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UNIT 13
HYDROCARBONS
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Hydrocarbons are the important sources of energy.
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After studying this unit, you will be
able to
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• name hydrocarbons according to The term ‘hydrocarbon’ is self-explanatory which means
IUPAC system of nomenclature; compounds of carbon and hydrogen only. Hydrocarbons
• recognise and write structures
pu play a key role in our daily life. You must be familiar with
of isomers of alkanes, alkenes, the terms ‘LPG’ and ‘CNG’ used as fuels. LPG is the
alkynes and aromatic
abbreviated form of liquified petroleum gas whereas CNG
hydrocarbons;
stands for compressed natural gas. Another term ‘LNG’
be T
alkenes, alkynes and aromatic Petrol, diesel and kerosene oil are obtained by the fractional
hydrocarbons on the basis of distillation of petroleum found under the earth’s crust.
physical and chemical properties; Coal gas is obtained by the destructive distillation of coal.
tt E
• draw and differentiate between Natural gas is found in upper strata during drilling of oil
various conformations of ethane; wells. The gas after compression is known as compressed
• appreciate the role of natural gas. LPG is used as a domestic fuel with the least
C
hydrocarbons as sources of pollution. Kerosene oil is also used as a domestic fuel but
energy and for other industrial
it causes some pollution. Automobiles need fuels like petrol,
applications;
diesel and CNG. Petrol and CNG operated automobiles
no N
• comprehend the structure of hydrocarbons are used as solvents for paints. They are also
benzene, explain aromaticity used as the starting materials for manufacture of many
and understand mechanism dyes and drugs. Thus, you can well understand the
of electrophilic substitution importance of hydrocarbons in your daily life. In this unit,
reactions of benzene;
you will learn more about hydrocarbons.
• predict the directive influence of
substituents in monosubstituted 13.1 CLASSIFICATION
benzene ring;
• learn about carcinogenicity and Hydrocarbons are of different types. Depending upon the
toxicity. types of carbon-carbon bonds present, they can be
classified into three main categories – (i) saturated
366 CHEMISTRY
(ii) unsaturated and (iii) aromatic general formula for alkane family or
hydrocarbons. Saturated hydrocarbons homologous series? The general formula for
contain carbon-carbon and carbon-hydrogen alkanes is CnH2n+2, where n stands for number
single bonds. If different carbon atoms are of carbon atoms and 2n+2 for number of
joined together to form open chain of carbon hydrogen atoms in the molecule. Can you
atoms with single bonds, they are termed as recall the structure of methane? According to
alkanes as you have already studied in VSEPR theory (Unit 4), methane has a
Unit 12. On the other hand, if carbon atoms tetrahedral structure (Fig. 13.1) which is
form a closed chain or a ring, they are termed multiplanar, in which carbon atom lies at the
d
as cycloalkanes. Unsaturated hydrocarbons centre and the four hydrogen atoms lie at the
contain carbon-carbon multiple bonds – four corners of a regular tetrahedron. All
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double bonds, triple bonds or both. Aromatic H-C-H bond angles are of 109.5°.
hydrocarbons are a special type of cyclic
compounds. You can construct a large number
of models of such molecules of both types
(open chain and close chain) keeping in mind
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that carbon is tetravalent and hydrogen is
monovalent. For making models of alkanes,
you can use toothpicks for bonds and
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plasticine balls for atoms. For alkenes, alkynes
and aromatic hydrocarbons, spring models can
be constructed.
pu Fig. 13.1 Structure of methane
In alkanes, tetrahedra are joined together
13.2 ALKANES in which C-C and C-H bond lengths are
As already mentioned, alkanes are saturated 154 pm and 112 pm respectively (Unit 12). You
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open chain hydrocarbons containing have already read that C–C and C–H σ bonds
re
3
carbon - carbon single bonds. Methane (CH4) are formed by head-on overlapping of sp
o R
is the first member of this family. Methane is a hybrid orbitals of carbon and 1s orbitals of
gas found in coal mines and marshy places. If hydrogen atoms.
you replace one hydrogen atom of methane by
tt E
replacing one hydrogen atom by -CH3 group. are given in parenthesis. First three alkanes
Go on constructing alkanes by doing this – methane, ethane and propane have only
theoretical exercise i.e., replacing hydrogen one structure but higher alkanes can have
atom by –CH3 group. The next molecules will more than one structure. Let us write
©
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In how many ways, you can join five Problem 13.1
carbon atoms and twelve hydrogen atoms of Write structures of different chain isomers
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C5H12? They can be arranged in three ways as of alkanes corresponding to the molecular
shown in structures III–V formula C6H14. Also write their IUPAC
III names.
