kech202

256 chemistry
ni 8
U
t
Organic hemistry – me Basic
C
So
Princi les and Techniques
p
In the previous unit you have learnt that the element
carbon has the unique property called catenation due to
which it forms covalent bonds with other carbon atoms.
After studying this unit, you will It also forms covalent bonds with atoms of other elements
be able to
like hydrogen, oxygen, nitrogen, sulphur, phosphorus
• understand reasons for and halogens. The resulting compounds are studied
tetravalence of carbon and under a separate branch of chemistry called organic
shapes of organic molecules; chemistry. This unit incorporates some basic principles
• write structures of organic and techniques of analysis required for understanding the
molecules in various ways; formation and properties of organic compounds.
• classify the organic compounds;
• name the compounds according
8.1 General n roduc ion
to IUPAC system of nomenclature
I
t
t
and also derive their structures Organic compounds are vital for sustaining life on earth
from the given names; and include complex molecules like genetic information
• understand the concept of bearing deoxyribonucleic acid (DNA) and proteins that
organic reaction mechanism; constitute essential compounds of our blood, muscles and
• explain the influence of electronic skin. Organic compounds appear in materials like clothing,
displacements on structure and fuels, polymers, dyes and medicines. These are some of
reactivity of organic compounds; the important areas of application of these compounds.
• recognise the types of organic Science of organic chemistry is about two hundred
reactions; years old. Around the year 1780, chemists began to
• learn the techniques of distinguish between organic compounds obtained from
purification of organic plants and animals and inorganic compounds prepared
compounds;
from mineral sources. Berzilius, a Swedish chemist
• write the chemical reactions
proposed that a ‘vital force’ was responsible for the
involved in the qualitative
formation of organic compounds. However, this notion
analysis of organic compounds;
was rejected in 1828 when F. Wohler synthesised an
• understand the principles
involved in quantitative analysis
organic compound, urea from an inorganic compound,
of organic compounds. ammonium cyanate.
NH4CNO NH2CONH2
Ammonium cyanate Urea
The pioneering synthesis of acetic acid by Kolbe
(1845) and that of methane by Berthelot (1856) showed
conclusively that organic compounds could be synthesised
from inorganic sources in a laboratory.
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organic chemistry – some basic principles and techniques 257
The development of electronic theory of Thus, in H2C=CH2 molecule all the atoms
covalent bonding ushered organic chemistry must be in the same plane. The p orbitals are
into its modern shape. mutually parallel and both the p orbitals are
perpendicular to the plane of the molecule.
8.2 V OF BO :
Rotation of one CH2 fragment with respect
TETRA
ALENCE
CAR
N
P OF O O PO
to other interferes with maximum overlap
SHA
ES
RGANIC
C
M
UNDS
8.2.1 The Shapes of Carbon Compounds of p orbitals and, therefore, such rotation
The knowledge of fundamental concepts of about carbon-carbon double bond (C=C) is
molecular structure helps in understanding restricted. The electron charge cloud of the π
and predicting the properties of organic bond is located above and below the plane of
compounds. You have already learnt theories bonding atoms. This results in the electrons
of valency and molecular structure in Unit 4. being easily available to the attacking
Also, you already know that tetravalence of reagents. In general, π bonds provide the most
carbon and the formation of covalent bonds reactive centres in the molecules containing
by it are explained in terms of its electronic multiple bonds.
configuration and the hybridisation of s and p
orbitals. It may be recalled that formation and
Problem 8.1
the shapes of molecules like methane (CH4),
ethene (C2H4), ethyne (C2H2) are explained How many σ and π bonds are present in
in terms of the use of sp3, sp2 and sp hybrid each of the following molecules?
orbitals by carbon atoms in the respective (a) HC≡CCH=CHCH3 (b) CH2=C=CHCH3
molecules.
olution
Hybridisation influences the bond length
S
and bond enthalpy (strength) in compounds. (a) σC – C: 4; σC–H : 6; πC=C :1; π C≡C:2
The sp hybrid orbital contains more s (b) σC – C: 3; σC–H: 6; πC=C: 2.
character and hence it is closer to its nucleus
and forms shorter and stronger bonds than Problem 8.2
the sp3 hybrid orbital. The sp2 hybrid orbital What is the type of hybridisation of each
is intermediate in s character between sp carbon in the following compounds?
and sp3 and, hence, the length and enthalpy
of the bonds it forms, are also intermediate (a) CH3Cl, (b) (CH3)2CO, (c) CH3CN,
between them. The change in hybridisation (d) HCONH2, (e) CH3CH=CHCN
affects the electronegativity of carbon. The
olution
greater the s character of the hybrid orbitals,
S
the greater is the electronegativity. Thus, a (a) sp3, (b) sp3, sp2, (c) sp3, sp, (d) sp2, (e)
carbon atom having an sp hybrid orbital with sp3, sp2, sp2, sp
50% s character is more electronegative than Problem 8.3
that possessing sp2 or sp3 hybridised orbitals.
This relative electronegativity is reflected in Write the state of hybridisation of carbon
several physical and chemical properties of in the following compounds and shapes
the molecules concerned, about which you of each of the molecules.
will learn in later units. (a) H2C=O, (b) CH3F, (c) HC≡N.
8.2.2 ome haracteristic Features of π olution
S
C
S
Bonds
(a) sp2 hybridised carbon, trigonal planar;
In a π (pi) bond formation, parallel orientation (b) sp3 hybridised carbon, tetrahedral; (c)
of the two p orbitals on adjacent atoms is sp hybridised carbon, linear.
necessary for a proper sideways overlap.
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258 chemistry
8.3 e resen O Similarly, CH3CH2CH2CH2CH2CH2CH2CH3

STRUCTURAL
R
p
TATI
NS
OF rganic O PO o
s can be further condensed to CH3(CH2)6CH3.
C
M
UND
8.3.1 omplete, ondensed and Bond-line For further simplification, organic chemists
use another way of r epr esenting the
C
C
tructural Formulas
structures, in which only lines are used.
S
Structures of organic compounds are
In this bond-line structural representation
represented in several ways. The Lewis
of organic compounds, carbon and
structure or dot structure, dash structure,
hydrogen atoms are not shown and the
condensed structure and bond line structural
lines representing carbon-carbon bonds are
formulas are some of the specific types. The
drawn in a zig-zag fashion. The only atoms
Lewis structures, however, can be simplified
specifically written are oxygen, chlorine,
by representing the two-electron covalent
nitrogen etc. The terminals denote methyl
bond by a dash (–). Such a structural formula
(–CH3) groups (unless indicated otherwise by
focuses on the electrons involved in bond
a functional group), while the line junctions
formation. A single dash represents a single
denote carbon atoms bonded to appropriate
bond, double dash is used for double bond
number of hydrogens required to satisfy the
and a triple dash represents triple bond. Lone-
valency of the carbon atoms. Some of the
pairs of electrons on heteroatoms (e.g., oxygen,
examples are represented as follows:
nitrogen, sulphur, halogens etc.) may or may
not be shown. Thus, ethane (C2H6), ethene (i) 3-Methyloctane can be represented in
(C2H4), ethyne (C2H2) and methanol (CH3OH) various forms as:
can be represented by the following structural (a) CH3CH2CHCH2CH2CH2CH2CH3
formulas. Such structural representations are |
called complete structural formulas. CH3
(b)
Ethane Ethene

(c)
Ethyne Methanol
These structural formulas can be further

abbreviated by omitting some or all of the
dashes representing covalent bonds and by
(ii) Various ways of representing 2-bromo
indicating the number of identical groups
butane are:
attached to an atom by a subscript. The
resulting expression of the compound is
called a condensed structural formula. Thus,
(a) CH3CHBrCH2CH3 (b)
ethane, ethene, ethyne and methanol can be
written as:
CH3CH3 H2C=CH2 HC≡CH CH3OH
(c)
Ethane Ethene Ethyne Methanol
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In cyclic compounds, the bond-line formulas

may be given as follows:
(b)
olution
S
Condensed formula:
Cyclopropane (a) HO(CH2)3CH(CH3)CH(CH3)2
(b) HOCH(CN)2
Bond-line formula:
(a)
Cyclopentane
(b)
chlorocyclohexane
Problem 8.6
Problem 8.4
Expand each of the following bond-line
Expand each of the following condensed formulas to show all the atoms including
formulas into their complete structural carbon and hydrogen
formulas. (a)
(a) CH3CH2COCH2CH3
(b) CH3CH=CH(CH2)3CH3
olution (b)
S
(a)
(c)
(b) (d)
olution
S
Problem 8.5
For each of the following compounds,
write a condensed formula and also their
bond-line formula.
(a) HOCH2CH2CH2CH(CH3)CH(CH3)CH3
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260 chemistry
Molecular Models
Molecular models are physical devices
that are used for a better visualisation and
perception of three-dimensional shapes
of organic molecules. These are made of
wood, plastic or metal and are commercially
available. Commonly three types of molecular
models are used: (1) Framework model, (2)
Ball-and-stick model, and (3) Space filling
model. In the framework model only the
bonds connecting the atoms of a molecule
and not the atoms themselves are shown.
This model emphasizes the pattern of
bonds of a molecule while ignoring the size
of atoms. In the ball-and-stick model, both
the atoms and the bonds are shown. Balls
represent atoms and the stick denotes a
bond. Compounds containing C=C (e.g.,
ethene) can best be represented by using
8.3.2 Three-Dimensional
springs in place of sticks. These models are
Representation of Organic referred to as ball-and-spring model. The
Molecules space-filling model emphasises the relative
The three-dimensional (3-D) structure of size of each atom based on its van der Waals
organic molecules can be represented on radius. Bonds are not shown in this model.
paper by using certain conventions. For It conveys the volume occupied by each atom
example, by using solid ( ) and dashed in the molecule. In addition to these models,
computer graphics can also be used for
( ) wedge formula, the 3-D image of a
molecular modelling.
molecule from a two-dimensional picture
can be perceived. In these formulas the
solid-wedge is used to indicate a bond
projecting out of the plane of paper, towards
the observer. The dashed-wedge is used to
depict the bond projecting out of the plane of
the paper and away from the observer. Wedges
are shown in such a way that the broad end of
the wedge is towards the observer. The bonds Framework model Ball and stick model
lying in plane of the paper are depicted by
using a normal line (—). 3-D representation of
methane molecule on paper has been shown
in Fig. 8.1
Space filling model
Fig. 8.2
Fig. 8.1 Wedge-and-dash representation of CH4
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8.4 Classifi ation of rgani (homocyclic).
c
O
c
Compounds
The existing large number of organic
compounds and their ever -increasing
numbers has made it necessary to classify
them on the basis of their structures. Organic Cyclopropane Cyclohexene Cyclohexane
compounds are broadly classified as follows:
Sometimes atoms other than carbon are
also present in the ring (heterocylic).
Tetrahydrofuran given below is an example
of this type of compound:
Tetrahydrofuran
These exhibit some of the properties similar
to those of aliphatic compounds.
(b) romatic compounds
A
Aromatic compounds are special types of
compounds. You will learn about these
compounds in detail in Unit 9. These include
benzene and other related ring compounds
(benzenoid). Like alicyclic compounds,
aromatic comounds may also have hetero
atom in the ring. Such compounds are called
. Acyclic or open chain compounds hetrocyclic aromatic compounds. Some of
I
the examples of various types of aromatic
These compounds are also called as aliphatic
compounds are:
compounds and consist of straight or
branched chain compounds, for example: Benzenoid aromatic compounds
CH3CH3
Ethane
Isobutane
Benzene Aniline Naphthalene
Non-benzenoid compound
Acetaldehyde Acetic acid

