaction of 1, 1,
(c) n − octane 1 - trichloroethane with silver powder is [2014]
(d) 2,2,3,3-tetramethyl butane (a) Acetylene (b) Ethene

5. Which of the following compounds is insoluble even in hot (c) 2-Butyne (d) 2-Butene
concentrated H 2 SO 4 [1983]
13. n-propyl bromide on treatment with ethanolic potassium
hydroxide produces [1987]
(a) Ethylene (b) Benzene
(a) Propane (b) Propene
(c) Hexane (d) Aniline
(c) Propyne (d) Propanol
6. The number of possible enantiomeric pairs that can be
produced during monochlorination of 2-methylbutane is 14. Alcoholic solution of KOH is used for [1990]
[1997] (a) Dehydration (b) Dehydrogenation
(a) 2 (b) 3 (c) Dehydrohalogenation (d) Dehalogenation
(c) 4 (d) 1 15. During debromination of meso-dibromobutane, the major

compound formed is [1997]
7. What is the chief product obtained when n-butane is treated
with bromine in the presence of light at 130 o C [1995] (a) n-butane (b) 1-butane
(c) cis-2-butene (d) trans-2-butene
Hydrocarbons | 143
16. The dehydrohalogenation of neopentyl bromide with OH
|
alcoholic KOH mainly gives [1990] (c) CH3 − CH2 − C − CH − CH3
| |
(a) 2-methyl-1-butene (b) 2-methyl-2-butene CH3 Cl
(c) 2, 2-dimethyl-1-butene (d) 2-butene CH3 OH

| |
17. In the following sequence of reactions, the alkene affords the (d) CH3 − C − CH − CH3
|
compound ‘B’ CH3
O⎯
CH3 CH = CHCH3 ⎯⎯3 H2⎯
→ A ⎯⎯ O
⎯→ B 23. One mole of a symmetrical alkene on ozonolysis gives two
Zn
moles of an aldehyde having a molecular mass of 44u. The
The compound B is [2008] alkene is [2010]
(a) Ethene (b) Propene

(a) CH3COCH3 (b) CH3CH2COCH3
(c) 1-butene (d) 2-butene
(c) CH3CHO (d) CH3CH2CHO
24. The reaction of propene with HOCl proceeds via the addition
18. The halogen which is most reactive in the halogenation of of [2001]
alkenes under sunlight is [1981]
(a) H + in the first step
(a) Chlorine (b) Bromine
(b) Cl + in the first step
(c) Iodine (d) All equal
(c) OH − in the first step
19. The product of acid catalyzed hydration of 2-phenyl propene
is [2004] (d) Cl + and OH − in a single step
(a) 3-phenyl-2-propanol (b) 1-phenyl-2-propanol 25. Which one of the following alkenes will react fastest with H2
under catalytic hydrogenation condition [2000]
(c) 2-phenyl-2-propanol (d) 2-phenyl-1-propanol
20. In which of the following, addition of HBr does not take R R R H
place against Markownikoff’s rule [1985]

(a) (b) H
H H R
(a) Propene (b) But-1-ene
(c) But-2-ene (d) Pent-2-ene R R R R
(c) (d)
21. CH 3 − CH = CH 2 + NOCl → P. Identify the product
R H R R
[2006]
(a) CH3 − CH − CH 2 (b) CH3 − CH − CH 2 26. The intermediate during the addition of HCl to propene in the
| | | | presence of peroxide is [1997]
Cl NO NO Cl
• +
(a) CH3 CHCH2 Cl (b) CH3CHCH3
NO
| • +
(c) CH 3 − CH 2 − CH (d) CH2 − CH2 − CH2 (c) CH3CH2 CH2 (d) CH3CH2 CH2
| | |
Cl NO Cl 27. In the presence of peroxide, hydrogen chloride and hydrogen
iodide do not give anti-Markownikov’s addition to alkenes
22. The predominant product formed, when 3-methyl-2-pentene because [2001]
reacts with HOCl, is [1995]
(a) Both are highly ionic
Cl OH (b) One is oxidising and the other is reducing
| |
(a) CH3 − CH2 − C − CH − CH3 (c) One of the steps is endothermic in both the cases
|
CH3 (d) All the steps are exothermic in both the cases
28. The compound having both sp and sp 2 hybridised carbon

Cl Cl
| | atom is [1981]
(b) CH3 − CH2 − C − CH − CH3
| (a) Propene (b) Propyne
CH3
(c) Propadiene (d) None of these
Hydrocarbons | 144
29. Reaction of one molecule of HBr with one molecule of 1,3- 35. In the reaction,
o
butadiene at 40 C gives predominantly [2005] LiAlH Alc . KOH PCl
CH3 COOH ⎯⎯⎯⎯
4 →
A ⎯⎯⎯
⎯
5 → B ⎯⎯ ⎯⎯⎯→ C,
(a) 3-bromobutene under kinetically controlled conditions the product C is [2014]
(b) 1-bromo-2-butene under thermodynamically controlled (a) Acetaldehyde (b) Acetylene
conditions
(c) Ethylene (d) Acetyl chloride
(c) 3-bromobutene under thermodynamically controlled
conditions 36. The treatment of CH 3 MgX with CH 3 C  C − H produces
[2008]
(d) 1-bromo-2-butene under kinetically controlled conditions
H H
| |
30. The number of optically active products obtained from the
(a) CH3C  C − CH3 (b) CH 3 − C = C − CH 3
complete ozonolysis of the given compound is
(c) CH4 (d) CH3 − CH = CH2
CH3 H
37. The product(s) obtained via oxymercuration
CH3 − CH = CH − C − CH = CH − C − CH = CH − CH3 (HgSO 4 + H 2 SO 4 ) of 1-butyne would be [1999]
H CH3 O
||
[2012] (a) CH 3 − CH 2 − C − CH 3
(a) 0 (b) 1
(b) CH3 − CH2 − CH2 − CHO
(c) 2 (d) 4
31. 3-Methyl-pent-2-ene on reaction with HBr in presence of (c) CH3 − CH2 − CHO + HCHO
peroxide forms an addition product. The number of possible
(d) CH3CH2COOH + HCOOH
stereoisomers for the product is
[2017] 38. When propyne reacts with aqueous H 2 SO 4 in the presence
(a) Zero (b) Two of HgSO 4 , the major product is [1983]
(c) Four (d) Six (a) Propanal (b) Propyl hydrogen sulphate
32. The synthesis of 3-octyne is achieved by adding a (c) Acetone (d) Propanol
bromoalkane into a mixture of sodium amide and an alkyne. 39. Which of the following reactions will yield 2, 2-
The bromoalkane and alkyne respectively are dibromopropane [2007]
[2010] (a) HC  CH + 2HBr →
(a) BrCH2CH2CH2CH2CH3 and CH3CH2C  CH (b) CH3C  CH + 2HBr →
(b) BrCH2CH2CH3 and CH3CH2CH2C  CH (c) CH3CH = CH2 + HBr →
(c) BrCH2CH2CH2CH2CH3 and CH3C  CH (d) CH3CH = CHBr + HBr →
(d) BrCH2CH2CH2CH3 and CH3CH2C  CH 40. 2 − Hexyne gives trans − 2 − Hexene on treatment with
[2012]
33. A gas formed by the action of alcoholic KOH on ethyl iodide,
(a) Pt / H2 (b) Li / NH3
decolourises alkaline KMnO 4 solution. The gas is
[1982] (c) Pd / BaSO4 (d) LiAlH4
(a) CH4 (b) C2H6
Hg 2+ / H +
41. Ph − C  C − CH 3 ⎯⎯ ⎯ ⎯⎯→ A . A is [2002]
(c) C2H4 (d) C2H2
O
34. The hydrocarbon which can react with sodium in liquid
(a) Ph (b) Ph O
ammonia is [2008]
(a) CH3CH2C  CH H 3C H 3C
(b) CH3CH = CHCH3 OH

(c) Ph (d) Ph OH
(c) CH3CH2C  CCH2CH3
(d) CH3CH2CH2C  CCH2CH2CH3 H 3C H 3C
Hydrocarbons | 145
42. Which of these will not react with acetylene [2002] 48. The trans–alkenes are formed by the reduction of alkynes with
[2018]
(a) NaOH (b) Ammonical AgNO 3
(a) Na / liq . NH 3 (b) Sn − HCl
(c) Na (d) HCl
(c) H 2 − Pd / C, BaSO 4 (d) NaBH 4
43. What is the product when acetylene reacts with hypochlorous
acid [2002]
49. The bond order of individual carbon-carbon bonds in
(a) CH3COCl (b) ClCH2CHO benzene is [1981]
(c) Cl2CHCHO (d) ClCHCOOH (a) One (b) Two
44. The most strained cycloalkane is [1981] (c) Between one and two (d) One and two, alternately
(a) Cyclopropane (b) Cyclobutane 50. Amongst the following the most basic compound is
[2005]
(c) Cyclopentane (d) Cyclohexane
(a) Benzylamine (b) Aniline
45. Cyclohexene on ozonolysis followed by reaction with zinc dust
and water gives compound E. Compound E on further (c) Acetanilide (d) p-nitroaniline
treatment with aqueous KOH yields compound F. Compound
F is [2007] 51. Which of the following molecules, in pure form, is (are)
unstable at room temperature [2012]
(a) (b)
CHO CHO
(a) (b)
CO2H
(c) COOH (d)
CO2H O O
(c) (d)
46. The product of the reaction given below is
52. Presence of a nitro group in a benzene ring [2007]
(a) Activates the ring towards electrophilic substitution

[2016]
(b) Renders the ring basic
OH O
(a) (b) (c) Deactivates the ring towards nucleophilic substitution
(d) Deactivates the ring towards electrophilic substitution
53. Amongst the following, the compound that can be most

CO2H
readily sulphonated is [1982]
(c) (d)
(a) Benzene (b) Nitrobenzene
(c) Toluene (d) Chlorobenzene

47. Which compound would give 5 – keto – 2 – methyl hexanal
upon ozonolysis [2015] 54. Among the following statements on the nitration of aromatic
compounds, the false one is [1997]
(a) The rate of nitration of benzene is almost the same as that