Solution
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(i) CH3 – CH2 – CH2 – CH2– CH2– CH3
n-Hexane
Pentane (n-pentane)
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(b.p. 309 K)
IV
pu 2-Methylpentane
be T
3-Methylpentane
re
o R
2-Methylbutane (isopentane)
(b.p. 301 K)
2,3-Dimethylbutane
tt E
V
C
2,2 - Dimethylbutane
no N
(b.p. 282.5 K)
(3°) or quaternary (4°). Carbon atom attached
Structures I and II possess same to no other carbon atom as in methane or to
molecular formula but differ in their boiling only one carbon atom as in ethane is called
points and other properties. Similarly primary carbon atom. Terminal carbon atoms
structures III, IV and V possess the same are always primary. Carbon atom attached to
molecular formula but have different two carbon atoms is known as secondary.
properties. Structures I and II are isomers of Tertiary carbon is attached to three carbon
butane, whereas structures III, IV and V are atoms and neo or quaternary carbon is
isomers of pentane. Since difference in attached to four carbon atoms. Can you identify
properties is due to difference in their 1°, 2°, 3° and 4° carbon atoms in structures I
368 CHEMISTRY
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atoms in alkanes or other classes of following problem:
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Problem 13.2
Write structures of different isomeric alkyl groups corresponding to the molecular formula
C5H11. Write IUPAC names of alcohols obtained by attachment of –OH groups at different
carbons of the chain.
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Solution
Structures of – C5H11 group Corresponding alcohols Name of alcohol
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(i) CH3 – CH2 – CH2 – CH2– CH2 – CH3 – CH2 – CH2 – CH2– CH2 – OH Pentan-1-ol
(ii) CH3 – CH – CH2 – CH2 – CH3 CH3 – CH – CH2 – CH2– CH3 Pentan-2-ol
pu | |
OH
be T
(iii) CH3 – CH2 – CH – CH2 – CH3 CH3 – CH2 – CH – CH2– CH3 Pentan-3-ol
| |
re
OH
o R
| | butan-1-ol
(v) CH3 – CH2 – CH – CH2 – CH3 – CH2 – CH – CH2– OH
no N
OH
CH3 CH3 2,2- Dimethyl-
| | propan-1-ol
(vii) CH3 – C – CH2 – CH3 – C – CH2OH
| |
CH3 CH3
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Lowest sum and
(b) CH3 – 7CH2 – 6CH2 – 5CH – 4CH –
8 3
C – 2CH2 – 1CH3 alphabetical
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arrangement
(3,3-Diethyl-5-isopropyl-4-methyloctane)
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sec is not considered
(c) CH3–2CH2–3CH2–4CH–5CH–6CH2–7CH2–8CH2–9CH2–10CH3
1
while arranging
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alphabetically;
isopropyl is taken
5-sec– Butyl-4-isopropyldecane
pu as one word
(d) CH3–2CH2–3CH2–4CH2–5CH–6CH2–7CH2–8CH2–9CH3
1
Further numbering
to the substituents
be T
5-(2,2– Dimethylpropyl)nonane
(e) 1
CH3 – 2CH2 – 3CH – 4CH2 – 5CH – 6CH2 – 7CH3
Alphabetical
tt E
priority order
3–Ethyl–5–methylheptane
C
iii) Attach ethyl group at carbon 3 and two Longest chain is of six carbon atoms and
methyl groups at carbon 2 not that of five. Hence, correct name is
CH3 3-Methylhexane.
| 7 6 5 4 3 2 1
1 2 3 4 5
C – C– C– C– C (ii) CH3 – CH2 – CH – CH2 – CH – CH2 – CH3
| |
CH3 C2 H5
iv) Satisfy the valence of each carbon atom by
putting requisite number of hydrogen Numbering is to be started from the end
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atoms : which gives lower number to ethyl group.
Hence, correct name is 3-ethyl-5-
CH3
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| methylheptane.
CH3 – C – CH – CH2 – CH3
| | 13.2.2 Preparation
CH3 C2H5
Petroleum and natural gas are the main
Thus we arrive at the correct structure. If
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sources of alkanes. However, alkanes can be
you have understood writing of structure from prepared by following methods :
the given name, attempt the following
1. From unsaturated hydrocarbons
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problems.