Cyclic or closed chain or ring
II
compounds
(a) licyclic compounds Tropone
A
Alicyclic (aliphatic cyclic) compounds contain
carbon atoms joined in the form of a ring
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262 chemistry
Heterocyclic aromatic compounds so because it is found in citrus fruits and the

acid found in red ant is named formic acid
since the Latin word for ant is formica. These
names are traditional and are considered
as trivial or common names. Some common
Furan Thiophene Pyridine names are followed even today. For example,
Organic compounds can also be classified Buckminsterfullerene is a common name
on the basis of functional groups, into families given to the newly discovered C60 cluster (a
or homologous series. form of carbon) noting its structural similarity
8.4.1 unctional roup to the geodesic domes popularised by the
famous architect R. Buckminster Fuller.
F
G
The functional group is an atom or a group Common names are useful and in many
of atoms joined to the carbon chain which is cases indispensable, particularly when the
responsible for the characteristic chemical alternative systematic names are lengthy and
properties of the organic compounds. The complicated. Common names of some organic
examples are hydroxyl group (–OH), aldehyde compounds are given in Table 8.1.
group (–CHO) and carboxylic acid group (–
COOH) etc. T
able 8.1 Common or rivial ames of ome
T
N
S
rganic Compounds
8.4.2 Homologous eries
O
S
A group or a series of organic compounds each
containing a characteristic functional group
forms a homologous series and the members of
the series are called homologues. The members
of a homologous series can be represented by
general molecular formula and the successive
members differ from each other in molecular
formula by a –C 2 unit. There are a number
h
of homologous series of organic compounds.
Some of these are alkanes, alkenes, alkynes,
haloalkanes, alkanols, alkanals, alkanones,
alkanoic acids, amines etc.
It is also possible that a compound contains
two or more identical or different functional
groups. This gives rise to polyfunctional
compounds.
8.5 E C E C
NOM
N
LATUR
OF
ORGANI
C
OMPOUNDS
Organic chemistry deals with millions of 8.5.1 he C ystem of omenclature
compounds. In order to clearly identify
T
IUPA
S
N
A systematic name of an organic compound
them, a systematic method of naming has
is generally derived by identifying the parent
been developed and is known as the C
hydrocarbon and the functional group(s)
IUPA
( nternational nion of ure and pplied
attached to it. See the example given below.
I
U
P
A
Chemistry) system of nomenclature. In this
systematic nomenclature, the names are
correlated with the structure such that the
reader or listener can deduce the structure
from the name.
Before the IUPAC system of nomenclature,
however, organic compounds were assigned
names based on their origin or certain
properties. For instance, citric acid is named
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By further using prefixes and suffixes, the In order to name such compounds, the names
parent name can be modified to obtain the of alkyl groups are prefixed to the name of
actual name. Compounds containing carbon parent alkane. An alkyl group is derived
and hydrogen only are called hydrocarbons. from a saturated hydrocarbon by removing
A hydrocarbon is termed saturated if it a hydrogen atom from carbon. Thus, CH4
contains only carbon-carbon single bonds. becomes -CH3 and is called methyl group. An
The IUPAC name for a homologous series of alkyl group is named by substituting ‘yl’ for
such compounds is alkane. Paraffin (Latin: ‘ane’ in the corresponding alkane. Some alkyl
little affinity) was the earlier name given to groups are listed in Table 8.3.
these compounds. Unsaturated hydrocarbons able 8.3 ome lkyl roups
T
S
A
G
are those, which contain at least one carbon-
carbon double or triple bond.
8.5.2 P omenclature of lkanes
IU
AC
N
A
Straight chain hydrocarbons: The names
of such compounds are based on their chain
structure, and end with suffix ‘-ane’ and carry
a prefix indicating the number of carbon
atoms present in the chain (except from CH4
to C4H10, where the prefixes are derived from
trivial names). The IUPAC names of some
straight chain saturated hydrocarbons are
Abbreviations are used for some alkyl
given in Table 8.2. The alkanes in Table
groups. For example, methyl is abbreviated as
8.2 differ from each other by merely the
Me, ethyl as Et, propyl as Pr and butyl as Bu.
number of -CH2 groups in the chain. They are
The alkyl groups can be branched also. Thus,
homologues of alkane series.
propyl and butyl groups can have branched
able 8.2 P ames of ome nbranched structures as shown below.
T
IU
AC
N
S
U
Saturated Hydrocarbons CH3-CH- CH3-CH2-CH- CH3-CH-CH2-
  
CH3 CH3 CH3
Isopropyl- sec-Butyl- Isobutyl-
CH3 CH3
 
CH3-C- CH3-C-CH2-
 
CH3 CH3
tert-Butyl- Neopentyl-
Branched chain hydrocarbons: In a Common branched groups have specific
branched chain compound small chains of trivial names. For example, the propyl groups
carbon atoms are attached at one or more can either be n-propyl group or isopropyl
carbon atoms of the parent chain. The small group. The branched butyl groups are called
carbon chains (branches) are called alkyl sec-butyl, isobutyl and tert-butyl group.
groups. For example: We also encounter the structural unit,
–CH2C(CH3)3, which is called neopentyl group.
CH3–CH–CH2–CH3 CH3–CH–CH2–CH–CH3
   Nomenclature of branched chain alkanes:
We encounter a number of branched chain

CH3 CH2CH3 CH3
alkanes. The rules for naming them are given

(a) (b) below.

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264 chemistry
1. First of all, the longest carbon chain in separated from the groups by hyphens
the molecule is identified. In the example and there is no break between methyl
(I) given below, the longest chain has nine and nonane.]
carbons and it is considered as the parent 4. If two or more identical substituent
or root chain. Selection of parent chain as groups are present then the numbers
shown in (II) is not correct because it has are separated by commas. The names of
only eight carbons. identical substituents are not repeated,
instead prefixes such as di (for 2), tri
(for 3), tetra (for 4), penta (for 5), hexa (for
6) etc. are used. While writing the name
of the substituents in alphabetical order,
these prefixes, however, are not considered.
Thus, the following compounds are
named as:
CH3 CH3 CH3 CH3
   
CH3-CH-CH2-CH-CH3 CH3 C CH2CH CH3

1 2 3 4 5 1 2 3 4 5
2,4-Dimethylpentane 2,2,4-Trimethylpentane
2. The carbon atoms of the parent chain are
numbered to identify the parent alkane H3C H2C CH3
and to locate the positions of the carbon  
CH3CH2CHCCH2CH2CH3

atoms at which branching takes place due

to the substitution of alkyl group in place 1 2 3 4 5 6 7

of hydrogen atoms. The numbering is CH3

done in such a way that the branched 3-Ethyl-4,4-dimethylheptane
carbon atoms get the lowest possible
numbers. Thus, the numbering in the 5. If the two substituents are found in
above example should be from left to right equivalent positions, the lower number
(branching at carbon atoms 2 and 6) and is given to the one coming first in the
not from right to left (giving numbers alphabetical listing. Thus, the following
4 and 8 to the carbon atoms at which compound is 3-ethyl-6-methyloctane and
branches are attached). not 6-ethyl-3-methyloctane.
1 2 3 4 5 6 7 8 9
CCCCCCCCC 1 2 3 4 5 6 7 8
  CH3 — CH2—CH—CH2—CH2—CH—CH2 —CH3
 

C CC

CH2CH3 CH3

9 8 7 6 5 4 3 2 1

CCCCCCCCC 6. The branched alkyl groups can be
  named by following the above mentioned

C CC procedures. However, the carbon atom

3. The names of alkyl groups attached of the branch that attaches to the root
as a branch are then prefixed to the alkane is numbered 1 as exemplified
name of the parent alkane and position below.
of the substituents is indicated by the
4 3 2 1
appropriate numbers. If different alkyl
CH3–CH–CH2–CH–
groups are present, they are listed in
alphabetical order. Thus, name for the  

compound shown above is: 6-ethyl-2- CH3 CH3
1,3-Dimethylbutyl-
methylnonane. [Note: the numbers are
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The name of such branched chain alkyl group Cyclic Compounds: A saturated monocyclic
is placed in parenthesis while naming the compound is named by prefixing ‘cyclo’ to the
compound. While writing the trivial names corresponding straight chain alkane. If side
of substituents’ in alphabetical order, the chains are present, then the rules given above
prefixes iso- and neo- are considered to be are applied. Names of some cyclic compounds
the part of the fundamental name of alkyl are given below.
group. The prefixes sec- and tert- are not
considered to be the part of the fundamental
name. The use of iso and related common
prefixes for naming alkyl groups is also
allowed by the IUPAC nomenclature as long
as these are not further substituted. In multi-
substituted compounds, the following rules
may aso be remembered:
• If there happens to be two chains of equal
size, then that chain is to be selected which
contains more number of side chains.
3-Ethyl-1,1-dimethylcyclohexane
• After selection of the chain, numbering (not 1-ethyl-3,3-dimethylcyclohexane)
is to be done from the end closer to the
substituent. Problem 8.7
Structures and IUPAC names of some
hydrocarbons are given below. Explain
why the names given in the parentheses
are incorrect.
2,5,6- Trimethyloctane
[and not 3,4,7-Trimethyloctane]
5-(2-Ethylbutyl)-3,3-dimethyldecane
[and not 5-(2,2-Dimethylbutyl)-3-ethyldecane]
3-Ethyl-5-methylheptane
[and not 5-Ethyl-3-methylheptane]
Solution
(a) Lowest locant number, 2,5,6 is
lower than 3,5,7, (b) substituents are
5-sec-Butyl-4-isopropyldecane in equivalent position; lower number is
given to the one that comes first in the
name according to alphabetical order.
8.5.3 Nomenclature of Organic