(a) (b) of hexadeuterobenzene
(b) The rate of nitration of toluene is greater than that of

benzene
(c) The rate of nitration of benzene is greater than that of

(c) (d) hexadeuterobenzene
(d) Nitration is an electrophilic substitution reaction
Hydrocarbons | 146
55. The electrophile, E  attacks the benzene ring to generate the COOH OCH3
intermediate  -complex. Of the following, which  -
(d)
complex is of lowest energy [2008]
HO H3C NO2
NO2
NO2
H H
(a) + (b)
E + E O NO2
NO2 NO2
58. The reaction of toluene with Cl 2 in presence of FeCl 3 gives
predominantly [2007]
(c) + H (d) + (a) Benzoyl chloride (b) Benzyl chloride
E
E
(c) o–and p–chlorotoluene (d) m–chlorotoluene
H
56. Nitrobenzene can be prepared from benzene by using a 59. The compound formed as a result of oxidation of ethyl
mixture of conc. HNO 3 and conc. H 2 SO 4 . In the nitrating benzene by KMnO4 is [2007]
mixture, HNO 3 acts as a [1997]
(a) Benzophenone (b) Acetophenone
(a) Base (b) Acid
(c) Benzoic acid (d) Benzyl alcohol
(c) Reducing agent (d) Catalyst 60. Which of the following molecules is least resonance stabilized
[ 2017]
57. The compounds P, Q and S
(a) (b)
COOH OCH3 N
O O
HO H3C S
P Q
(c) (d)
were separately subjected to nitration using HNO 3 / H 2 SO 4
O
mixture. The major product formed in each case respectively,
is [2010]
COOH OCH3 JEE Advanced
(a)
More than one correct answers
HO H3C
NO2 NO2
1. An aromatic molecule will [1999]
O (a) Have 4n-electrons (b) Have(4n+2)- electrons
O2N (c) Be planar (d) Be cyclic

COOH OCH3 2. The E will attack which ring in the following compounds
(b) and what is the rate of ESR in this
HO NO2 H3C
NO2
Y Q
O X P
A B
NO2
(a) In A, ring X will take part in electrophillic substitution
COOH OCH3 reaction
(b) In A, ring Y will take part in electrophillic substitution
HO H3C NO2 reaction
(c) NO2 NO2
(c) In B, ring Q will take part in electrophillic substitution
reaction
O
(d) Compound B is more reactive than compound A
Hydrocarbons | 147
3. Among P , Q, R and S, the aromatic compound(s) is/are 6. Which of the following show diastereomers
[2013]
(a)
(a) P (b) Q
(c) R (d) S
(b) Me
Cl
N NH2
AlCl 3
⎯⎯⎯⎯ → P Me
Me
NaH Q
⎯⎯⎯⎯→ (c)
R Me
( NH ) CO
⎯⎯ ⎯4⎯2 ⎯⎯
3
→ O2N
O O 100 −115 º C Me
(d) N NH NO2
O
Me
HCl
⎯⎯⎯→ S 7. 1
Me 1 4 1
2 Me H Me Me
Br H 2 3 3 2
4. Among the following, reaction(s) which gives (give) tert- EtONa + EtOH
+
3
butyl benzene as the major product is (are) [2016] D H 4
H Me H D
Br
4
Cl Me
(a) NaOC2H5 (b) AlCl3
(A) (I) (II)
Erythro – 2 – bromo – 3 trans – But – 2 – ene cis – But – 2 – ene
– deuteriobutane or –2–d
Erythro – 2 –
OH bromobutane – 3 – d
(c) H2SO4 BF3.OEt2
D 1 4 1
3 H Me Me Me H
4 2 1 2 3 2 3
+ + +
Br / h Me 4
5. C6 H12( A) ⎯⎯2⎯⎯→ One isomer (B) H
Monobromination H H H D Me
Br / h (III) (IV) (V)
C6 H12(C) ⎯⎯2⎯⎯→ Number of isomers including But – 1 – ene – 3 – d cis – But – 2 – ene trans – But – 2 –
Monobromination
ene – 2 – d
geometrical isomers
Both (A) and (C ) do not decolourise Baeyer’s reagent or Which statements are correct
(a) (I), (II) with small amount of (III) are formed
Br2 solution.
(b) (IV) and (V) with small amount of (III) are formed
Which of the statements is/are correct (c) The two groups undergoing elimination ( H and Br
(a) Compounds (A) and (B) are, respectively or D and Br ) must lie in an anti – periplanar
arrangement
Br
(d) Compound (A) has two conformations in which H
or D is anti – periplanar to bromine. These are ( A1 )
and
and ( A2 )
Me 4
Br
1 Me Br
4 Me 2
3 2 1
Me H D
(b) Compound (C ) is Me
D
3 H H
(c) The total number of isomers obtained by H
monobromination of (C ) is six including geometrical (A1)
isomer Br
1 H Br
2
(d) The major product of monobromination of (C ) is Me 4 3 2 1
H H Me
Me
Me
Me Br 3 D H
4
D
(A2)
Hydrocarbons | 148
3 2 1
NaNH + Liq. NH (a) The melting point of trans – but –2 – ene is greater
8. CH 2 == C == CH 2 ⎯⎯ ⎯2⎯ ⎯ ⎯⎯
3
→(B)
Propa − 1, 2 − diene than that of the cis – isomer due to symmetrical
(A) packing in the crystal lattice of the crystal the trans –
Which of the following statements is/are correct form
(a) Product (B) is CH 2 == CH −− CH 3 (b) The boiling point of cis – but – 2 – ene is greater than
that of the trans – isomer due to steric strain in the cis–
(b) Product (B) is propyne
isomer because of van der Waals repulsion force of
(c) Product (B) is more stable than (A) large group on the same side of the double bond and
(d) Compound (A) has a more negative heat of the cis – isomer becomes less stable because of the
hydrogenation than the compound (B) increasing repulsive force
9. Which of the following does not react with aqueous (c) The boiling point of the cis – isomer is greater than
KMnO4 that of the trans – isomer due to the relatively high
polarity of the cis – isomer compared to its trans –
Me
isomer
(d) The boiling point of
(a) (b) F2C == CF2 H Me
(I)
(c) (d) H Cl
N
Me H
Is greater than that of (II)
10. POCl3
Me H (B) (Major)
H Cl
H OH
(A) 13. 6
2 4
1 Me 1 mol
Me (B)
Which of the following statements is/are correct 3 5
HCl
Hexa –2, 4– diene

(a) (B) is (I) (A)
Product (B) is
Me
(a) Me
Me
(b) (B) is (II)
Cl
Me Me
(c) (I) is Saytzeff’s elimination product, while (II) is Hof– (b) Me
mann’s elimination product Cl
(d) (II) is predominant because the two eliminating groups Cl

(H and OH) are in syn – position
Me
11. In which of the following, does the first compound have a (c) Me
higher dipole moment than the second
(d) Cl Me
(a) NO2 and CH3 NO2
14. Which of the following decolourise (s) Br2 solution
(b) Cl and Me Cl
Ph
(a) (b)
(c) O and O
O N
Ph
CHO H
(d) Me CHO
and
Me (c) (d)
12. Which of the following statement (s) is/are wrong
Hydrocarbons | 149
15. Decreasing acidity of H atom in (B) is as follows
H at C − 1  H at C − 2  H at C − 3 .
Reagent
(A)
17. The correct statement(s) for the following addition reactions
is (are) [2017]
O H3C H
Reagent Br2/CHCl3
(i) M and N
(B)
H CH3
Reagent H3C CH3