Dihydrogen gas adds to alkenes and alkynes
Problem 13.4 in the presence of finely divided catalysts like
Write structural formulas of the following
pu platinum, palladium or nickel to form alkanes.
compounds : This process is called hydrogenation. These
metals adsorb dihydrogen gas on their surfaces
(i) 3, 4, 4, 5–Tetramethylheptane
and activate the hydrogen – hydrogen bond.
be T
(13.1)
Ethene Ethane
C
Propene Propane
(ii) CH3 – CH – CH2 – CH2 – CH – CH3
no N
(13.2)
Problem 13.5
CH3 − C ≡ C − H + 2H2 ⎯⎯⎯⎯ → CH3 − CH2 − CH3
Pt/Pd/Ni
Write structures for each of the following
Propyne Propane
©
+
C 2 H 5 − Cl + H 2 ⎯⎯ ⎯
Zn, H
→ C 2 H 6 + HCl containing even number of carbon atoms
Chloroethane Ethane (13.5) at the anode.
Zn,H+
2CH3 COO− Na+ + 2H2 O
CH3 CH2 CH2 Cl + H2 ⎯⎯→ CH3 CH2 CH3 + HCl Sodium acetate
1-Chloropropane Propane
(13.6) ↓ Electrolysis
CH3 −CH3 + 2CO2 + H2 + 2NaOH (13.9)
ii) Alkyl halides on treatment with sodium
metal in dry ethereal (free from moisture) The reaction is supposed to follow the
following path :
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solution give higher alkanes. This reaction
is known as Wurtz reaction and is used O
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for the preparation of higher alkanes ||
−
containing even number of carbon i) 2CH3 COO Na+ 2CH3 −C − O− + 2Na+
atoms.
dry ether ii) At anode:
CH3 Br +2Na + BrCH3 ⎯⎯⎯⎯ →CH3 −CH3 +2NaBr
O O
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Bromomethane Ethane || ||
• •
(13.7) –2e
2CH3 −C −O ⎯⎯
– −
→2CH3 −C −O: ⎯⎯
→2CH3 + 2CO2 ↑
••
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dry ether
C2 H5 Br + 2Na + BrC2 H5 ⎯⎯⎯⎯ →C2 H5 −C2 H5
Acetate ion Acetate Methyl free
Bromoethane n-Butane free radical radical
pu (13.8) • •
iii) H3 C + CH3 ⎯⎯
→ H3 C −CH3 ↑
What will happen if two different alkyl halides
are taken? iv) At cathode :
•
H2 O + e– → – OH + H
be T
chemical equation for the reaction. or more are solids at 298 K. They are colourless
and odourless. What do you think about
Solution solubility of alkanes in water based upon non-
Butanoic acid, polar nature of alkanes? Petrol is a mixture of
−
CH3 CH2 CH2 COO Na + + NaOH ⎯⎯
CaO
→ hydrocarbons and is used as a fuel for
automobiles. Petrol and lower fractions of
CH3 CH2 CH3 + Na2 CO3
petroleum are also used for dry cleaning of
clothes to remove grease stains. On the basis
ii) Kolbe’s electrolytic method An aqueous of this observation, what do you think about
solution of sodium or potassium salt of a the nature of the greasy substance? You are
carboxylic acid on electrolysis gives alkane correct if you say that grease (mixture of higher
372 CHEMISTRY
alkanes) is non-polar and, hence, hydrophobic reducing agents. However, they undergo the
in nature. It is generally observed that in following reactions under certain
relation to solubility of substances in solvents, conditions.
polar substances are soluble in polar solvents,
1. Substitution reactions
whereas the non-polar ones in non-polar
solvents i.e., like dissolves like. One or more hydrogen atoms of alkanes can
be replaced by halogens, nitro group and
Boiling point (b.p.) of different alkanes are
sulphonic acid group. Halogenation takes
given in Table 13.2 from which it is clear that
there is a steady increase in boiling point with place either at higher temperature
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increase in molecular mass. This is due to the (573-773 K) or in the presence of diffused
fact that the intermolecular van der Waals sunlight or ultraviolet light. Lower alkanes do
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forces increase with increase of the molecular not undergo nitration and sulphonation
size or the surface area of the molecule. reactions. These reactions in which hydrogen
atoms of alkanes are substituted are known
You can make an interesting observation
as substitution reactions. As an example,
by having a look on the boiling points of
chlorination of methane is given below:
is
three isomeric pentanes viz., (pentane,
2-methylbutane and 2,2-dimethylpropane). It Halogenation
is observed (Table 13.2) that pentane having a hν
CH4 + Cl2 ⎯⎯ → +
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CH3 Cl HCl
continuous chain of five carbon atoms has the
highest boiling point (309.1K) whereas Chloromethane (13.10)
2,2 – dimethylpropane boils at 282.5K. With
pu hν
increase in number of branched chains, the CH 3 Cl + Cl2 ⎯ ⎯⎯
→ CH 2 Cl2 + HCl
molecule attains the shape of a sphere. This Dichloromethane (13.11)
results in smaller area of contact and therefore
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lower temperatures.