Compounds having Functional
Group(s)
A functional group, as defined earlier, is an
atom or a group of atoms bonded together in
5-(2,2-Dimethylpropyl)nonane a unique manner which is usually the site of
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266 chemistry
chemical reactivity in an organic molecule. class suffix. In such cases the full name of the
Compounds having the same functional parent alkane is written before the class suffix.
group undergo similar reactions. For example, For example CH2(OH)CH2(OH) is named as
CH 3OH, CH 3CH 2OH, and (CH 3) 2CHOH — ethane–1,2–diol. However, the ending – ne of
all having -OH functional group liberate the parent alkane is dropped in the case of
hydrogen on reaction with sodium metal. compounds having more than one double or
The presence of functional groups enables triple bond; for example, CH2=CH-CH=CH2 is
systematisation of organic compounds into named as buta–1,3–diene.
different classes. Examples of some functional
groups with their prefixes and suffixes along Problem 8.8
with some examples of organic compounds Write the IUPAC names of the compounds
possessing these are given in Table 8.4. i-iv from their given structures.
First of all, the functional group present
in the molecule is identified which determines
the choice of appropriate suffix. The longest
chain of carbon atoms containing the
functional group is numbered in such a way
that the functional group is attached at the S
olution
carbon atom possessing lowest possible • The functional group present is an
number in the chain. By using the suffix as alcohol (OH). Hence the suffix is ‘-ol’.
given in Table 8.4, the name of the compound • The longest chain containing -OH
is arrived at. has eight carbon atoms. Hence the
In the case of polyfunctional compounds, corresponding saturated hydrocar-
one of the functional groups is chosen as the bon is octane.
principal functional group and the compound • The -OH is on carbon atom 3. In
is then named on that basis. The remaining addition, a methyl group is attached
functional groups, which are subordinate at 6th carbon.
functional groups, are named as substituents Hence, the systematic name of this
using the appropriate prefixes. The choice of compound is 6-Methyloctan-3-ol.
principal functional group is made on the basis
of order of preference. The order of decreasing
priority for some functional groups is:
- OO , – O3 , - OO ( =alkyl group), O l,
C
H
S
H
C
R
R
C
C
-CONH2, - ,- =O, > =O, -O , - 2
, >
CN
HC
C
H
NH
= <, - ≡C- . olution
S
C
C
C
The –R, C6H5-, halogens (F, Cl, Br, I), –NO2, The functional group present is ketone
alkoxy (–OR) etc. are always prefix (>C=O), hence suffix ‘-one’. Presence
substituents. Thus, a compound containing of two keto groups is indicated by ‘di’,
both an alcohol and a keto group is named hence suffix becomes ‘dione’. The two
as hydroxyalkanone since the keto group is keto groups are at carbons 2 and 4.
preferred to the hydroxyl group. The longest chain contains 6 carbon
For example, HOCH2(CH2)3CH2COCH3 will atoms, hence, parent hydrocarbon is
be named as 7-hydroxyheptan-2-one and not hexane. Thus, the systematic name is
as 2-oxoheptan -7-ol. Similarly, BrCH2CH=CH2 Hexane-2,4-dione.
is named as 3-bromoprop-1-ene and not
1-bromoprop-2-ene.
If more than one functional group of the
same type are present, their number is
indicated by adding di, tri, etc. before the
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able 8.4 ome Functional roups and lasses of Organic ompounds
T
S
G
C
C
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268 chemistry
olution (iii) Six membered ring containing a

S
Here, two functional groups namely carbon-carbon double bond is implied
ketone and carboxylic acid are present. by cyclohexene, which is numbered as
The principal functional group is the shown in (I). The prefix 3-nitro means
carboxylic acid group; hence the parent that a nitro group is present on C-3.
chain will be suffixed with ‘oic’ acid. Thus, complete structural formula of the
Numbering of the chain starts from compound is (II). Double bond is suffixed
carbon of – COOH functional group. functional group whereas NO2 is prefixed
The keto group in the chain at carbon functional group therefore double bond
5 is indicated by ‘oxo’. The longest gets preference over –NO2 group:
chain including the principal functional
group has 6 carbon atoms; hence the
parent hydrocarbon is hexane. The
compound is, therefore, named as
5-Oxohexanoic acid.
(iv) ‘1-ol’ means that a -OH group is

olution present at C-1. OH is suffixed functional
S
The two C=C functional groups are group and gets preference over C=C
present at carbon atoms 1 and 3, while bond. Thus the structure is as shown
the C≡C functional group is present at in (II):
carbon 5. These groups are indicated by
suffixes ‘diene’ and ‘yne’ respectively. The
longest chain containing the functional
groups has 6 carbon atoms; hence the
parent hydrocarbon is hexane. The name
of compound, therefore, is Hexa-1,3-
dien-5-yne.
(v) ‘heptanal’ indicates the compound
Problem 8.9
to be an aldehyde containing 7 carbon
Derive the structure of (i) 2-Chlorohexane, atoms in the parent chain. The
(ii) Pent-4-en-2-ol, (iii) 3- Nitrocyclohexene, ‘6-hydroxy’ indicates that -OH group is
(iv) Cyclohex-2-en-1-ol, (v) 6-Hydroxy- present at carbon 6. Thus, the structural
heptanal. formula of the compound is: CH3CH(OH)
olution CH2CH2CH2CH2CHO. Carbon atom of –
S
CHO group is included while numbering
(i) ‘hexane’ indicates the presence of
the carbon chain.
6 carbon atoms in the chain. The
functional group chloro is present at
carbon 2. Hence, the structure of the 8.5.4 omenclature of ubstituted
compound is CH3CH2CH2CH2CH(Cl)CH3.
N
S
Benzene ompounds
C
(ii) ‘pent’ indicates that parent
For IUPAC nomenclature of substituted
hydrocarbon contains 5 carbon atoms
benzene compounds, the substituent is
in the chain. ‘en’ and ‘ol’ correspond to
the functional groups C=C and -OH at placed as prefix to the word benzene as shown
carbon atoms 4 and 2 respectively. Thus, in the following examples. However, common
the structure is names (written in bracket below) of many
substituted benzene compounds are also
CH2=CHCH2CH (OH)CH3. universally used.
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Substituent of the base compound is

assigned number1 and then the direction
of numbering is chosen such that the
next substituent gets the lowest number.
The substituents appear in the name in
Methylbenzene Methoxybenzene Aminobenzene alphabetical order. Some examples are given
(Toluene) (Anisole) (Aniline)
below.
Nitrobenzene Bromobenzene 1-Chloro-2,4-dinitrobenzene

(not 4-chloro,1,3-dinitrobenzene)
If benzene ring is disubstituted,
the position of substituents is defined
by numbering the carbon atoms of the
ring such that the substituents are
located at the lowest numbers possible.
For example, the compound(b) is named
as 1,3-dibromobenzene and not as
1,5-dibromobenzene.
2-Chloro-1-methyl-4-nitrobenzene
(not 4-methyl-5-chloro-nitrobenzene)
(a) (b) (c)

1,2-Dibromo- 1,3-Dibromo- 1,4-Dibromo-
benzene benzene benzene
In the trivial system of nomenclature
the terms ortho (o), meta (m) and para (p) 2-Chloro-4-methylanisole 4-Ethyl-2-methylaniline
are used as prefixes to indicate the relative
positions 1,2;1,3 and 1,4 respectively. Thus,
1,3-dibr omobenzene (b) is named as
m-dibromobenzene (meta is abbreviated as
m-) and the other isomers of dibromobenzene
1,2-(a) and 1,4-(c), are named as ortho (or
just o-) and para (or just p-)-dibromobenzene,
respectively.
For tri - or higher substituted benzene 3,4-Dimethylphenol
derivatives, these prefixes cannot be used
and the compounds are named by identifying When a benzene ring is attached to an
substituent positions on the ring by following alkane with a functional group, it is considered
the lowest locant rule. In some cases, common as substituent, instead of a parent. The name
name of benzene derivatives is taken as the for benzene as substituent is phenyl (C6H5-,
base compound. also abbreviated as Ph).
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270 chemistry
different carbon skeletons, these are referred

Problem 8.10
to as chain isomers and the phenomenon is
Write the structural formula of: termed as chain isomerism. For example,
(a) o-Ethylanisole, (b) p-Nitroaniline, C5H12 represents three compounds:
(c) 2,3 - Dibromo -1 - phenylpentane,
(d) 4-Ethyl-1-fluoro-2-nitrobenzene. CH3

olution

CH3CH2CH2CH2CH3 CH3−CHCH2CH3
S
Pentane Isopentane
(2-Methylbutane)
CH3

CH3 C CH3
(a) (b) 

CH3
Neopentane
(2,2-Dimethylpropane)
(ii) Position isomerism: When two or

more compounds differ in the position of
(c) (d) substituent atom or functional group on

the carbon skeleton, they are called position
8.6 O isomers and this phenomenon is termed
IS
MERISM
as position isomerism. For example, the
The phenomenon of existence of two or more molecular formula C3H 8O represents two
compounds possessing the same molecular alcohols:
formula but different properties is known
as isomerism. Such compounds are called OH
as isomers. The following flow chart shows 
different types of isomerism. CH3CH2CH2OH CH3−CH-CH3
Propan-1-ol Propan-2-ol
8.6.1 tructural somerism

S
I
Compounds having the same molecular (iii) Functional group isomerism: Two or
formula but different structures (manners more compounds having the same molecular
in which atoms are linked) are classified as formula but different functional groups
structural isomers. Some typical examples are called functional isomers and this
of different types of structural isomerism are phenomenon is termed as functional group
given below: isomerism. For example, the molecular
(i) Chain isomerism: When two or more formula C3H6O represents an aldehyde and
compounds have similar molecular formula but a ketone:
Isomerism
Structural isomerism Stereoisomerism
Chain Position Functional Metamerism Geometrical Optical

isomerism isomerism group isomerism isomerism
isomerism
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in understanding the reactivity of organic

O H compounds and in planning strategy for their

  synthesis.

CH3−C-CH3 CH3−CH2—C= O
In the following sections, we shall learn
Propanone Propanal
some of the principles that explain how these
(iv) Metamerism: It arises due to different reactions take place.
alkyl chains on either side of the functional
8.7.1 Fission of a Covalent Bond
group in the molecule. For example, C4H10O
represents methoxypropane (CH3OC3H7) and A covalent bond can get cleaved either by : (i)
ethoxyethane (C2H5OC2H5). heterolytic cleavage, or by (ii) homolytic
cleavage.
8.6.2 Stereoisomerism
In heterolytic cleavage, the bond breaks
The compounds that have the same in such a fashion that the shared pair of
constitution and sequence of covalent bonds electrons remains with one of the fragments.
but differ in relative positions of their atoms After heterolysis, one atom has a sextet
or groups in space are called stereoisomers. electronic structure and a positive charge and
This special type of isomerism is called as the other, a valence octet with at least one lone
stereoisomerism and can be classified as pair and a negative charge. Thus, heterolytic
geometrical and optical isomerism. +
cleavage of bromomethane will give C H3 and
8.7 F U N D A M E N TA L C O N C E P T S I N Br– as shown below.
ORGANIC REACTION MECHANISM
In an organic reaction, the organic molecule
(also referred as a substrate) reacts with an A species having a carbon atom possessing
appropriate attacking reagent and leads to sextext of electrons and a positive charge is
the formation of one or more intermediate(s) called a carbocation (earlier called carbonium
and finally product(s) ion). The H3 ion is known as a methyl cation
or methyl carbonium ion. Carbocations are
The general reaction is depicted as follows :
classified as primary, secondary or tertiary
Attacking depending on whether one, two or three
Reagent [Intermediate] Product(s)
Organic carbons are directly attached to the positively
molecule charged carbon. Some+ other examples of
(Substrate) Byproducts carbocations are: CH3C H2 (ethyl cation, a
+
primary carbocation), (CH3)2C H (isopropyl+
Substrate is that reactant which supplies cation, a secondary carbocation), and (CH3)3C
carbon to the new bond and the other reactant (tert-butyl cation, a tertiary carbocation).
is called reagent. If both the reactants Carbocations are highly unstable and
supply carbon to the new bond then choice reactive species. Alkyl groups directly
is arbitrary and in that case the molecule on attached to the positively charged carbon
which attention is focused is called substrate. stabilise the carbocations due to inductive
In such a reaction a covalent bond and hyperconjugation effects, which you will
between two carbon atoms or a carbon and be studying in the sections 8.7.5 and 8.7.9.
some other atom is broken and a new bond is The+ observed+ order of carbocation
+
stability
+
formed. A sequential account of each step, is: C H3 < CH3CH2 < (CH3)2CH < (CH3)3C. These
describing details of electron movement, carbocations have trigonal planar shape
energetics during bond cleavage and bond with positively charged carbon+ being sp 2
formation, and the rates of transformation hybridised. Thus, the shape of C H3 may be
of reactants into products (kinetics) is considered as being derived from the overlap
referred to as reaction mechanism. The of three equivalent C(sp2) hybridised orbitals
knowledge of reaction mechanism helps with 1s orbital of each of the three hydrogen
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272 chemistry
atoms. Each bond may be represented as curved arrow. Such cleavage results in
C(sp 2)–H(1s) sigma bond. The remaining the formation of neutral species (atom or
carbon orbital is perpendicular to the group) which contains an unpaired electron.
molecular plane and contains no electrons. These species are called free radicals. Like
[Fig. 8.3(a)]. carbocations and carbanions, free radicals are
also very reactive. A homolytic cleavage can be
shown as:
Alkyl