(C) O
Br2/CHCl3
(ii) O and P
Me
H H
Reagent
(D) (a) (M and O) and (N and P) are two pairs of enantiomers
(b) Bromination proceeds through trans-addition in both
the reactions
Which statements are correct for reagents A, B, C and D
(c) O and P are identical molecules
(A) (B) (C) (D)
(d) (M and O) and (N and P) are two pairs of diastereomers
(a) H 2 / Pt MMPP Cold alk. O2 + PdCl 2
+ CuCl 2 Reasoning type questions
KMnO4
(b) H 2 / Pd + HCO 2 H Hot alk. Dil. H 2 SO 4 Read the following statements carefully to mark the correct option
BaSO 4 + 2+ out of the options given below
KMnO4 + Hg
quinoline (a) Statement 1 is true, statement 2 is true ; statement 2 is
a correct explanation for statement 1
(c) Sia 2 BH + PhCO 3 H OsO4 / O2 + PdCl 2
(b) Statement 1 is true, statement 2 is true ; statement 2 is
NaHSO 3 + CuCl 2 + H 2 O not a correct explanation for statement 1
CH 3 COOH
(c) Statement 1 is true, statement 2 is false
(d) BH 3 + THF MCPBA OsO4 / Wecker process (d) Statement 1 is false, statement 2 is true
+ CH 3 H 2O2 18. Statement 1 : 1-Butene on reaction with HBr in the
COOH presence of a peroxide produces 1-
bromo-butane.
16. In the following sequence of reactions
Statement 2 : It involves the free radical mechanism.
Br
3 2 mol of Me [2000]
4 2 1 alc. KOH H
Me 19. Statement 1 : Addition of Br2 to 1-butene gives two
(A) (C)
(B) Br optical isomers.
1 mol of
Statement 2 : The product contains one asymmetric
alc. KOH
carbon. [1998]
(D)
(Major) 20. Statement 1 : Bromobenzene upon reaction with
Which of the statements are correct about the compound (D ) Br2 / Fe gives 1,4-dibromobenzene as
(D ) is the major product.
Br
(a) Statement 2 : In bromobenzene, the inductive effect
Me of the bromo group is more dominant
than the mesomeric effect in directing
Me
the incoming electrophile. [2008]
(b)
Br
Br
Comprehension type questions
(c)
Me
Passage - I
(d) In E 2 elimination, the most acidic H atoms is
removed. The inductive effect (− I ) of Br atom An acyclic hydrocarbon P, having molecular formula
C 6 H 10 , gave acetone as the only organic product through
increases the acidity of H atoms to which Br atoms
are bonded. the following sequence of reactions, in which Q is an
intermediate organic compound.
Hydrocarbons | 150
(i) conc H 2SO4
O 24. The correct statement with respect to product Y is [2014]
(catalytic amount)
P (i) dil. H2SO4 / HgSO 4
⎯⎯⎯⎯⎯⎯⎯→ Q ⎯⎯⎯⎯⎯⎯→
(− H 2O) (a) It gives a positive Tollens test and is a functional isomer
(C6 H10 ) (ii) NaBH 4 /ethanol (ii) O3
(iii) dil.acid
of X
(iii) Zn / H 2O
H3C CH3 (b) It gives a positive Tollens test and is a geometrical
isomer of X
21. The structure of compound P is [2011]
(c) It gives a positive iodoform test and is a functional
(a) CH 3 CH 2 CH 2 CH 2 − C  C − H isomer of X
(b) H 3 CH 2 C − C  CH 2 CH 3 (d) It gives a positive iodoform test and is a geometrical
H 3C isomer of X
(c) H C − C  C − CH 3 Passage - III
H 3C In the following reactions :
i. B2H6
Pd − BaSO4
H 3C C8 H6 ⎯⎯ ⎯⎯⎯→ C8 H8 ⎯⎯ ⎯⎯⎯⎯⎯ ⎯→ X
ii. H O , NaOH, H O
H2 2 2 2
(d) H 3C C − C  C − H
H 3C
22. The structure of the compound Q is [2011]
H 3C OH i. EtMgBr , H2O
| C8 H8 O ⎯⎯ ⎯+⎯⎯⎯→ Y
ii. H , heat
(a) H C − C − CH2CH3
|
H 3C H 25. Compound X is [2015]
H 3C OH O OH
|
(b) H 3C C − C − CH3 CH3 CH3
| (a) (b)
H 3C H
H3C OH
| CHO
(c) H C − CH2CHCH3 (c) (d)
H3C
26. The major compound Y is [2015]
OH
|
(d) CH 3 CH 2CH 2 CHCH 2 CH 3 (a) CH3 (b) CH3
Passage – II
CH2 CH3
Schemes 1 and 2 describe sequential transformation of
CH3
alkynes M and N. Consider only the major products formed CH3
(c) (d)
in each step for both the schemes.
1. NaNH2 (excess)
2. CH3CH2I (1 equivalent) Passage - IV
X Scheme-1
3. CH3I (1 equivalent)
Cl 2 +h
4. H2, Lindlar’s catalyst (i)Compound (A) (C6 H14 ) ⎯⎯ ⎯⎯→ (Five isomeric
hexyl chloride)
1. NaNH2 (2 equivalent) C6H13Cl
2. Zn + aq .CH 3 COOH
Y Scheme-2 (A)
3. (mild)
Cl 2 +h
4. Pd/C (ii)Compound (B)(C6 H14 ) ⎯⎯ ⎯⎯→ (Two isomeric
5.
23. The product X is [2014]
hexyl Chloride)
C6H13Cl
Zn+aq .CH3COOH
H3CO H
(B)
(a) (b) H H2 +Pt
(iii) Alkene (C ) and alkene (D ) (C6 H12 ) ⎯⎯ ⎯ ⎯→
H H H3CO
Compound
(B)
CH3CH2O H
27. Compound (A) is
(c) (d) H (a) 2, 3 − Dimethylbutane (b) 2 − Methylpentane
H H CH3CH2O (c) 2, 2 − Dimethylbutane (d) 3 − Methylpentane
Hydrocarbons | 151
28. Compound (B) is Me Me
(a) 2, 3 − Dimethylbutane (b) 2 − Methylpentane
(a)
(c) 2, 2 − Dimethylbutane (d) 3 − Methylpentane Me OH
29. Two isomeric hexyl chlorides obtained from (B) are Me Me
Me Me
(a) Cl (b) Me OH
Me and Me Me Me Me
Cl
Me Me Cl
Me OH
(c)
(b) Me Me and Me Me
Me Me
Cl
(d) Me OH
Me Me Me 32. The number of stereoisomers for (A) is
Cl (a) 2 (b) 4
(c) and
Me Me Me (c) 6 (d) 8
Cl
33. The products of (A) on ozonolysis followed by reduction
Me Me with LAH are
Me Cl Me a O O
(d) Me and O
Cl Me Me Me Me Me H OH
O H
30. The alkenes (C ) and (D ) are
Me Me Me b OH
(a) and HO
Me
Me Me Me H OH
Me Me
Me OH
Me
Me Me c OH O
(b) Me OH
and OH
Me Me Me Me Me O
H
Me Me d O
Me HO
(c) and Me OH OH
Me Me Me
Me
O
Me Me
(d)
and 34. The products of (A) on ozonolysis followed by oxidation
Me Me Me
with H 2O2 are
Passage - V a O HO
Compound (A) (C13 H 24 O) is a sex – attractant pheromone
Me OH OH
of codling moth. On hydrogenation, compound (A) Me Me
O
absorbs two molar equivalents of H 2 and is converted to
3– ethyl–7 –methyl decan –1 – ol. On reductive ozonolysis, b OH O
it gives the following compounds. O
O O OH
Me Me Me H
O OH H
H OH
Me Me Me c O O
O
O H
OH
(I) (II) (III) Me Me Me OH
31. (A) shows two structural isomers, one structure is OH
O
Me
Me
d O O O
Me (A1) OH O
Me Me Me OH OH
The other structure ( A2 ) is O
OH
Hydrocarbons | 152
Passage - VI Me Me
6 OMe OMe
5 Me
(c) H (d) D
1
4 2 D H
3
(A) 39. Which of the following is true regarding the hydroboration
1 – Methylcyclohexene oxidation of alkene
(i) BD3 + THF (i) BD3 + THF (i) Hg +(OAc)2 (i) Hg (OAc)2 (a) It leads to anti – hydration of alkene and occurs with a
+ THF + H2O + THF +CH3OH
regioselectivity opposite to Markovnikov’s rule
(ii) H2O2 + OH (ii) D2O2 + OD
(ii) NaBH4 + OH (ii) NaBD4 + OD (b) It leads to syn - addition (hydration) of alkene and
carbocation intermediates are involved
(B) (C) (D) (E)
(c) The H that becomes bonded to the C atom comes
35. Compound (B) is
from the borane and the (OH ) group from H 2O2
Me Me
(d) The H that becomes bonded to the C atom comes
D D
(a) (b) from the borane and the (OH ) groups from the
OH H
solvent (H 2 O)
H OH
40. Which of the following are true regarding hydroboration of
Me
alkene
Me
OH OH (a) Reaction proceeds through ionic intermediate and
(c) (d) syn– addition takes place
D H
(b) Reaction proceeds through cyclic intermediate
H D
transition state and syn– addition takes place
36. Compound (C ) is
Me Me (c) Reagent diborane in ether (THF ) exists as
OD OD
    
(a)
D
(b)
H  BH 2   BH 4 
   
H OD (d) Reagent exists in THF as borane – THF complex
Me Me
D D O BH3
(c) (d)
OD H
41. Which is the wrong statement about oxymercuration–
H OD
demercuration
37. Compound (D ) is (a) In the first step, oxymercuration occurs, i.e., water and
Hg(OAc)2 add to the double bond
Me Me
H H (b) In the second step, demercuration occurs, i.e., NaBH 4
(a) (b) reduces (HgOAc) group to hydrogen
OH H
H OH
(c) The net reaction is the addition of water according to
Markovnikov’s rule
Me Me (d) Rearrangement takes place
OH Passage - VII
(c) (d) OH
OH
The reaction of compound P with CH 3 MgBr (excess) in
H
H (C2 H 5 )2 O followed by addition of H 2 O gives Q. The
compound Q on treatment with H 2 SO 4 at 0ºC gives R. The
38. Compound (E ) is
reaction of R with CH 3 COCl in the presence of anhydrous
Me Me AlCl 3 in CH 2 Cl 2 followed by treatment with H 2 O
OH OH produces compound S. [Et in compound P is ethyl group]
(a) (b) (H3C)3C CO2Et
H D
Q R S
D H
P
Hydrocarbons | 153
42. The product S is [2017] OH
COCH3
(H3C)3C CH3 (c) (d)
(a)
O
Integer type questions

H3C CH
3
(b) (H3C)3C This section contains some integer type questions. The answer
to each of the questions is a single-digit integer, ranging from
0 to 9.
COCH3
46. The total number of alkenes possible by
dehydrobromination of 3-bromo-3-cyclopentylhexane
(c) HO3S
(H3C)3C CH3 using alcoholic KOH is [2011]
O
47. How many of the following on reductive ozonolysis will give
only glyoxal
COCH3 1, 3-butadiene, ethylene, acetylene, o-xylene, m-xylene,
p-xylene, benzene, cyclobutadiene, cyclooctatetraene
H3COC
(d) (H3C)3C CH3 48. How many of the following species are aromatic in nature
H3C
cyclopentadienyl cation, cyclopentadienyl anion, tropylium
cation, azulene, cyclopropenyl cation, tetrahydrofuran,
43. The reactions, Q to R and R to S, are [2017] cyclooctatetraene, furan, cycloheptatriene
(a) Aromatic sulfonation and Friedel-Crafts acylation 49. How many products are formed from the monobromination
(b) Friedel-Crafts alkylation and Friedel-Crafts acylation
of ethylcyclohexane (excluding stereoisomers)
(c) Friedel-Crafts alkylation, dehydration and Friedel-
Crafts acylation CH2CH3
(d) Dehydration and Friedel-Crafts acylation
Passage - VIII
Treatment of benzene with CO / HCl in the presence of
anhydrous AlCl 3 / CuCl followed by reaction with 50.
Et Et
Ac 2 O / NaOAc gives compound X as the major product. + HBr Products
R 2O 2
Compound X upon reaction with Br2 / Na 2 CO 3 followed Me Me (per – oxide)
by heating at 473 K with moist KOH furnishes Y as the

major product. Reaction of X with H 2 / Pd − C , followed How many products will be formed in above reaction
by H 3 PO 4 treatment gives Z as the major product .
Matrix Match type questions
44. The compound Y is [2018]
OH
In this section each question has some statements (A, B, C, D,...)
Br given in Column-I and some statements (p, q, r, s, t,...) in
COBr
Column-II. Any given statement in Column-I can have correct
(a) (b)
HO O matching with ONE OR MORE statement(s) in Column-II. For
example, if for a given question, statement B matches with the
Br statements given in q and r, then for that particular question against
statement B, darken the bubbles corresponding to q and r in the
COBr
ORS. i.e. answer will be q and r.
Br
(c) (d) ...
45. The compound Z is [2018]