Chemical properties hν
CHCl3 + Cl2 ⎯⎯⎯
→ CCl4 + HCl
As already mentioned, alkanes are generally Tetrachloromethane (13.13)
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and / or due to the following side reactions :
presence of oxidizing agents like HIO3 or HNO3.
The possible chain terminating steps are :
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CH4 + I2 CH3 I + HI (13.15) • •
(a) Cl + Cl → Cl − Cl
HIO3 +5HI → 3I2 + 3H2 O (13.16) • •
(b) H3 C + CH3 → H3 C − CH3
Halogenation is supposed to proceed via
• •
free radical chain mechanism involving three (c) H3 C + Cl → H3 C − Cl
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steps namely initiation, propagation and
termination as given below: Though in (c), CH3 – Cl, the one of the
products is formed but free radicals are
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Mechanism consumed and the chain is terminated. The
(i) Initiation : The reaction is initiated by above mechanism helps us to understand the
homolysis of chlorine molecule in the presence
pu reason for the formation of ethane as a
of light or heat. The Cl–Cl bond is weaker than byproduct during chlorination of methane.
the C–C and C–H bond and hence, is easiest to 2. Combustion
break.
be T
• •
Alkanes on heating in the presence of air or
hν dioxygen are completely oxidized to carbon
Cl −Cl ⎯⎯⎯⎯ → Cl + Cl
re
homolysis
dioxide and water with the evolution of large
o R
•
hν
•
Δc H V =−2875.84 kJ mol−1
( a) CH4 + Cl ⎯⎯⎯ →CH + H − Cl
3 (13.18)
no N
The methyl radical thus obtained attacks The general combustion equation for any
the second molecule of chlorine to form alkane is :
CH3 – Cl with the liberation of another chlorine
⎛ 3n +1⎞
free radical by homolysis of chlorine molecule. Cn H2n+2 + ⎜ ⎟O2 → nCO2 + (n +1) H2 O
©
⎝ 2 ⎠
• •
hν
(b) C H3 + Cl − Cl ⎯⎯⎯ → CH3 − Cl + C l (13.19)
Chlorine Due to the evolution of large amount of
free radical heat during combustion, alkanes are used
as fuels.
The chlorine and methyl free radicals
generated above repeat steps (a) and (b) During incomplete combustion of
respectively and thereby setup a chain of alkanes with insufficient amount of air or
reactions. The propagation steps (a) and (b) are dioxygen, carbon black is formed which is
those which directly give principal products, used in the manufacture of ink, printer ink,
but many other propagation steps are possible black pigments and as filters.
374 CHEMISTRY
Incomplete
CH4 (g) + O2 (g) ⎯⎯⎯⎯⎯ pressure in the presence of oxides of
combustion→C(s) + 2H2 O(l)
vanadium, molybdenum or chromium
(13.20) supported over alumina get dehydrogenated
and cyclised to benzene and its homologues.
3. Controlled oxidation
This reaction is known as aromatization or
Alkanes on heating with a regulated supply of
reforming.
dioxygen or air at high pressure and in the
presence of suitable catalysts give a variety of
oxidation products.
d
Cu/523K/100atm
(i) 2CH4 + O2 ⎯⎯⎯⎯⎯⎯⎯→ 2CH3 OH
Methanol
he
(13.21)
Mo2O3
(ii) CH4 + O2 ⎯⎯⎯→ HCHO + H2 O (13.26)
Δ
Methanal Toluene (C7H8) is methyl derivative of
is
(13.22) benzene. Which alkane do you suggest for
(CH3COO)2 Mn
(iii)2CH3 CH3 + 3O2 ⎯⎯⎯⎯⎯⎯→ 2 CH3 COOH preparation of toluene ?