free radical

Alkyl radicals are classified as primary,
secondary, or tertiary. Alkyl radical stability
increases as we proceed from primary to
Fig. 8.3 (a) Shape of methyl carbocation tertiary:
The heterolytic cleavage can also give a
,
species in which carbon gets the shared Methyl Ethyl Isopropyl Tert-butyl
pair of electrons. For example, when group free free free free
Z attached to the carbon leaves without radical radical radical radical
Organic reactions, which proceed by
homolytic fission are called free radical or
electron pair, the methyl anion is homopolar or nonpolar reactions.
formed. Such a carbon species carrying a 8.7.2 ubstrate and eagent
S
R
negative charge on carbon atom is called Ions are generally not formed in the reactions
carbanion. Carbon in carbanion is generally of organic compounds. Molecules as such
sp3 hybridised and its structure is distorted participate in the reaction. It is convenient to
tetrahedron as shown in Fig. 8.3(b). name one reagent as substrate and other as
reagent. In general, a molecule whose carbon
is involved in new bond formation is called
substrate and the other one is called reagent.
When carbon-carbon bond is formed, the
choice of naming the reactants as substrate
and reagent is arbitrary and depends on
molecule under observation. Example:
(i) CH2 = CH2 + Br2 →

Fig. 8.3 (b) Shape of methyl carbanion
CH2 Br – CH2Br
Substrate Reagent Product
Carbanions are also unstable and reactive
species. The organic reactions which proceed
through heterolytic bond cleavage are called (ii)
ionic or heteropolar or just polar reactions.
In homolytic cleavage, one of the electrons
of the shared pair in a covalent bond goes
with each of the bonded atoms. Thus, in
homolytic cleavage, the movement of a
single electron takes place instead of an Nucleophiles and Electrophiles
electron pair. The single electron movement Reagents attack the reactive site of the
is shown by ‘half-headed’ (fish hook: ) substrate. The reactive site may be electron
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deficient portion of the molecule (a positive

reactive site) e.g., an atom with incomplete Problem 8.11
electron shell or the positive end of the dipole Using curved-arrow notation, show the
in the molecule. If the attacking species is formation of reactive intermediates when
electron rich, it attacks these sites. If attacking the following covalent bonds undergo
species is electron deficient, the reactive site heterolytic cleavage.
for it is that part of the substrate molecule (a) CH3–SCH3, (b) CH3–CN, (c) CH3–Cu
which can supply electrons, e.g., π electrons Solution
in a double bond.
A reagent that brings an electron pair to
the reactive site is called a nucleophile (Nu:)
i.e., nucleus seeking and the reaction is then
called nucleophilic. A reagent that takes away
an electron pair from reactive site is called
electrophile (E+) i.e., electron seeking and the
reaction is called electrophilic. Problem 8.12
During a polar organic reaction, a Giving justification, categorise the
nucleophile attacks an electrophilic centre following molecules/ions as nucleophile
of the substrate which is that specific atom or electrophile:
or part of the substrate which is electron
deficient. Similarly, the electrophiles attack
at nucleophilic centre, which is the electron
rich centre of the substrate. Thus, the
electrophiles receive electron pair from the Solution
substrate when the two undergo bonding Nucleophiles: HS–,C2H5O–,(CH3)3N:H2N:–
interaction. A curved-arrow notation is used These species have unshared pair of
to show the movement of an electron pair electrons, which can be donated and
from the nucleophile to the electrophile. Some shared with an electrophile.
examples of nucleophiles are the negatively + + +
Electrophiles: BF 3 ,C1 H 3 –C =O,N O 2 .
charged ions with lone pair of electrons such Reactive sites have only six valence
as hydroxide (HO– ), cyanide (NC–) ions and electrons; can accept electron pair from
carbanions (R3C:–). Neutral molecules such a nucleophile.
as etc., can also act as
nucleophiles due to the presence of lone Problem 8.13
pair of electrons. Examples of electrophiles Identify electrophilic centre in the
+
include carbocations (C H 3 ) and neutral following: CH3CH=O, CH3CN, CH3I.
molecules having functional groups like Solution
carbonyl group (>C=O) or alkyl halides * *
A m o n g C H 3 H C = O , H 3 C C ≡N , a n d
(R 3C-X, where X is a halogen atom). The *
H3C –I, the starred carbon atoms are
carbon atom in carbocations has sextet
electrophilic centers as they will have
configuration; hence, it is electron deficient
and can receive a pair of electrons from the partial positive charge due to polarity of
nucleophiles. In neutral molecules such as the bond.
alkyl halides, due to the polarity of the C-X
bond a partial positive charge is generated 8.7.3 Electron Movement in Organic
on the carbon atom and hence the carbon Reactions
atom becomes an electrophilic centre at which The movement of electrons in organic
a nucleophile can attack. reactions can be shown by curved-arrow
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274 chemistry
notation. It shows how changes in bonding 8.7.5 nductive ffect
I
E
occur due to electronic redistribution during
When a covalent bond is formed between
the reaction. To show the change in position
atoms of different electronegativity, the
of a pair of electrons, curved arrow starts
electron density is more towards the more
from the point from where an electron pair is
electronegative atom of the bond. Such a shift
shifted and it ends at a location to which the
of electron density results in a polar covalent
pair of electron may move.
bond. Bond polarity leads to various electronic
Presentation of shifting of electron pair is effects in organic compounds.
given below : Let us consider cholorethane (CH3CH2Cl)
(i) from π bond to in which the C–Cl bond is a polar covalent
bond. It is polarised in such a way that the

adjacent bond position
carbon-1 gains some positive charge (δ +)

(ii) from π bond to and the chlorine some negative charge (δ–).

adjacent atom The fractional electronic charges on the two

(iii) from atom to adjacent atoms in a polar covalent bond are denoted
bond position by symbol δ (delta) and the shift of electron

Movement of single electron is indicated by density is shown by an arrow that points from
a single barbed ‘fish hooks’ (i.e. half headed δ+ to δ– end of the polar bond.
curved arrow). For example, in transfer of δδ+ δ+ δ−
hydroxide ion giving ethanol and in the CH3→CH2→Cl
dissociation of chloromethane, the movement 2 1
of electron using curved arrows can be In turn carbon-1, which has developed
depicted as follows: partial positive charge (δ + ) draws some
electron density towards it from the adjacent
C-C bond. Consequently, some positive charge
(δδ+ ) develops on carbon-2 also, where δδ+
symbolises relatively smaller positive charge
as compared to that on carbon – 1. In other
words, the polar C – Cl bond induces polarity
8.7.4 lectron isplacement ffects in in the adjacent bonds. Such polarisation of
σ-bond caused by the polarisation of adjacent
E
D
E
ovalent Bonds
σ-bond is referred to as the inductive effect.
C
The electron displacement in an organic This effect is passed on to the subsequent
molecule may take place either in the ground bonds also but the effect decreases rapidly
state under the influence of an atom or a as the number of intervening bonds increases
substituent group or in the presence of an and becomes vanishingly small after three
appropriate attacking reagent. The electron bonds. The inductive effect is related to the
displacements due to the influence of ability of substituent(s) to either withdraw or
an atom or a substituent group present in donate electron density to the attached carbon
the molecule cause permanent polarlisation atom. Based on this ability, the substitutents
of the bond. Inductive effect and resonance can be classified as electron-withdrawing or
effects are examples of this type of electron electron donating groups relative to hydrogen.
displacements. Temporary electron Halogens and many other groups such as
displacement effects are seen in a molecule nitro (- NO2), cyano (- CN), carboxy (- COOH),
when a reagent approaches to attack it. ester (COOR), aryloxy (-OAr, e.g. – OC6H5), etc.
This type of electron displacement is called are electron-withdrawing groups. On the other
electromeric effect or polarisability effect. hand, the alkyl groups like methyl (–CH3) and
In the following sections we will learn about ethyl (–CH2–CH3) are usually considered as
these types of electronic displacements. electron donating groups.

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benzene cannot be adequately represented

Problem 8.14 by any of these structures, rather it is
Which bond is more polar in the following a hybrid of the two structures (I and II)
pairs of molecules: (a) H3C-H, H3C-Br called resonance structures. The resonance
(b) H 3 C-NH 2 , H 3 C-OH (c) H 3 C-OH, structures (canonical structures or
H3C-SH contributing structures) are hypothetical
and individually do not represent any
olution
real molecule. They contribute to the actual
S
(a) C–Br, since Br is more electronegative structure in proportion to their stability.
than H, (b) C–O, (c) C–O Another example of resonance is provided
Problem 8.15 by nitromethane (CH 3NO 2) which can be
In which C–C bond of CH3CH2CH2Br, the represented by two Lewis structures, (I and
inductive effect is expected to be the least? II). There are two types of N-O bonds in these
structures.
olution
S
Magnitude of inductive effect diminishes
as the number of intervening bonds
increases. Hence, the effect is least in the
bond between carbon-3 and hydrogen.
owever, it is known that the two –O
H
N
8.7.6 esonance tructure bonds of nitromethane are of the same
length (intermediate between a –O single
R
S
N
There are many organic molecules whose bond and a =O double bond). he actual
N
T
behaviour cannot be explained by a single Lewis structure of nitromethane is therefore
structure. An example is that of a resonance hybrid of the two canonical
benzene. Its cyclic structure forms I and II.
containing alternating C–C single The energy of actual structure of the molecule
and C=C double bonds shown (the resonance hybrid) is lower than that of
is inadequate for explaining its Benzene any of the canonical structures. The difference
characteristic properties. in energy between the actual structure and the
As per the above representation, benzene lowest energy resonance structure is called the
should exhibit two different bond lengths, resonance stabilisation energy or simply
due to C–C single and C=C double bonds. the resonance energy. The more the number
However, as determined experimentally of important contributing structures, the
benzene has a uniform C–C bond distances more is the resonance energy. Resonance is
particularly important when the contributing
of 139 pm, a value intermediate between the
structures are equivalent in energy.
C–C single(154 pm) and C=C double (134
pm) bonds. Thus, the structure of benzene The following rules are applied while writing
cannot be represented adequately by the resonance structures:
The resonance structures have (i) the same
above structure. Further, benzene can be
positions of nuclei and (ii) the same number of
represented equally well by the energetically
unpaired electrons. Among the resonance
identical structures I and II. structures, the one which has more number
of covalent bonds, all the atoms with octet
of electrons (except hydrogen which has a
duplet), less separation of opposite charges, (a
negative charge if any on more electronegative
atom, a positive charge if any on more
Therefore, according to the resonance electropositive atom) and more dispersal of
theory (Unit 4) the actual structure of charge, is more stable than others.
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276 chemistry
Problem 8.16 olution
S
Write resonance structures of CH3COO– The two structures are less important
and show the movement of electrons by contributors as they involve charge
curved arrows. separation. Additionally, structure
I contains a carbon atom with an
olution
incomplete octet.
S
First, write the structure and put
unshared pairs of valence electrons on 8.7.7 esonance ffect
appropriate atoms. Then draw the arrows
R
E
The resonance effect is defined as ‘the polarity
one at a time moving the electrons to get
produced in the molecule by the interaction
the other structures.
of two π-bonds or between a π-bond and
lone pair of electrons present on an adjacent
atom’. The effect is transmitted through the
chain. There are two types of resonance or
mesomeric effect designated as R or M effect.
Problem 8.17 (i) Positive Resonance Effect (+R effect)
Write resonance structures of In this effect, the transfer of electrons is away
CH2=CH–CHO. Indicate relative stability from an atom or substituent group attached
of the contributing structures. to the conjugated system. This electron
displacement makes certain positions in the
olution
molecule of high electron densities. This effect
S
in aniline is shown as :
Stability: I > II > III (ii) Negative Resonance Effect (- R effect)