...
(a) (b)
O O
Hydrocarbons | 154
51. Each of the compounds given in Column-I with the Column-I Column-II
reaction(s) that they can undergo, given in Column-II.
[2009] Compound Structure
Column-I Column-II (A) C8 H 18 with only 1º H (p)
Br (p) Nucleophilic atoms
(A) substitution
O (B) C6 H12 with only 2º H (q) Me Me
OH (q) Elimination
(B) Me
atoms Me
Me Me
CHO (r) Nucleophilic
(C) addition (C) C6 H12 with only 1º and (r)
OH
2º H atoms
Br (s) Esterification with
(D) acetic anhydride (D) C8 H 14 with 12 secondary (s)
NO2
(t) Dehydrogenation and 2 tertiary H atoms
Me
52. Match the reactions in Column-I with appropriate type of
Me
steps/reactive intermediate involved in these reactions as
given in Column-II. [2011]
Column-I Column-II 54.
H3C O Column-I Column-II
(A) O
Reactant and Reagent
aq NaOH
⎯⎯ ⎯ ⎯→ (p) Nucleophilic
substitution product
O
(A) ? (p) Alkaline KMnO4
?
(B) (q) HI + P
O
(B) (C) (r) AlCl 3 + HCl at
?
(q) Electrophilic
CH2CH2CH2Cl 298 K
O substitution OH
(D) ? (s) NH2 .NH2 + EtO

O
CH3
O (E) Cl (t) AlCl 3 at 570 K

?
(C) CH2CH2CH218OH (r) Dehydration

18
O (u) Zn − Hg / HCl
55. Match the following fractional compounds of petroleum

obtained on fractional distillaties
CH2 CH2 CH2 C (CH3)2 Column-I Column-II
OH Fraction of Composition of carbon

(D) (s) Nucleophilic
petroleum
addition
(A) Gasoline (p) C10 − C13
H3C CH3
(B) Kerosene oil (q) C 30 onwards
(t) Carbanion
(C) Diesel oil (r) C18 − C30
53. Match the compounds in Column-I with their
structure/characteristic/reaction/stereochemistry etc. given (D) Paraffin wax (s) C7 − C9
in Column II.
(E) Bitumen (t) C13 − C18
Hydrocarbons | 155
56. 58.
Column-I Column-II
Column-I Column-II
Reactions Products
Reactions, reagents, and products Name of
(A) (p) OH
reaction H O
PhCO3H OH
(A) COONa (p)
Me Cyclo
Me or MMPP + H3O
Electrolysis H
O
Me aq. Soln. addition
COONa Me
reaction (B) (q)
+ CO2 + H2 H
Aq. H COOH + CO2
KMnO4
(B) Br Br (q) Kolbe’s
+ Mg + MgBr2 (C) (r)
electrolytic H H
Acidic
OH
reaction OH
KMnO4
(C) 1. Li CH3I (r) Electrocyclic

Me Cl (C2H5)2 CuLi (D) H (s)
2. CuI Me Me HOOC COOH + CO2
reaction Hot
Alk.KMnO4
(D) CHCl 3 ⎯⎯⎯

3 SbF
→ CHF2 Cl (s) Freud
HF (E) H (t) CO2
reaction CrO3
+CH3COOH
(E) ∆ (t) Swart’s
Me Br
+ NaI
+ NaBr 59.
Acetone Me I
reaction Column-I Column-II
Reactions Products
(F) hv (u) Finkelstein
(A) Br (p) But –1 – yne
reaction (1) 3 NaNH2
Br (2)H3O+
Me
(G) (v) Corey –

+ (B) Br (q) But–2–yne
House (1) 2 KOH(s)
synthesis Br
Me
57. (C) 
Bromoform + Ag ⎯⎯→ (r) Ethyne
Column-I Column-II
(Reactant and (Reagents) (D) Br Br
NaI
(s) Propyne
product) Acetone
Br Br
(A) ? (p) KI + Acetone
(E) Me Br
Br Br Mg + EtOH
Br Br
(B) (q) Zn + CH 3 COOH
Br
? 60.
Column-I Column-II
(C) Me Me (r) EtOK + EtOH Reactions Products
Br
(A) 2 mol of ethyne ⎯⎯⎯→ CuCl (p) H H
? NH 4 Cl
(B) Cu 2+
(q)
2 mol of ethyne ⎯⎯⎯→ H
O2
(D) Me (s) ONa OH
Br + 1 mol
(C) (r)
H HCl
?
Cl
(D) H H (s) H
(E) Cl (t) NaOH + CH 3 OH (1) 1 mol HCl
(2)H2 + Ni2B
Cl
?
Cl
Hydrocarbons | 156
15. Hydrocarbons – Answers Keys
1. Alkane 3. Alkyne
1 d 2 b 3 a 4 c 5 b 1 b 2 a 3 c 4 a 5 c
6 c 7 c 8 d 9 c 10 c 6 a 7 a 8 b 9 c 10 c
11 d 12 a 13 b 14 a 15 c 11 b 12 a 13 a 14 d 15 c
16 a 17 d 18 a 19 a 20 b 16 c 17 c 18 a 19 c 20 c
21 a 22 a 23 b 24 a 25 a 21 a 22 d 23 b 24 d 25 c
26 a 27 b 28 a 29 c 30 d 26 d 27 c 28 a 29 a 30 b
31 d 32 d 33 d 34 d 35 a 31 d 32 a 33 b 34 a 35 b
36 d 37 c 38 c 39 a 40 c 4. Aromatic Hydrocarbon
41 d 42 a 43 c 44 d 45 c 1 d 2 b 3 c 4 b 5 c
46 b 47 b 48 c 49 a 50 a 6 b 7 c 8 c 9 a 10 b
11 b 12 c 13 d 14 b 15 b
51 c 52 d 53 b 54 d 55 b
16 c 17 a 18 b 19 c 20 d
56 c
21 a 22 d 23 a 24 d 25 a
2. Alkene
26 c 27 d 28 c 29 b 30 b
1 a 2 a 3 d 4 a 5 c
31 d 32 c 33 c
6 c 7 b 8 d 9 a 10 b
5. IIT-JEE/ AIEEE
11 c 12 c 13 a 14 d 15 c
1 b 2 d 3 c 4 a 5 c
16 a 17 a 18 a 19 a 20 b 6 a 7 c 8 b 9 d 10 c
21 d 22 a 23 d 24 d 25 a 11 a 12 c 13 b 14 c 15 d
26 d 27 d 28 c 29 a 30 d 16 b 17 c 18 a 19 c 20 c
21 a 22 c 23 d 24 b 25 a
31 d 32 a 33 a 34 b
26 a 27 c 28 c 29 b 30 a
31 c 32 d 33 c 34 a 35 c
Hydrocarbons | 157
36 c 37 a 38 c 39 b 40 b
41 a 42 a 43 c 44 a 45 a
46 a 47 b 48 a 49 c 50 a
51 b 52 d 53 c 54 c 55 a
56 a 57 c 58 c 59 c 60 c
6. JEE Advanced
1 bcd 2 bcd 3 abcd 4 bcd 5 abcd
6 abc 7 acd 8 bc 9 abc 10 bc
11 abcd 12 ad 13 bd 14 b 15 acd
16 ad 17 bd 18 a 19 a 20 c
21 d 22 b 23 a 24 c 25 c
26 d 27 b 28 a 29 d 30 a
31 b 32 d 33 b 34 d 35 a
36 c 37 d 38 c 39 c 40 bd
41 d 42 b 43 b 44 c 45 a
46 5 47 4 48 5 49 6 50 4
51 A→ p, q, t; B→ p, s, t; C→ r, s; D→ p
52 A→ r, s, t; B→ p, s; C→ r, s; D→ q, r
53 A→ q; B→ r; C→ s; D→ p
54 A→ r, t; B→ r, t; C→ p; D→ q, s, u; E→ q
55 A→ s; B→ p; C→ t; D→ r; E→ q
56 A→ q; B→ s; C→ v; D→ t; E→ u; F→ r; G→ p
57 A→ s; B→ r, t; C→ r, t; D→ s; E→ p, q
58 A→ r; B→ p; C→ t; D→ s; E→ q
59 A→ p; B→ q; C→ r; D→ r; E→ s
60 A→ q; B→ p; C→ r; D→ r
Hydrocarbons | 158
16. Environmental Chemistry
Change in physical, chemical or biological characteristics of air, water and land that has the potentiality to harm human life, lives of other
desirable species, industrial processes, living conditions, cultural assets and natural resources is called pollution.
Effects of pollution is first and most marked on natural flora of a place.
Pollutant
Pollutant is a substance (e.g., fly ash), chemical (e.g., ozone, nitrogen oxides) or factor (e.g., radiation, noise, heat) which has the
potentiality to harmfully affect human life, lives of other desirable species, industrial processes, cultural assets and natural resources.
Pollutants are divisible into several categories. The important ones are as follows:
Primary Pollutant
Pollutant persisting in the environment in the form it is produced e.g., carbon monoxide.
Secondary Pollutant
Pollutant formed from a primary one through change or reaction. Nitrogen oxides and hydrocarbons react photochemically to
produce peroxyacyl nitrates and ozone. The secondary pollutants may be more toxic than the primary ones. The phenomenon is
called synergism.
Qualitative Pollutant
The pollutant is a harmful substance, chemical or factor that does not occur in nature but is added by human beings, e.g., insecticide,
herbicide.
Quantitative Pollutant
It is a normal component of nature that becomes pollutant when its concentration becomes higher than the normal, e.g., nitrogen
oxides, carbon monoxide.
Degradable Pollutant
The pollutant degrades after some time either automatically (e.g., heat) or through the agency of microorganisms (= biodegradable,
e.g., sewage, livestock wastes, market garbage). Biodegradable pollutants are easily disposed off or degraded through natural
processes or waste treatment plants. They can be turned into a resource, e.g., compost, manure.
Non-Degradable Pollutant
It is a pollutant which does not breakdown or get converted to harmless state by natural processes of dissipation, dispersal, oxidation
or biological decomposition, e.g., DDT, glass, plastic. It is also known as conservative or persistent pollutant.
Types of Pollution
Natural Pollution
It is pollution caused by natural sources, e.g., volcanic eruptions, release of methane by paddy fields and cattle, release of carbon
monoxide by plants and animals, emission of natural gas, ozone, nitrogen oxides, soil erosion, dust storms, cosmic rays, ultra-violet
rays, etc.
Anthropogenic or Man-Made Pollution
It is pollution caused by human activities like noise, automobiles, industries, smoking, pesticides etc. Anthropogenic pollution is
often quite small in quantity as compared to natural pollution. Example, 0.05% of atmospheric pollution is man-made while 99.95%
is natural pollution.
On the basis of source of pollution, it can be air, water, land, radioactive and noise pollution.
Environmental Chemistry | 160