Δ
Ethanoic acid 6. Reaction with steam
bl
+ 2H2 O Methane reacts with steam at 1273 K in the
(13.23) presence of nickel catalyst to form carbon
pu monoxide and dihydrogen. This method is
(iv) Ordinarily alkanes resist oxidation but used for industrial preparation of dihydrogen
alkanes having tertiary H atom can be gas
oxidized to corresponding alcohols by
be T
Ni
potassium permanganate. CH4 + H2 O ⎯⎯ → CO + 3H2 (13.27)
Δ
re
KMnO
(CH3 )3 CH ⎯⎯⎯⎯
Oxidation→
4
(CH3 )3 COH 7. Pyrolysis
o R
d
can change into one another. Such spatial three lines attached to it corresponding to three
arrangements of atoms which can be hydrogen atoms. The lines are inclined at an
he
converted into one another by rotation around angle of 120° to each other. Sawhorse projections
a C-C single bond are called conformations of eclipsed and staggered conformations of
or conformers or rotamers. Alkanes can thus ethane are depicted in Fig. 13.2.
have infinite number of conformations by
rotation around C-C single bonds. However,
is
it may be remembered that rotation around
a C-C single bond is not completely free. It is
hindered by a small energy barrier of
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–1
1-20 kJ mol due to weak repulsive
interaction between the adjacent bonds. Such
a type of repulsive interaction is called
pu
torsional strain.
Conformations of ethane : Ethane Fig. 13.2 Sawhorse projections of ethane
be T
ball and stick model of ethane, keep one C–C bond head on. The carbon atom nearer to
carbon atom stationary and rotate the other the eye is represented by a point. Three
carbon atom around the C-C axis. This hydrogen atoms attached to the front carbon
tt E
rotation results into infinite number of spatial atom are shown by three lines drawn at an
arrangements of hydrogen atoms attached to angle of 120° to each other. The rear carbon
one carbon atom with respect to the hydrogen atom (the carbon atom away from the eye) is
C
atoms attached to the other carbon atom. represented by a circle and the three hydrogen
These are called conformational isomers atoms are shown attached to it by the shorter
(conformers). Thus there are infinite number lines drawn at an angle of 120° to each other.
no N
of conformations of ethane. However, there are The Newman’s projections are depicted in
two extreme cases. One such conformation in Fig. 13.3.
which hydrogen atoms attached to two
carbons are as closed together as possible is
©
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carbon atoms. The double bond is shorter in
each other resulting in increase in electron bond length (134 pm) than the C–C single bond
cloud repulsions. To check the increased (154 pm). You have already read that the pi (π)
he
repulsive forces, molecule will have to possess bond is a weaker bond due to poor sideways
more energy and thus has lesser stability. As overlapping between the two 2p orbitals. Thus,
already mentioned, the repulsive interaction the presence of the pi (π) bond makes alkenes
between the electron clouds, which affects behave as sources of loosely held mobile
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stability of a conformation, is called torsional electrons. Therefore, alkenes are easily attacked
strain. Magnitude of torsional strain depends by reagents or compounds which are in search
upon the angle of rotation about C–C bond. of electrons. Such reagents are called
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This angle is also called dihedral angle or electrophilic reagents. The presence of
torsional angle. Of all the conformations of weaker π-bond makes alkenes unstable
ethane, the staggered form has the least
pu molecules in comparison to alkanes and thus,
torsional strain and the eclipsed form, the alkenes can be changed into single bond
maximum torsional strain. Thus it may be compounds by combining with the
inferred that rotation around C–C bond in electrophilic reagents. Strength of the double
be T
–1
ethane (bond enthalpy, 348 kJ mol ). Orbital
Even at ordinary temperatures, the ethane diagrams of ethene molecule are shown in
molecule gains thermal or kinetic energy Figs. 13.4 and 13.5.
tt E
13.3 ALKENES
Alkenes are unsaturated hydrocarbons
©
Fig. 13.5 Orbital picture of ethene showing formation of (a) π-bond, (b) π-cloud and (c) bond angles
and bond lengths
d
of alkanes. It may be remembered that first Solution
he
member of alkene series is: CH2 (replacing n
(i) 2,8-Dimethyl-3, 6-decadiene;
by 1 in CnH2n) known as methene but has a
very short life. As already mentioned, first (ii) 1,3,5,7 Octatetraene;
stable member of alkene series is C2H4 known (iii) 2-n-Propylpent-1-ene;
as ethylene (common) or ethene (IUPAC). (iv) 4-Ethyl-2,6-dimethyl-dec-4-ene;
is
IUPAC names of a few members of alkenes are
given below : Problem 13.8
Structure IUPAC name Calculate number of sigma (σ) and pi (π)
bl
CH3 – CH = CH2 Propene bonds in the above structures (i-iv).
CH3 – CH2 – CH = CH2 But – l - ene
pu Solution
CH3 – CH = CH–CH3 But-2-ene σ bonds : 33, π bonds : 2
CH2 = CH – CH = CH2 Buta – 1,3 - diene σ bonds : 17, π bonds : 4
be T
geometrical isomerism.