[I: Most stable, more number of covalent This effect is observed when the transfer of
bonds, each carbon and oxygen atom has electrons is towards the atom or substituent
an octet and no separation of opposite group attached to the conjugated system.
charge II: negative charge on more For example in nitrobenzene this electron
electronegative atom and positive charge displacement can be depicted as :
on more electropositive atom; III: does
not contribute as oxygen has positive
charge and carbon has negative charge,
hence least stable].
Problem 8.18
Explain why the following two structures,
I and II cannot be the major contributors The atoms or substituent groups, which
to the real structure of CH3COOCH3. represent +R or –R electron displacement
effects are as follows :
+R effect: – halogen, –OH, –OR, –OCOR, –NH2,
–NHR, –NR2, –NHCOR,
– R effect: – COOH, –CHO, >C=O, – CN, –NO2
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The presence of alternate single and system or to an atom with an unshared

double bonds in an open chain or cyclic system p orbital. The σ electrons of C—H bond of the
is termed as a conjugated system. These alkyl group enter into partial conjugation with
systems often show abnormal behaviour. the attached unsaturated system or with the
The examples are 1,3- butadiene, aniline unshared p orbital. Hyperconjugation is a
and nitrobenzene etc. In such systems, the permanent effect.
π-electrons are delocalised and the system To understand hyperconjugation effect, let
develops polarity. +
us take an example of CH3 C H2 (ethyl cation) in
8.7.8 lectromeric ffect ( effect) which the positively charged carbon atom has
E
E
E
It is a temporary effect. The organic compounds an empty p orbital. One of the C-H bonds of
having a multiple bond (a double or triple the methyl group can align in the plane of this
bond) show this effect in the presence of empty p orbital and the electrons constituting
an attacking reagent only. It is defined as the C-H bond in plane with this p orbital can
the complete transfer of a shared pair of then be delocalised into the empty p orbital
π-electrons to one of the atoms joined by a as depicted in Fig. 8.4 (a).
multiple bond on the demand of an attacking
reagent. The effect is annulled as soon as the
attacking reagent is removed from the domain
of the reaction. It is represented by E and the
shifting of the electrons is shown by a curved
arrow ( ). There are two distinct types of
electromeric effect.
(i) Positive Eelctromeric Effect (+E effect) In
this effect the π−electrons of the multiple
bond are transferred to that atom to which
the reagent gets attached. For example:
Fig. 8.4(a) Orbital diagram showing
hyperconjugation in ethyl cation
This type of overlap stabilises the

carbocation because electron density from
(ii) Negative Electromeric Effect (–E effect) In the adjacent σ bond helps in dispersing the
this effect the π - electrons of the multiple positive charge.
bond are transferred to that atom to which
the attacking reagent does not get attached.
For example:
When inductive and electromeric effects

operate in opposite directions, the electomeric
effect predominates.
In general, greater the number of alkyl
8.7.9 yperconjugation groups attached to a positively charged carbon
H
Hyperconjugation is a general stabilising atom, the greater is the hyperconjugation
interaction. It involves delocalisation of interaction and stabilisation of the cation.
σ electrons of C—H bond of an alkyl group Thus, we have the following relative stability
directly attached to an atom of unsaturated of carbocations :
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278 chemistry
Problem 8.19 +
Explain why (CH 3) 3C is more stable
+ +
than CH3C H2 and C H3 is the least stable
cation.
Hyperconjugation is also possible in olution
alkenes and alkylarenes. +
S
Hyperconjugation interaction in (CH3)3C is+
Delocalisation of electrons by +
greater than in CH3C H2 as the (CH3)3C
hyperconjugation in the case of alkene can +
has nine C-H bonds. In C H3, vacant p
be depicted as in Fig. 8.4(b).
orbital is perpendicular to the plane
in which C-H bonds lie; hence cannot
+
overlap with it. Thus, C H 3 lacks
hyperconjugative stability.
8.7.10 ypes of Organic eactions and
T
R
Mechanisms
Organic reactions can be classified into the
Fig. 8.4(b) Orbital diagram showing following categories:
hyperconjugation in propene (i) Substitution reactions
(ii) Addition reactions
There are various ways of looking at the (iii) Elimination reactions
hyperconjugative effect. One of the way is to (iv) Rearrangement reactions
regard C—H bond as possessing partial ionic
character due to resonance. You will be studying these reactions in
Unit 9 and later in class XII.
8.8 eth ds Puri icati n
M
o
of
f
o
of
Organic m unds
Co
po
Once an organic compound is extracted
from a natural source or synthesised in the
laboratory, it is essential to purify it. Various
methods used for the purification of organic
compounds are based on the nature of the
compound and the impurity present in it.
The common techniques used for
purification are as follows :
(i) Sublimation
(ii) Crystallisation
(iii) Distillation
(iv) Differential extraction and
(v) Chromatography
Finally, the purity of a compound is
ascertained by determining its melting or
boiling point. Most of the pure compounds
have sharp melting points and boiling points.
The hyperconjugation may also be New methods of checking the purity of an
regarded as no bond resonance. organic compound are based on different
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types of chromatographic and spectroscopic carefully. On boiling, the vapours of lower

techniques. boiling component are formed first. The
vapours are condensed by using a condenser
8.8.1 ublimation
and the liquid is collected in a receiver.
S
You have learnt earlier that on heating, some The vapours of higher boiling component
solid substances change from solid to vapour form later and the liquid can be collected
state without passing through liquid state. separately.
The purification technique based on the above
principle is known as sublimation and is used
to separate sublimable compounds from non-
sublimable impurities.
8.8.2 rystallisation
C
This is one of the most commonly used
techniques for the purification of solid organic
compounds. It is based on the difference in
the solubilities of the compound and the
impurities in a suitable solvent. The impure
compound is dissolved in a solvent in which it
is sparingly soluble at room temperature but
appreciably soluble at higher temperature.
The solution is concentrated to get a nearly
saturated solution. On cooling the solution,
pure compound crystallises out and is
removed by filtration. The filtrate (mother
liquor) contains impurities and small quantity
of the compound. If the compound is highly
soluble in one solvent and very little soluble
in another solvent, crystallisation can be Fig.8.5 Simple distillation. The vapours of a
satisfactorily carried out in a mixture of these substance formed are condensed and
the liquid is collected in conical flask.
solvents. Impurities, which impart colour to
the solution are removed by adsorbing over
activated charcoal. Repeated crystallisation Fractional Distillation: If the difference
becomes necessary for the purification in boiling points of two liquids is not much,
of compounds containing impurities of simple distillation cannot be used to separate
comparable solubilities. them. The vapours of such liquids are formed
within the same temperature range and are
8.8.3 istillation condensed simultaneously. The technique of
D
This important method is used to separate fractional distillation is used in such cases. In
(i) volatile liquids from nonvolatile impurities this technique, vapours of a liquid mixture are
and (ii) the liquids having sufficient difference passed through a fractionating column before
in their boiling points. Liquids having condensation. The fractionating column is
different boiling points vaporise at different fitted over the mouth of the round bottom
temperatures. The vapours are cooled and flask (Fig.8.6, page 280).
the liquids so formed are collected separately. Vapours of the liquid with higher boiling
Chloroform (b.p 334 K) and aniline (b.p. 457 point condense before the vapours of the
K) are easily separated by the technique of liquid with lower boiling point. The vapours
distillation (Fig 8.5). The liquid mixture is rising up in the fractionating column become
taken in a round bottom flask and heated richer in more volatile component. By the
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280 chemistry
unit in the fractionating column is called a

theoretical plate. Commercially, columns
with hundreds of plates are available.
One of the technological applications of
fractional distillation is to separate different
fractions of crude oil in petroleum industry.
Distillation under reduced
pressure: This method is
used to purify liquids having
very high boiling points and
those, which decompose at
or below their boiling points.
Such liquids are made to boil
at a temperature lower than
their normal boiling points
by reducing the pressure on
their surface. A liquid boils
at a temperature at which its
vapour pressure is equal to
the external pressure. The
pressure is reduced with
the help of a water pump
or vacuum pump (Fig.8.8).
Glycerol can be separated from
Fig.8.6 Fractional distillation. The vapours of lower boiling spent-lye in soap industry by
fraction reach the top of the column first followed by using this technique.
vapours of higher boiling fractions.
time the vapours reach to the top of the

fractionating column, these are rich in the
more volatile component. Fractionating
columns are available in various sizes and
designs as shown in Fig.8.7. A fractionating
column provides many surfaces for heat
exchange between the ascending vapours
and the descending condensed liquid. Some
of the condensing liquid in the fractionating
column obtains heat from the ascending
vapours and revaporises. The vapours thus
become richer in low boiling component. The
vapours of low boiling component ascend
to the top of the column. On reaching the
top, the vapours become pure in low boiling
component and pass through the condenser
and the pure liquid is collected in a receiver.
After a series of successive distillations, the
remaining liquid in the distillation flask gets
enriched in high boiling component. Each
Fig.8.7 Different types of fractionating columns.
successive condensation and vaporisation
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Fig.8.8 Distillation under reduced pressure. A liquid boils at a temperature below its
vapour pressure by reducing the pressure.
Steam Distillation: This technique is 8.8.4 ifferential xtraction