Air Pollution
Air or atmospheric pollution is the addition of materials or chemicals into atmosphere in such concentration that they begin to
exert adverse effect on human beings, other desirable species, human assets and resources. Total amount of air pollutants is
estimated to be 1 × 1012 tonnes, out of which pollutants added by human activities are only 5 × 10 8 tonnes or 0.05%.
Types of Air Pollutants
• Primary Air Pollutants
Air is polluted by poisonous gases and undesirable substances. They are released by burning fossil fuels. These substances
are called primary air pollutants. For example:
a) Soot released from unburned fuel.
b) Sulphur dioxide (SO2).

c) Benzopyrene (hydrocarbon) released from cigarette smoke.
d) Ammonia (NH3).
c) Oxides of nitrogen.
e) Carbon monoxide (CO).
f) Lead (Pb).
• Secondary Air Pollutants
Secondary air pollutants are poisonous substance formed from primary air pollutants. In bright sunlight nitrogen, nitrogen
oxides, hydrocarbons and O2 interact to produce more powerful photochemical oxidants like ozone (O3), peroxyacetyl
nitrate (PAN), aldehydes, sulphuric acid, peroxides, etc. All these constitute photochemical smog, which retard
photosynthesis in plants. PAN causes eye burning and checks hill reaction of photosynthesis.
Causes of Air Pollution
• Agriculture : Hydrocarbons released by plants, pollen grains, insecticides etc. cause air pollution.
• Dust : Dust in the air is increased by dust storms wind, volcanoes, automobiles, etc.
• Industries : Combustion of fossil fuels like coal, petroleum, etc. Industrial smoke is the main source of pollution.
• Automobiles : The combustion of petrol and diesel in automobiles releases harmful gases into the air. They also produce dust.
• Ionising Radiations : Ionising radiations include alpha particles, beta particles and gamma rays. They are released into
the air on testing atomic weapons.
• Freons : Use of freons and other chloro-fluoro-carbon compounds in refrigerants, coolants etc. cause pollution.
• Aerosols : Chemicals released in the atmosphere with force in the form of mist or vapours are called aerosols. Jet-
aeroplanes release aerosols which contain CFC. Aerosols are small particles of all sorts of solid or liquid substances
suspended in the air. They block the stomata of plants and prevent the gaseous exchange between plants and atmosphere.
They may also change the climate of an area. Aerosols reduce primary productivity by destroying leaf tissue, premature leaf
fall, reducing crop yields.
Biological Indicators
Some plants are sensitive to certain air pollutants. These plants are used to indicate the presence of these substances. These
plants are called biological indicators e.g.,
• The tissues present in the tip of dusheri mango turns black when they are exposed to sulphur dioxide (SO2) fumes.
• Pinto beans and Petunias are used to indicate the presence of peroxy acetyl nitrate (PAN).
• Tobacco and annual blue–grass plants are used to show the presence of ozone (O3). Lichens are biological indicators of air
pollution caused by SO2.
Ecological Effects of Air Pollution
• Death : When air is polluted with poisonous gases, death comes as a result immediately. Bhopal episode is a good example.
Bhopal episode – On 2nd December 1984 about 3000 human beings died, due to the leakage of methyl isocyanate (toxic
gas) into the air from an insecticide plant managed by Union Carbide Corporation.

• Chlorosis : The disappearance of chlorophyll is called chlorosis. It is caused by SO2, nitrogen dioxide, ozone and fluorides.
• Necrosis : The breakdown of cells is called necrosis. It is caused by SO2, nitrogen dioxide, ozone and fluorides.
• Crop Losses : Heavy loss of crop is caused by smog. Smog denotes a combination of smoke and fog. The important
components of smog are ozone and PAN (peroxy acetyl nitrate). They damage leafy vegetables, cereals, textile crops,
ornamental plants, fruits and forest trees.
• Deterioration of Buildings : SO2 also has adverse effect on buildings, sculptures, painted surfaces etc, where it causes
discolouration and deterioration. Yellowing and blackening of Taj Mahal at Agra is due to SO2 and other pollutants released
by Mathura refinery which is called ‘Stone cancer.’
• Respiratory Disorders : Excessive ethylene accelerates respiration causing premature senescence (old age) and
abscission (accumulation of yellow fluid (pus) in the body). Aldehydes irritate nasal and respiratory tracts. Chlorine and
phosgenes (carbonyl chloride) cause pulmonary oedema. Bronchitis is another bad effect of air pollution.
• Jaundice : Arsines induce RBC breakdown and jaundice.
• Oxygen Carrying Capacity : CO reduces O2 carrying capacity of RBC by its permanent combination with haemoglobin.
• Silicosis : It is caused by inhalation of dust containing free silica or silicon dioxide especially by workers engaged in mining,
ceremic industry, sand blasting and construction industries.
Some Important Ecological Effects
• Green House Effect : The green house effect was first described by the French Mathematician J. Fourier in 1827. Due
to heavy industrialization and transportation (modernization), CO2 concentration is increasing day by day in the
atmosphere. CO2 has capacity of absorbing heat radiations and thus increases temperature. This increase in global
temperature (global warming) mainly due to CO2 concentration is called green house effect. Besides CO2 , other important
gases associated with green house effect are CH 4 (methane), oxides of nitrogen ( NO x ) , CFC (chlorofluorocarbons)
and O3 (ozone) and these called ‘green house gases’.
It is estimated that by the end of 2100 A.D., atmospheric temperature will be increased by 1-5°C. As a result of
increase in global temperature, the ice caps will melt and all coastal cities will be under water.
• Depletion of Ozone Umbrella
In the atmosphere, about 30 km above the surface of the earth, the ozone molecules (O3) form an umbrella. It prevents the
penetration of harmful ultra violet radiation from the sun and thus protects the life of the earth. It is now feared that there is
danger of depletion of the ozone umbrella, which may occur by the use of freons and other CFC-compounds in refrigerants,
coolants in domestic refrigerators and cold storage facilities, and as filling agents in the form of plastics and in aerosol
packages. On reaching the ozone umbrella, they destroy ozone molecules as a result of photochemical reactions. A hole in
O3 layer has been discovered in Antarctica.
• Acid Rain
One of the major environmental issues facing human society at the national and international level is the problem of rain
water having low pH. The rainwater is always slightly acidic as CO2 in the atmosphere gets dissolved in it. However during
recent years, it has been noted a further lowering of pH of rain water often as low as 2.4. This lowering of pH is due to the
dissolution of acids in the rain water. Precipitation of oxides of sulphur and nitrogen with rain is termed acid rain. Acid rain
is caused by air pollution. When atmospheric air contains sulphur dioxide (SO2) and oxides of nitrogen such as nitrous
oxide (N2O) and nitric oxide (NO), they dissolve in rain water forming sulphuric acid and nitric acid. The rain water falls as
acid rain. Ingredients of acid rain are 65% H 2SO4 , 30% HNO 3 and 5% HCl.
Acid rain affects both materials and organisms. It attacks building materials principally sandstone, limestone, marble, steel
and nickel. In plants, it leads to chlorosis or depigmentation of leaves.
Acid rain increases the acidity of lakes and rivers. Vast tracts of forests and lakes in Europe and North America have been
destroyed by acid rain. Acidity kills fish, bacteria and algae and the aquatic ecosystem collapses into sterility leaving a crystal
clear but ultimately a dead lake.
Control of Air Pollution
• The emission of exhaust from automobiles can be reduced by devices such as positive crankcase ventilation valve and
catalytic converter.

• Electrostatic precipitators can reduce smoke and dust from industries.
• Gaseous pollutants arising from industries can be removed by differential solubility of gases in water.
• A fine spray of water in the device called scrubber can separate many gases like NH3, SO2, etc. from the emitted exhaust.
• Vehicles based on compressed natural gas (CNG) should be used more.
Water Pollution
Water pollution is degradation of quality of water due to addition of substances (e.g., silt), chemicals (e.g., metals, inorganic and
organic chemicals) or factors (e.g., heat) and deprivation that makes it a health hazard, unfit for human use, use by animals and
industries as well as growth of aquatic biota. Water pollutants belong to three categories – biological, chemical and physical.
Biological
Various pathogens, e.g., viruses, bacteria, protozoa, helminthes, algae.
Chemical
Organic wastes, organic biocides (e.g., DDT, BHC) and polychlorinated biphenyls (PCBs), inorganic chemicals like As, Pb,
Cd, Ni, Hg, phosphates, nitrates, fluoride, etc.
Physical
Hot water, oil spills.
Water Pollution is of two Types, Natural and Anthropogenic
Natural Water Pollution
It is water pollution caused by natural processes of soil erosion and addition of clay or silt, run off and leaching.
Anthropogenic or Man-Made Pollution
It is water pollution caused by human activities like industrial effluents, domestic sewage, waste from animal sheds and slaughter
houses, detergents, pesticides and fertilizers, oil spills, etc.
Causes of Water Pollution
• Domestic Sewage
Domestic sewage consists of human faeces, urine, and the dirty used–up water in houses. It contains a large number of
bacteria and virus. The sewage is released into the rivers on the banks of which most of the cities are situated. Domestic
waste contains biodegradable pollutants. The high amount of E. coli in water is the indicator of sewage pollution.
• Industrial Effluents
All industrial plants produce some organic and inorganic chemical wastes. These non-usable chemicals are dumped in water
as a means of getting rid of them. The industrial wastes include heavy metals (Hg, Cu, lead, zinc etc), Detergents, Petroleum,
Acids, Alkalies, Phenols, Carbonates, Arsenic, Chlorine, etc.
• Thermal Pollution
Hot effluents and hot water (e.g., thermal plants/atomic reactors) bring about rise in water temperature. Warm water contains
less oxygen, has lower rate of putrescibility resulting in increased organic loading, replacement of green algae by blue-green
ones. Many animals fail to reproduce e.g., Trout, Salmon.
• Run off from Agricultural Fields
It is of three types – animal wastes, fertilizers and pesticides. Phosphate pollution is caused by sewage and agricultural
fertilizers.
• Radioactive Wastes
Liquid radioactive wastes are released into the sea around nuclear installations. The oceanic currents carry the radioactive
contaminants everywhere.
• Oil Pollution
Oil is a source of pollution in sea-water. Oil pollution is due to ship accidents, loading and discharging of oil at the harbour,
oil refineries and off-shore oil production.
• Eutrophication
Rich growth of micro-organisms consumes most of the dissolved oxygen, so as to deprive other organisms. It generally
occurs at the bottom layers of deep lakes. Addition of excessive plant nutrients intensifies eutrophication. It is harmful to fish
and other aquatic life.
Effect of Water Pollution
• Chemical Pollutants
Many chemicals present in industrial effluents are poisonous causing various types of deformities, e.g., mercury (minimata
disease first reported in 1952 due to eating of fish captured from Hg-contaminated Minimata Bay of Japan), lead
(plumbism), cadmium (itai-itai, ouch-ouch, first reported in 1947 in Toyoma city of Japan) nickel, arsenic, chromium,
etc.
Some chemicals like acids contained in industrial effluents are corrosive. They damage water treatment plants.
Persistent pesticides enter food chains, undergo bio-magnification and harm the aquatic life as well as land animals
dependent on it.
Organic sulphur inhibits nitrification.
a) Odour
Free chlorine, ammonia, hydrogen sulphide, phenols, growth of algae and microorganisms produce unpleasant
odour.
b) Turbidity
Water becomes muddy or turbid due to suspension of mineral dust, silt and related colloidal particles. Turbidity hinders
penetration of light. It causes clogging of gills in fishes. Therefore, both plant and animal life is destroyed. Turbid
water is also not suitable for drinking or industrial use.
c) Colour
Dyes, iron and chromium compounds and anaerobic decomposition cause colouration of water. The coloured water
is not suitable for recreational, drinking and industrial uses.
d) Taste
It is impaired due to occurrence of pollutants like free chlorine, phenol, iron, manganese, detergents, hydrocarbons,
oils and decomposition products.
e) Foam
It develops over the surface of water due to mixing of detergents, soaps and alkalies. Foam makes the water unfit for
various human uses.
• BOD & COD of Water
Biochemical Oxygen Demand (BOD) is the amount of dissolved oxygen needed by aerobic biological organisms to break
down organic material present in a given water sample at certain temperature over a specific time period. The BOD value
is most commonly expressed in milligrams of oxygen consumed per litre of sample during 5 days of incubation at 20 °C and
is often used to measure the degree of organic pollution of water.
BOD can be used as a gauge of the effectiveness of wastewater treatment plants.
BOD is similar in function to chemical oxygen demand (COD), in that both measure the amount of organic compounds in
water. However, COD is less specific, since it measures everything that can be chemically oxidized, rather than just levels of
biodegradable organic matter.
Soil Pollution or Land Pollution
It is alteration in soil caused by removal or addition of substances and factors which decreases its productivity, quality of plants and
ground water.
Negative Soil Pollution
It is reduction in soil productivity due to erosion and over use.