Problem 13.7
Structural isomerism : As in alkanes, ethene
C
y
C4H8 as molecular formula can be written in
CH3 – CH – CH
the following three ways:
|
C2H5 I. 1 2 3 4
©
But-1-ene
(iii) CH2 = C (CH2CH2CH3)2 (C4H8)
(iv) CH3 CH2 CH2 CH2 CH2CH3
| | II. 1 2 3 4
CH3 – CHCH = C – CH2 – CHCH3 CH3 – CH = CH – CH3
|
CH3 But-2-ene
(C4H8)
378 CHEMISTRY
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structures I and II are position isomers. geometry if atoms or groups around C=C bond
can be rotated but rotation around C=C bond
Problem 13.9
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is not free. It is restricted. For understanding
Write structures and IUPAC names of this concept, take two pieces of strong
different structural isomers of alkenes cardboards and join them with the help of two
corresponding to C5H10. nails. Hold one cardboard in your one hand
and try to rotate the other. Can you really rotate
is
Solution
the other cardboard ? The answer is no. The
(a) CH2 = CH – CH2 – CH2 – CH3 rotation is restricted. This illustrates that the
Pent-1-ene restricted rotation of atoms or groups around
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(b) CH3 – CH=CH – CH2 – CH3 the doubly bonded carbon atoms gives rise to
Pent-2-ene different geometries of such compounds. The
stereoisomers of this type are called
pu
(c) CH3 – C = CH – CH3
|
geometrical isomers. The isomer of the type
(a), in which two identical atoms or groups lie
CH3
be T
CH3
in their properties like melting point, boiling
2-Methylbut-1-ene point, dipole moment, solubility etc.
no N
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13.3.4 Preparation
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1. From alkynes: Alkynes on partial
reduction with calculated amount of
cis-But-2-ene trans-But-2-ene dihydrogen in the presence of palladised
(μ = 0.33D) (μ = 0) charcoal partially deactivated with poisons
is
In the case of solids, it is observed that like sulphur compounds or quinoline give
the trans isomer has higher melting point alkenes. Partially deactivated palladised
charcoal is known as Lindlar’s catalyst.
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than the cis form.
Alkenes thus obtained are having cis
Geometrical or cis-trans isomerism
geometry. However, alkynes on reduction
is also shown by alkenes of the types
with sodium in liquid ammonia form trans
pu
XYC = CXZ and XYC = CZW
alkenes.
Problem 13.10
be T
IUPAC names :
(i) CHCl = CHCl (13.30)
(ii) C2H5CCH3 = CCH3C2H5
tt E
Solution
C
(13.31)
no N
Pd/C
iii) CH ≡ CH + H2 ⎯⎯⎯ → CH2 = CH2 (13.32)
Ethyne Ethene
©
Pd/C
iv) CH3 − C ≡ CH + H2 ⎯⎯⎯ →CH3 − CH = CH2
Propyne Propene
(13.33)
Will propene thus obtained show
geometrical isomerism? Think for the
Problem 13.11 reason in support of your answer.
Which of the following compounds will
show cis-trans isomerism? 2. From alkyl halides: Alkyl halides (R-X)
on heating with alcoholic potash
(i) (CH3)2C = CH – C2H5
(potassium hydroxide dissolved in alcohol,
380 CHEMISTRY
say, ethanol) eliminate one molecule of takes out one hydrogen atom from the
halogen acid to form alkenes. This reaction β-carbon atom.
is known as dehydrohalogenation i.e.,
removal of halogen acid. This is example of
β-elimination reaction, since hydrogen
atom is eliminated from the β carbon atom
(carbon atom next to the carbon to which
halogen is attached).
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(13.37)
13.3.5 Properties
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Physical properties
Alkenes as a class resemble alkanes in physical
properties, except in types of isomerism and
(13.34) difference in polar nature. The first three
is
members are gases, the next fourteen are
Nature of halogen atom and the alkyl
liquids and the higher ones are solids. Ethene
group determine rate of the reaction. It is
is a colourless gas with a faint sweet smell. All
bl
observed that for halogens, the rate is:
other alkenes are colourless and odourless,
iodine > bromine > chlorine, while for alkyl
insoluble in water but fairly soluble in non-
groups it is : tert > secondary > primary.
pu polar solvents like benzene, petroleum ether.