D
E
applied to separate substances which are When an organic compound is present in an
steam volatile and are immiscible with water. aqueous medium, it is separated by shaking
In steam distillation, steam from a steam it with an organic solvent in which it is more
generator is passed through a heated flask soluble than in water. The organic solvent and
containing the liquid to be distilled. The the aqueous solution should be immiscible
mixture of steam and the volatile organic with each other so that they form two distinct
compound is condensed and collected. The layers which can be separated by separatory
compound is later separated from water using funnel. The organic solvent is later removed
a separating funnel. In steam distillation, by distillation or by evaporation to get back
the liquid boils when the sum of vapour the compound. Differential extraction is
pressures due to the organic liquid (p1) carried out in a separatory funnel as shown in
and that due to water (p2) becomes equal to Fig. 8.10 (Page 282). If the organic compound
the atmospheric pressure (p), i.e. p =p1+ p2. is less soluble in the organic solvent, a very
Since p1 is lower than p, the organic liquid large quantity of solvent would be required
vaporises at lower temperature than its to extract even a very small quantity of the
boiling point. compound. The technique of continuous
Thus, if one of the substances in the extraction is employed in such cases. In this
mixture is water and the other, a water technique same solvent is repeatedly used for
insoluble substance, then the mixture will boil extraction of the compound.
close to but below, 373K. A mixture of water 8.8.5 hromatography
C
and the substance is obtained which can Chromatography is an important technique
be separated by using a separating funnel. extensively used to separate mixtures into
Aniline is separated by this technique from their components, purify compounds and
aniline – water mixture (Fig.8.9, Page 282). also to test the purity of compounds. The
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282 chemistry
Fig.8.9 Steam distillation. Steam volatile component volatilizes, the vapours condense
in the condenser and the liquid collects in conical flask.
name chromatography is based on the Greek
word chroma, for colour since the method
was first used for the separation of coloured
substances found in plants. In this technique,
the mixture of substances is applied onto a
stationary phase, which may be a solid or a
liquid. A pure solvent, a mixture of solvents,
or a gas is allowed to move slowly over the
stationary phase. The components of the
mixture get gradually separated from one
another. The moving phase is called the
mobile phase.
Based on the principle involved,
chromatography is classified into different
categories. Two of these are:
(a) Adsorption chromatography, and Fig.8.10 Differential extraction. Extraction of com-
(b) Partition chromatography. pound takes place based on difference
in solubility
a) Adsorption Chromatography: Adsor-
ption chromatography is based on the fact
that different compounds are adsorbed on distances over the stationary phase. Following
an adsorbent to different degrees. Commonly are two main types of chromatographic
used adsorbents are silica gel and alumina. techniques based on the principle of differential
When a mobile phase is allowed to move adsorption.
over a stationary phase (adsorbent), the (a) Column chromatography, and
components of the mixture move by varying (b) Thin layer chromatography.
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Column Chromatography: Column The glass plate is then placed in a closed jar
chromatography involves separation of containing the eluant (Fig. 8.12a). As the
a mixture over a column of adsorbent eluant rises up the plate, the components of
(stationary phase) packed in a glass tube. the mixture move up along with the eluant to
The column is fitted with a stopcock at its different distances depending on their degree
lower end (Fig. 8.11). The mixture adsorbed of adsorption and separation takes place.
on adsorbent is placed on the top of the The relative adsorption of each component
adsorbent column packed in a glass tube. of the mixture is expressed in terms of its
An appropriate eluant which is a liquid or a retardation factor i.e. Rf value (Fig.8.12 b).
mixture of liquids is allowed to flow down the Rf = Distance moved by the substance from base line (x)
column slowly. Depending upon the degree to Distance moved by the solvent from base line (y)
which the compounds are adsorbed, complete
separation takes place. The most readily
adsorbed substances are retained near the top
and others come down to various distances
in the column (Fig.8.11).
Fig.8.12 (a) T h i n l a y e r c h ro m a t o g r a p h y .
Chromatogram being developed.
Fig.8.11 Column chromatography. Different

stages of separation of components Fig.8.12 (b) Developed chromatogram.
of a mixture.
The spots of coloured compounds are
Thin Layer Chromatography: Thin layer visible on TLC plate due to their original colour.
chromatography (TLC) is another type of The spots of colourless compounds, which are
adsorption chromatography, which involves invisible to the eye but fluoresce in ultraviolet
separation of substances of a mixture over light, can be detected by putting the plate under
a thin layer of an adsorbent coated on glass ultraviolet light. Another detection technique
plate. A thin layer (about 0.2mm thick) of is to place the plate in a covered jar containing
an adsorbent (silica gel or alumina) is spread a few crystals of iodine. Spots of compounds,
over a glass plate of suitable size. The plate which adsorb iodine, will show up as brown
is known as thin layer chromatography plate spots. Sometimes an appropriate reagent
or chromaplate. The solution of the mixture may also be sprayed on the plate. For example,
to be separated is applied as a small spot amino acids may be detected by spraying the
about 2 cm above one end of the TLC plate. plate with ninhydrin solution (Fig.8.12b).
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284 chemistry
Partition Chromatography: Partition spot on the chromatogram. The spots of the

chromatography is based on continuous separated colourless compounds may be
differential partitioning of components of observed either under ultraviolet light or by
a mixture between stationary and mobile the use of an appropriate spray reagent as
phases. Paper chromatography is a type discussed under thin layer chromatography.
of partition chromatography. In paper
8.9 ualitati e nalysis Organic
chromatography, a special quality paper
Q
v
A
of
m unds
known as chromatography paper is used.
Co
po
Chromatography paper contains water trapped The elements present in organic compounds
in it, which acts as the stationary phase. are carbon and hydrogen. In addition to
A strip of chromatography paper spotted these, they may also contain oxygen, nitrogen,
at the base with the solution of the mixture is sulphur, halogens and phosphorus.
suspended in a suitable solvent or a mixture 8.9.1 etection of arbon and ydrogen
D
C
H
of solvents (Fig. 8.13). This solvent acts as the Carbon and hydrogen are detected by heating
mobile phase. The solvent rises up the paper the compound with copper(II) oxide. Carbon
by capillary action and flows over the spot. The present in the compound is oxidised to
paper selectively retains different components carbon dioxide (tested with lime-water, which
according to their differing partition in the develops turbidity) and hydrogen to water
two phases. The paper strip so developed is (tested with anhydrous copper sulphate,
known as a chromatogram. The spots of the which turns blue).
separated coloured compounds are visible at C + 2CuO 2Cu + CO2
different heights from the position of initial 2H + CuO Cu + H2O
CO2 + Ca(OH)2 CaCO3↓ + H2O
5H2O + CuSO4 CuSO4.5H2O
White Blue
8.9.2 etection of Other lements
D
E
Nitrogen, sulphur, halogens and phosphorus
present in an organic compound are detected
by “ assaigne’s test”. The elements present
L
in the compound are converted from covalent
form into the ionic form by fusing the
compound with sodium metal. Following
reactions take place:
Na + C + N NaCN
2Na + S Na2S
Na + X Na X

(X = Cl, Br or I)

C, N, S and X come from organic compound.
Cyanide, sulphide and halide of sodium so
formed on sodium fusion are extracted from
the fused mass by boiling it with distilled
water. This extract is known as sodium fusion
extract.
(A) Test for Nitrogen
Fig.8.13 Paper chromatography.
Chromatography paper in two different The sodium fusion extract is boiled with
shapes. iron(II) sulphate and then acidified with
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concentrated sulphuric acid. The formation bromine and a yellow precipitate, insoluble
of Prussian blue colour confirms the presence in ammonium hydroxide shows the presence
of nitrogen. Sodium cyanide first reacts of iodine.
with iron(II) sulphate and forms sodium X– + Ag+ → AgX
hexacyanidoferrate(II). On heating with X represents a halogen – Cl, Br or I.
concentrated sulphuric acid some iron(II)
If nitrogen or sulphur is also present in the
ions are oxidised to iron(III) ions which
compound, the sodium fusion extract is
react with sodium hexacyanidoferrate(II)
first boiled with concentrated nitric acid to
to produce iron(III) hexacyanidoferrate(II) decompose cyanide or sulphide of sodium
(ferriferrocyanide) which is Prussian blue in formed during Lassaigne’s test. These ions
colour. would otherwise interfere with silver nitrate
6CN– + Fe2+ → [Fe(CN)6]4– test for halogens.
3[Fe(CN)6]4– + 4Fe3+ Fe4[Fe(CN)6]3.xH2O (D) Test for Phosphorus
Prussian blue The compound is heated with an oxidising

(B) Test for Sulphur agent (sodium peroxide). The phosphorus
(a) The sodium fusion extract is acidified present in the compound is oxidised to
with acetic acid and lead acetate is added phosphate. The solution is boiled with nitric
to it. A black precipitate of lead sulphide acid and then treated with ammonium
indicates the presence of sulphur. molybdate. A yellow colouration or precipitate
indicates the presence of phosphorus.
S2– + Pb2+ → PbS

Black Na3PO4 + 3HNO3 → H3PO4+3NaNO3

(b) On treating sodium fusion extract with H3PO4 + 12(NH4)2MoO4 + 21HNO3 →
sodium nitroprusside, appearance of Ammonium
a violet colour further indicates the molybdate

presence of sulphur. (NH4)3PO4.12MoO3 + 21NH4NO3 + 12H2O
S2– + [Fe(CN)5NO]2– → [Fe(CN)5NOS]4– Ammonium
Violet phosphomolybdate

In case, nitrogen and sulphur both are 8.10 uantitati e nalysis
Q
v
A
present in an organic compound, sodium
Quantitative analysis of compounds is very
thiocyanate is formed. It gives blood red colour
important in organic chemistry. It helps
and no Prussian blue since there are no free
chemists in the determination of mass per
cyanide ions.
cent of elements present in a compound. You
Na + C + N + S → NaSCN
have learnt in Unit-1 that mass per cent of
Fe +SCN
3+ –
→ [Fe(SCN)]2+ elements is required for the determination of
Blood red emperical and molecular formula.