Positive Soil Pollution
It is reduction in soil productivity due to addition of undesirable substances.

Soil pollution is direct if the pollutants are passed over it directly e.g., industrial effluents, fertilizers. It is indirect if the pollutants
reach soil from other resources like air and water, e.g., acid rain.
Sources of Pollution
The main sources of land pollution are pesticides, radioactive elements and fertilizers.
• Pesticides
Pesticides are the chemical substances which contaminates our food as well as drinking water. Their major role is to kill or
block the reproductive processes in organism which are not needed and thus, save the soil from pests. Pesticides have been
divided into three types:
a) Insecticides : These are the chemical substances which protect the crops from various insects. The best known
insecticide is D.D.T. (Dichloro diphenyl trichloro ethane) and B.H.C. (Benzene hexachloride). These insecticides
accumulate in the environment and affect many non target organisms, not just the target pests.
b) Herbicides : These are made to kill weeds. Common herbicides are sodium chlorate (NaClO3) and sodium arsenite
(Na3AsO3). But these are toxic towards mammals also. At present organic herbicides like trazines are used as weed
killers and have no adverse effect on human beings.
c) Fungicides : Fungi are the plant without chlorophyll. Thus, fungi do not play any role to convert carbondioxide and
water into carbohydrates by making use of solar energy. The general fungicides are the compounds of mercury. But
these are of poisonous nature and many death have been reported all over the world by the use of these fungicides.
• Ecological Effects of Pesticides
a) Mutation : Insecticides induce gene mutation in human beings (Wurster, 1974).
b) Cancer : DDT produces cancer in human tissues.
c) Congenital Birth Defects : Certain herbicides like diozan increase birth defects in both people and livestock.
d) Calcium Metabolism : DDT interferes with calcium metabolism resulting in calcium deficiency. DDT causes
hormonal disturbances resulting in delayed ovulation and inhibition of gonad development.
e) Biomagnification : The pesticides are non–degradable. They have much affinity towards fat. Hence they tend to
move into the living organisms. They are concentrated as they pass up the food chains. For example, at each trophic
level, the accumulation of insecticides increases by 10 times. For example if the goat gets one part per million (PPM)
of DDT from the grasses, it will have 10 ppm in its tissues. The man, eating the goat will have 100 ppm. The man-
eating tiger will have 1000 ppm. If the food chain is still greater, the accumulation will still be higher. This increasing
accumulations of insecticides in higher organisms is called biomagnification or biological amplification.
f) Fertilizers
Excessive use causes soil deterioration through decrease of natural microflora. Leaching down causes pollution of
underground water (third poison). Salts entering crop plants in excess may prove harmful.
Excessive use of nitrogen fertilizers has increased levels of nitrates in soil, which is responsible for ‘blue baby
syndrome’. From soil, these nitrates go to leaves and fruits and then to human beings. In alimentary canal, bacteria
convert nitrates into toxic nitrites, which combine with haemoglobin of blood to form methaemoglobin due to which
oxygen transport is reduced.
g) Radio Active Elements
They are present in ores, coal, waste of mineral purification and uranium mines, etc. A lot of radio -isotopes are
also used in research and medicine. Despite best precautions some radio-nuclides constantly enter soil and are
transferred to food chain.
Control of Soil Pollution
Soil pollution caused by solid wastes can be corrected by the following methods.
• Salvage : Articles which can be recycled should be removed from garbage, e.g., metals, glass, polythene, paper, rags, etc.
It provides employment to rag pickers and helps in recycling of wastes.

• Construction Material : Flyash is being converted into bricks for construction work. Flyash, industrial effluents containing
toxic chemicals and hazardous metals can be used as bedding material for road construction.
• Dumping (Landfilling) : Dumping is piling of waste on selected low lying land.
• Pyrolysis : The waste is heated anaerobically at a temperature of 1650°C. It yields industrial gas, alcohols and a number
of other chemicals. The bulk of the waste is reduced. Residue is disposed off in land-fill.
• Incineration : Waste is burnt aerobically at 900-1000°C. The hot gases and smoke are further passed into a chamber
where the temperature is 1300°C. It burns the smoke particles. Ash formed in incinerator is collected and disposed off in
land filling.
• Recycling of Wastes : Paper, glass, polythene and metals can be recycled. Though paper recycling is a bit costlier, it saves
a lot of wood. For example one ton of recycled paper saves 17 medium sized trees from felling. Recycling of metals not only
saves the scarce resource but is also cheaper and less polluting.
• Biogas Plants : Cow dung, human excreta and putrescible garbage can be mixed and used for generation of biogas.
Manure is produced as a by-product.
Radioactive Pollution
It is degradation of environment due to release of radioactivity (emission of -particles, -particles and gamma rays) by changes in
nuclides of unstable/radioactive elements causing short-range and long range harmful effects on living beings including humans.
Types of Radiations
• Background Radiation : It is radiation level found naturally in biosphere due to cosmic rays reaching earth and radio-
nuclides found in earth's crust. Maximum background radiation is found in Kerala beach where 75% of thorium deposits of
the world are found.
• Man-made radiations : They are due to mining and refining of radioactive elements like Plutonium, Uranium and
Thorium, nuclear power plants and fuels, preparation of radio-active isotopes, production and explosion of nuclear
weapons.
Nuclear Weapons
Radiations are released during atmospheric testing of nuclear weapons and their actual use. Atmospheric testing of nuclear
weapons has been banned because of release of destructive radiations. Nuclear weapons use uranium-235 and plutonium-
239 for fission (atom bomb) and additional hydrogen or lithium for fusion (hydrogen bomb). A nuclear explosion gives rise to
radioactive gaseous matter rising up as a mushroom like cloud that disperses later on to spread radioactivity far and wide,
polluting air, water and soil of all the places. Radioactivity passes into food chains and affects the whole biota.
• Atomic Reactors
They employ controlled radioactive fission or fusion for liberation of energy.
a) The coolant water causes thermal pollution.
b) Small amount of radioactivity enters coolant water which undergoes biomagnification to some 75000 times in birds.
c) Mishaps do occur in nuclear reactors. One of the causes is core melting, e.g., Chernobyl in Ukraine (26 April 1986).
• Radio-Isotopes
They are used in research (e.g., metabolic pathways, induction of mutations in plants and microorganisms, radiotherapy,
etc.) e.g., Co-60, P-32, C-14, I-125.
• X-rays
They are employed for detecting diseases of lungs, heart, kidneys, joints and fractures. Repeated exposure to X-rays is
harmful. Radiologists are prone to radiation disorders.
• Types of Radiations
This pollution occurs through radiations. Radiations are of two types.