3. From vicinal dihalides: Dihalides in They show a regular increase in boiling point
which two halogen atoms are attached to with increase in size i.e., every – CH2 group
two adjacent carbon atoms are known as added increases boiling point by 20–30 K. Like
be T
vicinal dihalides. Vicinal dihalides on alkanes, straight chain alkenes have higher
treatment with zinc metal lose a molecule
re
boiling point than isomeric branched chain
o R
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Markovnikov, a Russian chemist made a
generalisation in 1869 after studying such
reactions in detail. These generalisations led
he
Markovnikov to frame a rule called
Markovnikov rule. The rule states that
(13.38) negative part of the addendum (adding
molecule) gets attached to that carbon atom
is
(ii) CH3 − CH = CH2 + Cl − Cl ⎯⎯→CH3 − CH − CH2 which possesses lesser number of hydrogen
| | atoms. Thus according to this rule, product I
Cl Cl i.e., 2-bromopropane is expected. In actual
bl
Propene 1,2-Dichloropropane
practice, this is the principal product of the
(13.39) reaction. This generalisation of Markovnikov
3. Addition of hydrogen halides:
pu rule can be better understood in terms of
Hydrogen halides (HCl, HBr,HI) add up to mechanism of the reaction.
alkenes to form alkyl halides. The order of Mechanism
reactivity of the hydrogen halides is +
be T
unsymmetrical alkenes
Addition reaction of HBr to symmetrical
C
alkenes
Addition reactions of HBr to symmetrical
(a) less stable (b) more stable
alkenes (similar groups attached to double
primary carbocation secondary carbocation
no N
d
the University of Chicago. This reaction 1-bromopropane as the major product. It may
is known as peroxide or Kharash effect be noted that the peroxide effect is not observed
he
or addition reaction anti to Markovnikov in addition of HCl and HI. This may be due
rule. to the fact that the H–Cl bond being
–1
(C H CO) O stronger (430.5 kJ mol ) than H–Br bond
CH3 –CH = CH2 + HBr ⎯⎯⎯⎯⎯⎯
6 5 2 2
→CH3 – CH2 –1
(363.7 kJ mol ), is not cleaved by the free
x radical, whereas the H–I bond is weaker
is
–1
CH2 Br (296.8 kJ mol ) and iodine free radicals
1-Bromopropane combine to form iodine molecules instead of
bl
(13.43) adding to the double bond.
Mechanism : Peroxide effect proceeds via free
radical chain mechanism as given below:
pu Problem 13.12
Write IUPAC names of the products
(i) obtained by addition reactions of HBr to
hex-1-ene
be T
Solution
tt E
• •
(ii) C6 H5 + H – Br ⎯⎯⎯⎯
Homolysis
⎯→C6 H6 + Br
C
no N
©
(13.49)
(13.44) KMnO /H+
CH3 – CH = CH – CH3 ⎯⎯⎯⎯⎯
4
→2CH3 COOH
d
But -2-ene Ethanoic acid
(13.50)
he
7. Ozonolysis : Ozonolysis of alkenes involves
the addition of ozone molecule to alkene to
form ozonide, and then cleavage of the
ozonide by Zn-H2O to smaller molecules.
is
This reaction is highly useful in detecting
(13.45) the position of the double bond in alkenes
or other unsaturated compounds.
bl
5. Addition of water : In the presence of a
few drops of concentrated sulphuric acid
alkenes react with water to form alcohols,
pu
in accordance with the Markovnikov rule.
be T
re
o R
(13.51)
(13.46)
tt E
(13.52)
(13.47) 8. Polymerisation: You are familiar with
polythene bags and polythene sheets.
Polythene is obtained by the combination
of large number of ethene molecules at high
temperature, high pressure and in the
presence of a catalyst. The large molecules
(13.48) thus obtained are called polymers. This
b) Acidic potassium permanganate or acidic reaction is known as polymerisation. The
potassium dichromate oxidises alkenes to simple compounds from which polymers
384 CHEMISTRY
are made are called monomers. Other are named as derivatives of the corresponding
alkenes also undergo polymerisation. alkanes replacing ‘ane’ by the suffix ‘yne’. The
High temp./pressure
position of the triple bond is indicated by the
n(CH2 = CH2 ) ⎯⎯⎯⎯⎯⎯⎯⎯
Catalyst → —( CH2 –CH2 —
)n first triply bonded carbon. Common and
Polythene IUPAC names of a few members of alkyne series
(13.53) are given in Table 13.2.