If sodium fusion is carried out with excess The percentage composition of elements
of sodium, the thiocyanate decomposes to present in an organic compound is determined
yield cyanide and sulphide. These ions give by the following methods:
their usual tests.
NaSCN + 2Na → NaCN+Na2S 8.10.1 arbon and Hydrogen
C
(C) Test for Halogens Both carbon and hydrogen are estimated in
one experiment. A known mass of an organic
The sodium fusion extract is acidified with
compound is burnt in the presence of excess
nitric acid and then treated with silver nitrate.
of oxygen and copper(II) oxide. Carbon and
A white precipitate, soluble in ammonium
hydrogen in the compound are oxidised to
hydroxide shows the presence of chlorine,
carbon dioxide and water respectively.
a yellowish precipitate, sparingly soluble in
ammonium hydroxide shows the presence of CxHy + (x + y/4) O2 → x CO2 + (y/2) H2O
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286 chemistry
Fig.8.14 Estimation of carbon and hydrogen. Water and carbon dioxide formed on oxidation of substance
are absorbed in anhydrous calcium chloride and potassium hydroxide solutions respectively
contained in U tubes.
The mass of water produced is determined 8.10.2 itrogen
N
by passing the mixture through a weighed There are two methods for estimation of
U-tube containing anhydrous calcium chloride. nitrogen: (i) Dumas method and (ii) Kjeldahl’s
Carbon dioxide is absorbed in another U-tube method.
containing concentrated solution of potassium (i) Dumas method: The nitrogen containing
hydroxide. These tubes are connected in series organic compound, when heated with copper
(Fig. 8.14). The increase in masses of calcium oxide in an atmosphere of carbon dioxide,
chloride and potassium hydroxide gives the yields free nitrogen in addition to carbon
amounts of water and carbon dioxide from dioxide and water.
which the percentages of carbon and hydrogen
CxHyNz + (2x + y/2) CuO →
are calculated.
Let the mass of organic compound be x CO2 + y/2 H2O + z/2 N2 + (2x + y/2) Cu
m g, mass of water and carbon dioxide
Traces of nitrogen oxides formed, if
produced be m1 and m2 g respectively;
any, are reduced to nitrogen by passing the
12 × m2 × 100 gaseous mixture over a heated copper gauze.
Percentage of carbon=
44 × m The mixture of gases so produced is collected
2 × m1 × 100 over an aqueous solution of potassium
Percentage of hydrogen = hydroxide which absorbs carbon dioxide.
18 × m Nitrogen is collected in the upper part of the
Problem 8.20 graduated tube (Fig.8.15).
On complete combustion, 0.246 g of an Let the mass of organic compound = m g
organic compound gave 0.198g of carbon Volume of nitrogen collected = V1 mL
dioxide and 0.1014g of water. Determine
Room temperature = T1K
the percentage composition of carbon
and hydrogen in the compound. 1 1 × 273
PV
Volume of nitrogen at STP =
olution 760 × T1
S
12 × 0.198 × 100 (Let it be V mL)
Percentage of carbon =
44 × 0.246 Where p 1 and V 1 are the pressure and
= 21.95% volume of nitrogen, p1 is different from the
atmospheric pressure at which nitrogen gas
2 × 0.1014 × 100 is collected. The value of p1 is obtained by
Percentage of hydrogen =
18 × 0.246 the relation;
= 4.58% p1= Atmospheric pressure – Aqueous tension
22400 mL N2 at STP weighs 28 g.
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Fig. 8.15 Dumas method. The organic compound yields nitrogen gas on heating it with
copper(II) oxide in the presence of CO2 gas. The mixture of gases is collected over
potassium hydroxide solution in which CO2 is absorbed and volume of nitrogen
gas is determined.
28 × V
V mL N 2 at STP weighs = g 28 × 41.9
22400 41.9 mL of nitrogen weighs = g
22400
28 × V × 100
Percentage of nitrogen = 28 × 41.9 × 100
22400 × m Percentage of nitrogen =
22400 × 0.3
Problem 8.21 = 17.46%
In Dumas’ method for estimation of
nitrogen, 0.3g of an organic compound
gave 50mL of nitrogen collected at 300K
temperature and 715mm pressure. (ii) Kjeldahl’s method: The compound
Calculate the percentage composition containing nitrogen is heated with concentrated
of nitrogen in the compound. (Aqueous sulphuric acid. Nitrogen in the compound
tension at 300K=15 mm) gets converted to ammonium sulphate
(Fig. 8.16). The resulting acid mixture is then
olution
heated with excess of sodium hydroxide.
S
Volume of nitrogen collected at 300K and The liberated ammonia gas is absorbed in
715mm pressure is 50 mL an excess of standard solution of sulphuric
Actual pressure = 715-15 =700 mm acid. The amount of ammonia produced is
273 × 700 × 50 determined by estimating the amount of
Volume of nitrogen at STP sulphuric acid consumed in the reaction. It
300 × 760
is done by estimating unreacted sulphuric
41.9 mL
acid left after the absorption of ammonia by
22,400 mL of N2 at STP weighs = 28 g titrating it with standard alkali solution. The
difference between the initial amount of acid
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288 chemistry
Fig.8.16 Kjeldahl method. Nitrogen-containing compound is treated with concentrated H2SO4 to get
ammonium sulphate which liberates ammonia on treating with NaOH; ammonia is absorbed
in known volume of standard acid.
taken and that left after the reaction gives the 14 × M × 2(V − V1 / 2) 100
amount of acid reacted with ammonia. Percentage of N = ×
1000 m
Organic compound + H2SO4 → (NH4)2SO4
1.4 × M × 2 (V − V / 2)
Na2SO4 + 2NH3 + 2H2O =
m
2NH3 + H2SO4 → (NH4)2SO4
Kjeldahl method is not applicable to
Let the mass of organic compound taken = m g compounds containing nitrogen in nitro and
Volume of H2SO4 of molarity, M, azo groups and nitrogen present in the ring
taken = V mL (e.g. pyridine) as nitrogen of these compounds
Volume of NaOH of molarity, M, used for does not change to ammonium sulphate
titration of excess of H2SO4 = V1 mL under these conditions.
V1mL of NaOH of molarity M
Problem 8.22
= V1 /2 mL of H2SO4 of molarity M
Volume of H 2 SO 4 of molarity M unused During estimation of nitrogen present
= (V - V1/2) mL in an organic compound by Kjeldahl’s
method, the ammonia evolved from
(V- V1/2) mL of H2SO4 of molarity M 0.5 g of the compound in Kjeldahl’s
= 2(V-V1/2) mL of NH3 solution of estimation of nitrogen, neutralized 10 mL
molarity M. of 1 M H2SO4. Find out the percentage of
1000 mL of 1 M NH 3 solution contains nitrogen in the compound.
17g NH3 or 14 g of N olution
S
2(V-V1/2) mL of NH3 solution of molarity M 1 M of 10 mL H2SO4=1M of 20 mL NH3
contains: 1000 mL of 1M ammonia contains 14 g
14 × M × 2(V − V1 / 2) nitrogen
gN
1000 20 mL of 1M ammonia contains
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14 × 20 Percentage of halogen
g nitrogen
1000 atomic mass of X × m1g
=
14×20×100 molecular mass of AgX
Percentage of nitrogen = = 56.0%
1000×0.5
Problem 8.23
8.10.3 alogens In Carius method of estimation of
H
Carius method: A known mass of an organic halogen, 0.15 g of an organic compound
compound is heated with fuming nitric acid in gave 0.12 g of AgBr. Find out the
the presence of silver nitrate contained in a hard percentage of bromine in the compound.
glass tube known as Carius tube, (Fig.8.17) olution
S
Molar mass of AgBr = 108 + 80
= 188 g mol-1
188 g AgBr contains 80 g bromine
80 × 0.12
0.12 g AgBr contains g bromine
188
80 × 0.12 × 100
Percentage of bromine =
188×0.15
= 34.04%
8.10.4 ulphur
S
A known mass of an organic compound is
heated in a Carius tube with sodium peroxide
or fuming nitric acid. Sulphur present in the
compound is oxidised to sulphuric acid. It
is precipitated as barium sulphate by adding
excess of barium chloride solution in water.
The precipitate is filtered, washed, dried and
weighed. The percentage of sulphur can be
Fig. 8.17 Carius method. Halogen containing calculated from the mass of barium sulphate.
organic compound is heated with fuming
nitric acid in the presence of silver
Let the mass of organic
nitrate. compound taken = m g

and the mass of barium
in a furnace. Carbon and hydrogen present in sulphate formed = m1g

the compound are oxidised to carbon dioxide 1 mol of BaSO4 = 233 g BaSO4 = 32 g sulphur
and water. The halogen present forms the 32 × m1 × 100
corresponding silver halide (AgX). It is filtered, m1 g BaSO4 contains g sulphur
233 × m
washed, dried and weighed.
32 × m1 × 100
Let the mass of organic Percentage of sulphur =
compound taken = m g 233 × m
Mass of AgX formed = m1 g
1 mol of AgX contains 1 mol of X
Mass of halogen in m1g of AgX Problem 8.24
atomic mass of X × m1g In sulphur estimation, 0.157 g of an
= organic compound gave 0.4813 g of
molecular mass of AgX
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290 chemistry
percentage composition (100) and the sum of

barium sulphate. What is the percentage
the percentages of all other elements. However,
of sulphur in the compound?
oxygen can also be estimated directly as follows:
olution A definite mass of an organic compound is
S
Molecular mass of BaSO4 = 137+32+64 decomposed by heating in a stream of nitrogen
gas. The mixture of gaseous products containing
= 233 g
oxygen is passed over red-hot coke when all

233 g BaSO4 contains 32 g sulphur the oxygen is converted to carbon monoxide.
32 × 0.4813 This mixture is passed through warm iodine
0.4813 g BaSO4 contains g pentoxide (I2O5) when carbon monoxide is
g sulphur 233
oxidised to carbon dioxide producing iodine.
32 × 0.4813 × 100 Compound  heat
→ O2 + other gaseous

Percentage of sulphur = products
233 × 0.157

2C + O2 
1373 K
→ 2CO]× 5 (A)
= 42.10%

I2O5 + 5CO → I2 + 5CO2]× 2 (B)
8.10.5 Phosphorus On making the amount of CO produced in