a) Non Ionising Radiations : UV rays, IR rays, etc. UV rays cause skin burning, IR rays increase atmospheric
temperature and leads to the green house effect.
b) Ionising Radiation :  – rays,  -rays,  -rays, X − rays cause genetic injury on mutation.
• Harmful Effects
Many plants are killed even at low level of radioactivity. Young and recently divided cells are more easily damaged. The
most adverse effect of radioactive pollutant is gene mutation.
a) Short Range Effects : Loss of nails and hair, subcutaneous bleeding, changed proportion of blood cells, changed
metabolism, damage to all organs, death in high dose.
b) Long Range/ Delayed Effects : Tumours, cancers, mutations, genetic deformities, shorter life span.
Control of Radiation Pollution
There is no cure for radiation damage. Therefore, the only solution is prevention of radioactive pollution.
• Waste Disposal
a) Substances with very low radiation level can be discharged into municipal sewers.
b) Low activity wastes should be stored for sometime as to reduce their activity further before final disposal.
c) Radionuclides should be separated through precipitation, coagulation or concentration. The concentrated wastes are
then changed into glass, ceramic or concrete. This transforms the radioactive waste into non-absorbable and un-
leachable form. The locked waste is then put in concrete filled drums which are sealed and buried in sea at least 1000
fathoms deep.
Noise Pollution
Noise is unwanted annoying sound of generally 80 dB and above. Audible sound is having intensity of 0 dB. Scooters, Cars etc,
have intensity of sound upto 60 dB. Aeroplanes etc, have intensity of sound as 80–100 dB whereas jet aeroplanes have intensity of
120 dB. It is a physical non-persistent pollution which affects the receiver directly. Upto a certain limit, the effect depends upon the
mood and upbringing of the person.
Table 16.1 Noise Levels in Decibel.
Noise Levels (in decibels) Average noise levels in some

major cities
Threshold of hearing 1 Delhi 90 – 95 dB
Normal breathing 10 Kolkata 100 dB
Whispering 30 Mumbai 80 – 90 dB
Quiet office 40 Kanpur 90 – 100 dB
Homes 45 Level of noise recommended
Normal conversation 50 Residence 25 – 30 dB
Automobiles 70 Living Room 35 – 45 dB
Heavy Automobiles 100 Library 30 – 40 dB
Jet air craft 150 Bed Room 40 dB
Thunder Clap 120 Class Room 40 – 50 dB
Hooting of trains 130 Hospitals 25 – 35 dB
Rocket Engine 180 Work Shop 55 – 75 dB
Effects
• Damage to ear drum and impairment of hearing (a ten year exposure to 80 dB impairs hearing by 15 dB).
• Emotional disturbance, development of anxiety and stress (first effect).
• Damage to eye sight, colour perception, night vision, etc.

• Hypertension, changes in peripheral circulation and breathing pattern, decreased heart output and gastric problems.
• Startle reaction.
• Headache, sleeplessness, annoyance and irritability.
• Reduced productive performance.
Control of Noise Pollution
The various methods of controlling noise pollution are as follows :

• Sound Absorption : The sound entering residential areas and dwelling units should be reduced. Acoustic furnishing should
be undertaken to absorb sound and reduce noise pollution.
• Sound Diversion : High intensity sound should be deflected away from residential areas.
• Quieter Machines : Efforts should be made to develop quieter machines.
• Loud Speakers : Their use should be restricted. Under no condition the sound level be raised above 90 dB during the day
and 60 dB during the night.
• Occupational Exposures : In case a person works in industry producing high intensity sound, ear plugs and ear muffs
should be used for protection of ears.
• Traffic : Highway traffic is not allowed to pass through towns and cities. It is diverted through by passes and over-bridges.
Pressure horns are not allowed inside towns and cities.
• Green Muffler : 4 – 5 rows of trees and shrubs are grown along roads, rails, around industrial area and residential
complexes in order to decrease the intensity of sound.
Green Chemistry
Green chemistry is also called as sustainable chemistry or it is an alternative tool for reducing pollution. By green chemistry we mean "The
production of substances in everyday life use by chemical reactions which neither employ toxic chemicals nor release the same to the
atmosphere.
Important Principles
It is good to prevent waste then to treat waste after it is formed.
Synthetic methods should be made to maximize the incorporation of all materials used in the process into the final product.
Chemical substances should be made to preserve efficiency of function while reducing toxicity.
The use of solvents and separating agent should be avoided as far as possible.
Chemical substances should be made so, that at the end of their function they do not persist in the environment and should
break down into harmless degradation products.
Achievements of Green Chemistry
A commonly used dry cleaning agent is tetrachloro ethene (Cl 2 C = CCl 2 ) . It pollutes water and is also carcinogenic. This has
been replaced by some other detergents which contain liquid carbondioxide. These agents do not pollute water and give better
results.
Ionic catalysts in the form of Pd +2 and Cu +2 salts have been used for the formation of acetaldehyde (ethanal) from ethene
by carrying oxidation with oxygen. The yield of ethanal is excellent (about 90%).
Bleaching powder is commonly used in laundries for bleaching clothes. Now it is replaced by hydrogenperoxide and needs
less amount of water.
Development of a new method of synthesizing ibuprofen with a 99% yield avoiding the usage of large quantities of solvents
and wastes associated with the traditional stiochiometric use of solvents and separating agents.

16. Environmental Chemistry– Multiple Choice
Questions
7. Most harmful pollutant is
Air Pollution
(a) CO2 (b) SO3
1. Which of the following strategy is not a correct approach to
(c) NO2 (d) CH4
reduce global warming
(a) Reducing the green house gas emission by limiting the use (e) SO2
of fossil fuels 8. Most hazardous metal pollutant of automobile exhaust is
(b) Increase the vegetation cover particularly the forest for
(a) Mercury (b) Lead
photosynthetic utilization of CO2
(c) Minimizing the use of nitrogen fertilizers in agriculture for (c) Cadmium (d) Copper
reducing N2O emission 9. This pollutant causes burning sensation of throat and eyes and
(d) Increasing the use of air conditioners, refrigeration unit vomiting sensation
and production of plastic foams and propellants in aerosol
(a) Hydrogen sulphide (b) Sulphur
spray cans
(c) Hydrogen cyanide (d) Arsenic substances
(e) Developing substitutes for chlorofluorocarbons
2. It is said, the Taj Mahal may be destroyed due to 10. Which of the following is most poisonous
(a) Flood in Yamuna river (a) CO (b) CO 2
(b) Decomposition of marble as a result of high temperature

(c) C (d) SO 2
(c) Air pollutants released from oil refinery of Mathura
11. In almost all Indian metropolitan cities like Delhi, the major
(d) All the above
atmospheric pollutant(s) is/ are
3. Carbon monoxide (CO) is harmful to man because
(a) Suspended particulate matter (SPM)
(a) It forms carbolic acid
(b) Oxides of sulphur
(b) It generates excess CO2
(c) Carbon dioxide and carbon monoxide
(c) It is carcinogenic
(d) Oxides of nitrogen
(d) It competes with O2 for haemoglobin
4. What are the chief pollutants of the atmosphere which are 12. How carbon monoxide, emitted by automobiles, prevents
most likely to deplete the ozone layer transport of oxygen in the body tissues
(a) Sulphur dioxide (a) By changing oxygen into carbon dioxide
(b) Nitrogen oxide and fluorocarbons (b) By destroying the haemoglobin

(c) Carbon dioxide (c) By forming a stable compound with haemoglobin
(d) Carbon monoxide
(d) By obstructing the reaction of oxygen with haemoglobin
5. The pollutants emitted by jet aeroplanes in outer atmosphere
13. Metal generally present in polluted air is
are known as
(a) Smog (b) Photochemical oxidants (a) Cadmium (b) Lead
(c) Aerosols (d) Loess (c) Mercury (d) Zinc
6. Which of the following group of gases cause photochemical 14. Which one of the following is not a device used to control a
smog particulate matter
(a) O 3 , PAN and CO (b) HC, NO and PAN (a) Arresters (b) Scrubbers
(c) O 2 , PAN and NO 2 (d) O 2 , PAN and NO 3 (c) Filters (d) Electrostatic precipitator
(e) O 3 , PAN and NO 2 (e) Incinerator

15. Which of the following statements is not true about classical 22. Which of the following gases is not a green house gas
smog
(a) CO (b) O3
(a) Its main components are produced by the action of
sunlight on emissions of automobiles and factories (c) CH 4 (d) H 2 O vapour
(b) Produced in cold and humid climate 23. Photochemical smog occurs in warm, dry and sunny climate.
(c) It contains compounds of reducing nature One of the following is not amongst the components of
photochemical smog, identify it
(d) It contains smoke, fog and sulphur dioxide
(a) NO2 (b) O3
16. Dinitrogen and dioxygen are main constituents of air but these
do not react with each other to form oxides of nitrogen (c) SO2 (d) Unsaturated hydrocarbon
because…….
24. Which of the following statement (s) is/are wrong
(a) The reaction is endothermic and requires very high
temperature (a) Ozone is not responsible for green house effect
(b) The reaction can be initiated only in presence of a catalyst (b) Ozone can oxidies sulphur dioxide present in the
(c) Oxides of nitrogen are unstable atmosphere to sulphur trioxide
(d) N 2 and O2 are unreactive (c) Ozone hole is thinning of ozone layer present in
stratosphere
17. The pollutants which come directly in the air from sources are
called primary pollutants. Primary pollutants are sometimes (d) Ozone is produced in upper stratosphere by the action of
converted into secondary pollutants. Which of the following UV rays on oxygen
belongs to secondary air pollutants 25. The gaseous envelope around the earth is known as
(a) CO (b) Hydrocarbon atmosphere. The lowest layer of this is extended upto 10 km
from sea level, this layer is
(c) Peroxyacetyl nitrate (d) NO
(a) Stratosphere (b) Troposphere
18. The chemical entities present in thermosphere of the
atmosphere are (c) Mesosphere (d) Hydrosphere
(a) O2+ , O + , NO + (b) O3 Water Pollution
(c) N 2 , O2 , CO 2 , H 2 O (d) O3 , O2+ , O2 1. Brewery and sugar factory waste alters the quality of a water
body by increasing
19. In a coal fired power plant electrostatic precipitators are
(a) Temperature (b) Turbidity
installed to control emission of
(c) pH (d) COD and BOD
(a) SO2 (b) NOx
(c) SPM (d) CO 2. When huge amount of sewage is dumped into a river, the
BOD will
20. Acid rain is caused by or recent reports of acid rain in some
industrial cities are due to the effect of atmospheric pollution (a) Increase (b) Remain unchanged
by (c) Slightly decrease (d) Decrease
(a) Excessive release of CO2 by burning of fuels like wood and 3. A dental disease characterised by mottling of teeth is due to
charcoal, cutting of forests and increased animal
presence of a certain chemical element in drinking water.
population
Which is that element
(b) Excessive release of NO2 and SO2 in atmosphere by
burning of fossil fuel (a) Boron (b) Chlorine
(c) Excessive release of NH3 by industrial plants and coal gas (c) Fluorine (d) Mercury
(d) Excessive release of CO in atmosphere by incomplete
4. The high amount of E. coli in water is the indicator of
combustion of coke, charcoal and other carbonaceous
fuel in paucity of oxygen (a) Hardness of water
21. 70% component of acid rain is (b) Industrial pollution
(a) HNO3 (b) H2SO4 (c) Sewage pollution
(d) Presence of chlorine in water