A known mass of an organic compound is equation (A) equal to the amount of CO used
heated with fuming nitric acid whereupon in equation (B) by multiplying the equations
phosphorus present in the compound is (A) and (B) by 5 and 2 respectively; we find
oxidised to phosphoric acid. It is precipitated that each mole of oxygen liberated from
as ammonium phosphomolybdate, (NH4)3 the compound will produce two moles of
PO 4 .12MoO 3 , by adding ammonia and carbondioxide.
ammonium molybdate. Alter natively, Thus 88 g carbon dioxide is obtained if 32 g
phosphoric acid may be precipitated as oxygen is liberated.
MgNH4PO4 by adding magnesia mixture which Let the mass of organic compound taken be m g
on ignition yields Mg2P2O7. Mass of carbon dioxide produced be m1 g
Let the mass of organic compound taken ∴ m 1 g carbon dioxide is obtained from
= m g and mass of ammonium phospho 32 × m1
molydate = m1g g O2
88
Molar mass of (NH4)3PO4.12MoO3 = 1877g 32 × m1 × 100
∴Percentage of oxygen = %
31 × m1 × 100 88 × m
Percentage of phosphorus = %
1877 × m The percentage of oxygen can be derived
from the amount of iodine produced also.
If phosphorus is estimated as Mg2P2O7,
Presently, the estimation of elements in
62 × m1 × 100 an organic compound is carried out by using
Percentage of phosphorus = ×%
222 microquantities of substances and automatic
where, 222 u is the molar mass of Mg2P2O7, experimental techniques. The elements,
m, the mass of organic compound taken, carbon, hydrogen and nitrogen present in a
m1, the mass of Mg2P2O7 formed and 62, the compound are determined by an apparatus
mass of two phosphorus atoms present in the known as CHN elemental analyser. The
compound Mg2P2O7. analyser requires only a very small amount
of the substance (1-3 mg) and displays the
8.10.6 Oxygen values on a screen within a short time. A
The percentage of oxygen in an organic compound detailed discussion of such methods is beyond
is usually found by difference between the total the scope of this book.
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ummary
S
In this unit, we have learnt some basic concepts in structure and reactivity of organic
compounds, which are formed due to covalent bonding. The nature of the covalent bonding
in organic compounds can be described in terms of orbitals hybridisation concept,
according to which carbon can have sp3, sp2 and sp hybridised orbitals. The sp3, sp2 and sp
hybridised carbons are found in compounds like methane, ethene and ethyne respectively.
The tetrahedral shape of methane, planar shape of ethene and linear shape of ethyne can
be understood on the basis of this concept. A sp3 hybrid orbital can overlap with 1s orbital
of hydrogen to give a carbon - hydrogen (C–H) single bond (sigma, σ bond). Overlap of a sp2
orbital of one carbon with sp2 orbital of another results in the formation of a carbon–carbon
σ bond. The unhybridised p orbitals on two adjacent carbons can undergo lateral (side-
by-side) overlap to give a pi (π) bond. Organic compounds can be represented by various
structural formulas. The three dimensional representation of organic compounds on paper
can be drawn by wedge and dash formula.
Organic compounds can be classified on the basis of their structure or the functional
groups they contain. A functional group is an atom or group of atoms bonded together in a
unique fashion and which determines the physical and chemical properties of the compounds.
The naming of the organic compounds is carried out by following a set of rules laid down by
the International Union of Pure and Applied Chemistry ( P ). In IUPAC nomenclature,
IU
AC
the names are correlated with the structure in such a way that the reader can deduce the
structure from the name.
Organic reaction mechanism concepts are based on the structure of the substrate
molecule, fission of a covalent bond, the attacking reagents, the electron displacement effects
and the conditions of the reaction. These organic reactions involve breaking and making
of covalent bonds. A covalent bond may be cleaved in heterolytic or homolytic fashion.
A heterolytic cleavage yields carbocations or carbanions, while a homolytic cleavage gives
free radicals as reactive intermediate. Reactions proceeding through heterolytic cleavage
involve the complimentary pairs of reactive species. These are electron pair donor known as
nucleophile and an electron pair acceptor known as electrophile. The inductive, resonance,
electromeric and hyperconjugation effects may help in the polarisation of a bond making
certain carbon atom or other atom positions as places of low or high electron densities.
Organic reactions can be broadly classified into following types; substitution, addition,
elimination and rearrangement reactions.
Purification, qualitative and quantitative analysis of organic compounds are carried out
for determining their structures. The methods of purification namely : sublimation, distillation
and differential extraction are based on the difference in one or more physical properties.
Chromatography is a useful technique of separation, identification and purification of
compounds. It is classified into two categories : adsorption and partition chromatography.
Adsorption chromatography is based on differential adsorption of various components of a
mixture on an adsorbent. Partition chromatography involves continuous partitioning of the
components of a mixture between stationary and mobile phases. After getting the compound
in a pure form, its qualitative analysis is carried out for detection of elements present in it.
Nitrogen, sulphur, halogens and phosphorus are detected by assaigne’s test. Carbon and
L
hydrogen are estimated by determining the amounts of carbon dioxide and water produced.
Nitrogen is estimated by umas or Kjeldahl’s method and halogens by Carius method.
D
Sulphur and phosphorus are estimated by oxidising them to sulphuric and phosphoric acids
respectively. The percentage of oxygen is usually determined by difference between the total
percentage (100) and the sum of percentages of all other elements present.
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292 chemistry
Ex
ercises
8.1 What are hybridisation states of each carbon atom in the following compounds ?
CH2=C=O, CH3CH=CH2, (CH3)2CO, CH2=CHCN, C6H6
8.2 Indicate the σ and π bonds in the following molecules :
C6H6, C6H12, CH2Cl2, CH2=C=CH2, CH3NO2, HCONHCH3
8.3 Write bond line formulas for : Isopropyl alcohol, 2,3-Dimethylbutanal, Heptan-4-one.
8.4 Give the IUPAC names of the following compounds :
(a) (b) (c)
(d) (e) (f) Cl2CHCH2OH
8.5 Which of the following represents the correct IUPAC name for the compounds
concerned ? (a) 2,2-Dimethylpentane or 2-Dimethylpentane (b)
2,4,7-Trimethyloctane or 2,5,7-Trimethyloctane (c) 2-Chloro-4-methylpentane or
4-Chloro-2-methylpentane (d) But-3-yn-1-ol or But-4-ol-1-yne.
8.6 Draw formulas for the first five members of each homologous series beginning with
the following compounds. (a) H–COOH (b) CH3COCH3 (c) H–CH=CH2
8.7 Give condensed and bond line structural formulas and identify the functional group(s)
present, if any, for :
(a) 2,2,4-Trimethylpentane
(b) 2-Hydroxy-1,2,3-propanetricarboxylic acid
(c) Hexanedial
8.8 Identify the functional groups in the following compounds
(a) (b) (c)
8.9 Which of the two: O2NCH2CH2O– or CH3CH2O– is expected to be more stable and
why?
8.10 Explain why alkyl groups act as electron donors when attached to a π system.
8.11 Draw the resonance structures for the following compounds. Show the electron shift
using curved-arrow notation.
+
(a) C 6 H 5 OH (b) C 6 H 5 NO 2 (c) CH 3 CH=CHCHO (d) C 6 H 5 –CHO (e) C 6 H 5 –CH 2
+
(f) CH3CH=CH C H2
8.12 What are electrophiles and nucleophiles ? Explain with examples.
8.13 Identify the reagents shown in bold in the following equations as nucleophiles or
electrophiles:
–
(a) CH3COOH + HO → CH3COO–+H2O
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–
(b) CH3COCH3+ CN → (CH3)2C(CN)(OH)
+
(c) C6H6 + CH3CO → C6H5COCH3
8.14 Classify the following reactions in one of the reaction type studied in this unit.
– –
(a) CH3CH2Br + HS → CH3CH2SH + Br
(b) (CH3)2C = CH2 + HCI → (CH3)2CIC – CH3
– –
(c) CH3CH2Br + HO → CH2 = CH2 + H2O + Br
(d) (CH3)3C– CH2OH + HBr → (CH3)2CBrCH2CH2CH3 + H2O
8.15 What is the relationship between the members of following pairs of structures ?
Are they structural or geometrical isomers or resonance contributors ?
(a)
(b)
(c)
8.16 For the following bond cleavages, use curved-arrows to show the electron flow and
classify each as homolysis or heterolysis. Identify reactive intermediate produced
as free radical, carbocation and carbanion.
(a)
(b)
(c)
(d)
8.17 Explain the terms Inductive and Electromeric effects. Which electron displacement
effect explains the following correct orders of acidity of the carboxylic acids?
(a) Cl3CCOOH > Cl2CHCOOH > ClCH2COOH
(b) CH3CH2COOH > (CH3)2CHCOOH > (CH3)3C.COOH
8.18 Give a brief description of the principles of the following techniques taking an
example in each case.
(a) Crystallisation (b) Distillation (c) Chromatography
8.19 Describe the method, which can be used to separate two compounds with different
solubilities in a solvent S.
8.20 What is the difference between distillation, distillation under reduced pressure and
steam distillation ?
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294 chemistry
8.21 Discuss the chemistry of Lassaigne’s test.

8.22 Differentiate between the principle of estimation of nitrogen in an organic compound
by (i) Dumas method and (ii) Kjeldahl’s method.
8.23 Discuss the principle of estimation of halogens, sulphur and phosphorus present
in an organic compound.
8.24 Explain the principle of paper chromatography.
8.25 Why is nitric acid added to sodium extract before adding silver nitrate for testing
halogens?
8.26 Explain the reason for the fusion of an organic compound with metallic sodium for
testing nitrogen, sulphur and halogens.
8.27 Name a suitable technique of separation of the components from a mixture of
calcium sulphate and camphor.
8.28 Explain, why an organic liquid vaporises at a temperature below its boiling point
in its steam distillation ?
8.29 Will CCl4 give white precipitate of AgCl on heating it with silver nitrate? Give reason
for your answer.
8.30 Why is a solution of potassium hydroxide used to absorb carbon dioxide evolved
during the estimation of carbon present in an organic compound?
8.31 Why is it necessary to use acetic acid and not sulphuric acid for acidification of
sodium extract for testing sulphur by lead acetate test?
8.32 An organic compound contains 69% carbon and 4.8% hydrogen, the remainder
being oxygen. Calculate the masses of carbon dioxide and water produced when
0.20 g of this substance is subjected to complete combustion.
8.33 A sample of 0.50 g of an organic compound was treated according to Kjeldahl’s
method. The ammonia evolved was absorbed in 50 ml of 0.5 M H2SO4. The residual
acid required 60 mL of 0.5 M solution of NaOH for neutralisation. Find the percentage
composition of nitrogen in the compound.
8.34 0.3780 g of an organic chloro compound gave 0.5740 g of silver chloride in Carius
estimation. Calculate the percentage of chlorine present in the compound.
8.35 In the estimation of sulphur by Carius method, 0.468 g of an organic sulphur
compound afforded 0.668 g of barium sulphate. Find out the percentage of sulphur
in the given compound.
8.36 In the organic compound CH2 = CH – CH2 – CH2 – C ≡ CH, the pair of hydridised
orbitals involved in the formation of: C2 – C3 bond is:
(a) sp – sp2 (b) sp – sp3 (c) sp2 – sp3 (d) sp3 – sp3
8.37 In the Lassaigne’s test for nitrogen in an organic compound, the Prussian blue
colour is obtained due to the formation of:
(a) Na4[Fe(CN)6] (b) Fe4[Fe(CN)6]3 (c) Fe2[Fe(CN)6] (d) Fe3[Fe(CN)6]4
8.38 Which of the+ following carbocation
+
is most+ stable ? +
(a) (CH3)3C. C H2 (b) (CH3)3C (c) CH3CH2CH2 (d) CH3CH CH2CH3

8.39 The best and latest technique for isolation, purification and separation of organic
compounds is:
(a) Crystallisation (b) Distillation (c) Sublimation (d) Chromatography
8.40 The reaction:
CH3CH2I + KOH(aq) → CH3CH2OH + KI
is classified as :
(a) electrophilic substitution (b) nucleophilic substitution
(c) elimination (d) addition
2024-25
Unit 8.indd 294 10/10/2022 10:37:40 AM

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256 chemistry

Unit 8.indd 256 2/24/2023 16:52:17

Unit 8.indd 257 10/10/2022 10:37:28 AM

8.3 e resen O Similarly, CH3CH2CH2CH2CH2CH2CH2CH3

These structural formulas can be further

Unit 8.indd 258 10/10/2022 10:37:29 AM

In cyclic compounds, the bond-line formulas

Unit 8.indd 259 10/10/2022 10:37:30 AM

Space filling model

Unit 8.indd 260 11/10/2022 15:19:57

8.4 Classifi ation of rgani (homocyclic).

Acetaldehyde Acetic acid

Unit 8.indd 261 11/10/2022 15:20:58

Heterocyclic aromatic compounds so because it is found in citrus fruits and the

Unit 8.indd 262 11/10/2022 15:20:58

Unit 8.indd 263 10/10/2022 10:37:31 AM

Unit 8.indd 264 10/10/2022 10:37:31 AM

8.5.3 Nomenclature of Organic

Unit 8.indd 265 10/27/2022 2:13:15 PM

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able 8.4 ome Functional roups and lasses of Organic ompounds

Unit 8.indd 267 10/10/2022 10:37:32 AM

olution (iii) Six membered ring containing a

(iv) ‘1-ol’ means that a -OH group is

Unit 8.indd 268 10/10/2022 10:37:32 AM

Substituent of the base compound is

Nitrobenzene Bromobenzene 1-Chloro-2,4-dinitrobenzene

(a) (b) (c)

Unit 8.indd 269 10/10/2022 10:37:33 AM

different carbon skeletons, these are referred

(ii) Position isomerism: When two or

Structural isomerism Stereoisomerism

Chain Position Functional Metamerism Geometrical Optical

Unit 8.indd 270 10/10/2022 10:37:33 AM

in understanding the reactivity of organic

Unit 8.indd 271 12/13/2022 10:12:45

(i) CH2 = CH2 + Br2 →

Unit 8.indd 272 10/10/2022 10:37:34 AM

deficient portion of the molecule (a positive

Unit 8.indd 273 11/10/2022 15:21:53

notation. It shows how changes in bonding 8.7.5 nductive ffect

Unit 8.indd 274 10/10/2022 10:37:34 AM

benzene cannot be adequately represented

Unit 8.indd 275 10/10/2022 10:37:34 AM

Problem 8.16 olution

Stability: I > II > III (ii) Negative Resonance Effect (- R effect)

Unit 8.indd 276 10/10/2022 10:37:35 AM

The presence of alternate single and system or to an atom with an unshared

This type of overlap stabilises the

When inductive and electromeric effects

Unit 8.indd 277 10/10/2022 10:37:35 AM

8.7.10 ypes of Organic eactions and

Unit 8.indd 278 10/10/2022 10:37:35 AM

types of chromatographic and spectroscopic carefully. On boiling, the vapours of lower

Unit 8.indd 279 10/10/2022 10:37:35 AM

unit in the fractionating column is called a

time the vapours reach to the top of the

Unit 8.indd 280 10/10/2022 10:37:35 AM

Steam Distillation: This technique is 8.8.4 ifferential xtraction

Unit 8.indd 281 10/10/2022 10:37:36 AM