(c) HCl (d) CO2

5. Biological Oxygen Demand (BOD) is a measure of 13. Which of the following metal is a water pollutant and causes
sterility in human being
(a) Industrial wastes poured into water bodies
(a) As (b) Mn
(b) Extent to which water is polluted with organic compounds
(c) Mg (d) Hg
(c) Amount of carbon monoxide inseparably combined with
haemoglobin 14. Eutrophication is caused by
(d) Amount of oxygen needed by green plants during night (a) Acid rain
6. Black-foot disease is caused due to groundwater (b) Nitrates and phosphates
contaminated with excess of
(c) Sulphates and carbonates
(a) Nitrate (b) Fluoride
(d) CO2 and CO
(c) Arsenic (d) Sulphur
15. Which of the following damages WBC, bone–marrows and
(e) Mercury lymph nodes
7. B.O.D. is connected with (a) I131 (b) Ca40
(a) Organic matter (b) Microbes (c) Caesium (d) Sr90
(c) Both (a) and (b) (d) None of these 16. Excessive accumulation of organic matter in water bodies
leads to
8. Minimata disease first occurred in
(a) Decrease in species diversity
(a) Japan (b) China
(b) Increase in species diversity
(c) Korea (d) Russia
(c) Green house effect
9. Sewage containing organic waste should not be disposed in
water bodies because it causes major water pollution. Fishes (d) No effect on species diversity
in such a polluted water die because of
17. Biochemical Oxygen Demand, (BOD) is a measure of
(a) Large number of mosquitoes organic material present in water. BOD value less than 5
(b) Increase in the amount of dissolved oxygen ppm indicates a water sample to be
(c) Decrease in the amount of dissolved oxygen in water (a) Rich in dissolved oxygen
(d) Clogging of gills by mud (b) Poor in dissolved oxygen
10. The process of ‘eutrophication’ is due to (c) Highly polluted
(a) Increase in concentration of insecticide in water (d) Not suitable for aquatic life
(b) Increase in concentration of fluoride ion in water
Different Types of Pollution and Pollutants
(c) The reduction in concentration of the dissolved oxygen in
water due to phosphate pollution in water 1. The most adverse effect of radioactive pollutant is
(d) Attack of younger leaves of a plant by peroxyacetyl nitrate (a) Gene mutation (b) Hepatitis
(e) Increase in concentration of radioactive substances in (c) Polio (d) T.B.

water
2. U238 emits
11. Excess nitrate in drinking water can cause
(a) Gamma–rays (b) Beta–rays
(a) Methemoglobinemia (b) Kidney damage
(c) Liver damage (d) Laxative effect (c) Alpha–rays (d) None of these
(e) Leucoderma 3. Most important causative pollutant of soil may be
12. Minamata disease was caused due to the consumption of (a) Plastics (b) Iron junks
(a) Sea food containing lot of cadmium (c) Detergents (d) Glass junks
(b) Fish contaminated with mercury
4. Permissible noise levels in a residential area at night time is
(c) Oysters with lot of pesticide
(a) 35 db (b) 40 db
(d) Sea food contaminated with selenium
(c) 45 db (d) 50 db

5. Which of the following causes outbreak of jaundice 14. Which of the following pollutants affect more to organisms of
the higher trophic level of a food chain due to biological
(a) Air pollution (b) Water pollution
amplification
(c) Thermal pollution (d) Soil pollution (a) Sewage and plant fertilizers
6. Which of the following does not cause pollution (b) Detergents
(a) Hydroelectric schemes (b) Automobiles (c) Heavy metals mercury salts and non- biodegradable
phenolic chemicals
(c) Nuclear energy project (d) Thermal power project
(d) Poisonous cyanides
7. Which of the following practices will not come under green
15. Exposure of an organism to UV system causes
chemistry
(a) Photodynamic action
(a) If possible, making use of soap made of vegetable oils
(b) Formation of thymidine
instead of using synthetic detergents
(c) Splitting of H–bonds of DNA
(b) Using H 2O2 for bleaching purpose instead of using
(d) Splitting of phosphodiester bonds
chlorine based bleaching agents
(c) Using bicycle for travelling small distances instead of using IIT-JEE/ AIEEE
petrol/diesel based vehicles
1. In 1984, Bhopal gas tragedy was caused due to leakage of
(d) Using plastic cans for neatly storing substances [2013]
8. ‘Heat islands’ are produced due to (a) Sodium monoxide (b) Sodium thiocyanate
(a) Air pollution (b) Water pollution (c) Potassium isocyanate (d) Methyl isocyanate
(c) Land pollution (d) All of the above 2. Identify the wrong statement in the following [2008]
(a) Greenhouse effect is responsible for global warming
9. Green muffler is used against which type of pollution
(b) Ozone layer does not permit infrared radiation from the
(a) Air (b) Water sun to reach on the earth
(c) Soil (d) Noise (c) Acid rain is mostly because of oxides of nitrogen and
10. The term "Bio-magnification" refers to the sulphur
(d) Chlorofluorocarbons are responsible for ozone layer
(a) Growth of organism due to food consumption
depletion
(b) Increase in population size
3. Frequent occurrence of water blooms in a lake indicates
(c) Blowing up of environmental issues by man [2003]
(d) Increase in the concentration of non-degradable pollutants (a) Nutrient deficiency
as they pass through food chain (b) Oxygen deficiency
(e) Decrease in population size (c) Excessive nutrient availability
11. Which of the following is the use of lichens in case of pollution (d) Absence of herbivores in the lake
(a) They treat the polluted water 4. A water sample has ppm level concentration of following
anions
(b) They act as bioindicators of pollutions
F − = 10 ; SO42 − = 100 ; NO3− = 50
(c) They promote pollution
The anion/anions that make/makes the water sample
(d) Lichens are not related with pollution unsuitable for drinking is/are [2017]
12. Bio-indicators are used for (a) Both SO42− and NO3−
(a) Oxygen demand (b) Air pollution
(b) Only F −
(c) Mineral present (d) All of these
(c) Only SO42−
13. Which one of the following statements pertaining to pollutants
is correct (d) Only NO3−
(a) DDT is non-biodegradable pollutant 5. What is DDT among the following [2012]
(a) Greenhouse gas
(b) Excess fluoride in drinking water causes ostoporosis
(b) A fertilizer
(c) Excess cadmium in drinking water causes black foot
(c) Biodegradable pollutant
disease
(d) Non-biodegradable pollutant
(d) Methyl mercury in water may causes ‘‘Itai-Itai disease’’

16. Environmental Chemistry – Answers Keys
1. Air Pollution 3. Different Types of Pollution and Pollutants
1 d 2 c 3 d 4 b 5 c 1 a 2 c 3 a 4 c 5 b
6 e 7 e 8 b 9 a 10 a 6 a 7 d 8 a 9 d 10 d
11 a 12 c 13 b 14 e 15 a 11 b 12 d 13 a 14 c 15 c
16 a 17 c 18 c 19 d 20 b 4. IIT-JEE/ AIEEE
21 b 22 a 23 c 24 a 25 b 1 d 2 b 3 b 4 b 5 d
2. Water Pollution
1 d 2 a 3 c 4 c 5 b
6 c 7 c 8 a 9 c 10 c
11 a 12 b 13 b 14 b 15 a
16 a 17 a

Booklet 5 - CH 14, 15, 16

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Booklet 5 - CH 14, 15, 16

Uploaded by

Copyright:

Available Formats

© Copyright Reserved.

1s2, 2s1, 2px1 2py1 2pz1.

Bonding in Organic Compounds

End to End Overlapping

Sidewise or Parallel or Lateral Overlapping

Table: 14.1 Difference between Sigma and Pi Bond

Stuctural Representation of Organic Compounds

Structure of organic compounds can be represented in following ways:

Complete Structural Formula

Example: Structure of ethane

General Organic Chemistry | 2

Example: CH 3 − CH 3 or C2 H 6 represents ethane.

Bond-line Structural Formula

Example: Structure of dichloroacetic acid (CHCl2COOH)

Wedge and Dash Representation

The 3D structure of organic compound can be represented on paper by this method.

Bonds lying in the plane of the paper indicated by ordinary lines.

Example: 3D representation of methane molecule

Hybridisation and Geometry of Organic Compounds

Table : 14.2 Type of Hybridisation for Carbon Atom

Type of hybridisation sp3 sp2 sp

(1) Size of the Hybrid Orbitals

General Organic Chemistry | 3

• Electronegativity of s-orbital is maximum.

• Electronegativity of hybrid orbitals  % s-character in hybrid orbitals

Bond Length Variation in Hydrocarbons

Bond Strength in Hydrocarbons

Table : 14.4 Bond Strength in Hydrocarbons

sp − s (in alkynes) 121 sp − sp (in alkynes) 123 – 199

• Hydrogen present on electronegative carbon is acidic in nature.

• Acidity of hydrocarbon  % of s-character

s- character and acidity in decreasing order

General Organic Chemistry | 4

Order of acidic nature of alkynes is,

The relative acidic character follows the order:

CH3CH2−  CH2 = CH −  NH2−  HC  C−  RO−  HO−

Dipole Moment of Organic Compounds

 = el (1D = 10−10 esu  10−8 cm = 10−18 esu.cm)

NH3 PH AsH3 SbH3

(4) Decreasing order of dipole moment in CH 3 Cl , CH 2Cl 2 , CHCl 3 and CCl 4 is

 = 1.86 D 1.62 D 1.03 0

(6)  cis   trans in geometrical isomers.

General Organic Chemistry | 5

(8) Dipole Moment of Disubstituted Benzene

Where,  1 = dipole moment of bond C − X ,  2 = dipole Y or Y

−derivative  m- derivative  p- derivative

 = 12 + 22 − 212 cos

o − derivative  m- derivative  p- derivative

Strained carbon due to

General Organic Chemistry | 6

Polarisation effect Polarisability effect

Inductive Mesomeric Hyperconjugative Inductomeric Electromeric

Important Features of Inductive Effect

• It operates through  bonds.

–I power of groups in decreasing order with respect to the reference H

+ I power in decreasing order with respect to the reference H

+ I power in decreasing order in same type of alkyl groups

General Organic Chemistry | 7

• Magnitude of Positive and Negative Charges

• Reactivity of Alkyl Halide

• Relative Strength of the Acids

Thus, acidic nature is,

HCOOH  CH 3 COOH  C 2 H 5 COOH  C 3 H 7 COOH  C 4 H 9 COOH