High temp./pressure
You have already learnt that ethyne and
n(CH3 –CH = CH2 ) ⎯⎯⎯⎯⎯⎯⎯⎯
Catalyst → —
( CH–CH2 —)n propyne have got only one structure but there
|
are two possible structures for butyne –
d
CH3
Polypropene (i) but-1-yne and (ii) but-2-yne. Since these two
compounds differ in their structures due to the
he
(13.54) position of the triple bond, they are known as
Polymers are used for the manufacture of position isomers. In how many ways, you can
plastic bags, squeeze bottles, refrigerator dishes, construct the structure for the next homologue
toys, pipes, radio and T.V. cabinets etc. i.e., the next alkyne with molecular formula
Polypropene is used for the manufacture of milk
is
C5H8? Let us try to arrange five carbon atoms
crates, plastic buckets and other moulded with a continuous chain and with a side chain.
articles. Though these materials have now Following are the possible structures :
become common, excessive use of polythene
bl
Structure IUPAC name
and polypropylene is a matter of great concern
for all of us. 1 2 3 4
I. HC ≡ C– CH – CH – CH Pent–1-yne
5
pu 2 2 3
13.4 ALKYNES 1 2 3 4 5
II. H C– C ≡ C– CH – CH Pent–2-yne
Like alkenes, alkynes are also unsaturated 3 2 3
isomers.
is ethyne which is popularly known as
acetylene. Acetylene is used for arc welding Problem 13.13
C
th
In common system, alkynes are named as 5 member of alkyne has the molecular
derivatives of acetylene. In IUPAC system, they formula C6H10. The possible isomers are:
Table 13.2 Common and IUPAC Names of Alkynes (CnH2n–2)
d
3-Methylpent-1-yne
he
4-Methylpent-1-yne
is
bl
4-Methylpent-2-yne
pu Fig. 13.6 Orbital picture of ethyne showing
(a) sigma overlaps (b) pi overlaps.
-1
enthalpy 823 kJ mol ) is more than those of
–1
13.4.2 Structure of Triple Bond C=C bond (bond enthalpy 681 kJ mol ) and
–1
C–C bond (bond enthalpy 348 kJ mol ). The
C
Each carbon atom of ethyne has two sp cylindrically symmetrical about the
hybridised orbitals. Carbon-carbon sigma (σ) internuclear axis. Thus, ethyne is a linear
bond is obtained by the head-on overlapping molecule.
of the two sp hybridised orbitals of the two
©
d
dehydrohalogenation. One molecule of to a greater extent than that of the sp
2
hydrogen halide is eliminated to form hybridised orbitals of carbon in ethene and the
he
alkenyl halide which on treatment with 3
sp hybridised orbital of carbon in ethane.
sodamide gives alkyne. Thus in ethyne, hydrogen atoms can be
liberated as protons more easily as compared
to ethene and ethane. Hence, hydrogen atoms
of ethyne attached to triply bonded carbon
is
atom are acidic in nature. You may note that
the hydrogen atoms attached to the triply
bonded carbons are acidic but not all the
bl
hydrogen atoms of alkynes.
–
pu HC ≡ CH + Na → HC ≡ C Na + + ½H2
13.4.4 Properties
Monosodium
Physical properties ethynide
Physical properties of alkynes follow the same
be T
– –
and the higher ones are solids. All alkynes are HC ≡ C – Na + + Na → Na + C ≡ C Na + + ½H2
colourless. Ethyene has characteristic odour. Disodium ethynide
Other members are odourless. Alkynes are
tt E
(13.60)
weakly polar in nature. They are lighter than
water and immiscible with water but soluble CH3 – C ≡ C − H + Na + NH2–
C
A. Acidic character of alkyne: Sodium about the above reactions with but-1-yne and
metal and sodamide (NaNH2) are strong bases. but-2-yne ? Alkanes, alkenes and alkynes
They react with ethyne to form sodium follow the following trend in their acidic
acetylide with the liberation of dihydrogen gas. behaviour :
These reactions have not been observed in case i) HC ≡ CH > H2 C = CH2 > CH3 –CH3
of ethene and ethane thus indicating that
ethyne is acidic in nature in comparison to ii) HC ≡ CH > CH3 – C ≡ CH >> CH3 – C ≡ C – CH3
ethene and ethane. Why is it so ? Has it B. Addition reactions: Alkynes contain a
something to do with their structures and the triple bond, so they add up, two molecules of
hybridisation ? You have read that hydrogen dihydrogen, halogen, hydrogen halides etc.
HYDROCARBONS 387
d
unsymmetrical alkynes takes place according
to Markovnikov rule. Majority of the reactions
of alkynes are the examples of electrophilic (13.66)
he
addition reactions. A few addition reactions are (iv) Addition of water
given below: Like alkanes and alkenes, alkynes are also
(i) Addition of dihydrogen immiscible and do not react with water.
Pt/Pd/Ni H2 However, one molecule of water adds to alkynes
HC ≡ CH+ H2 ⎯⎯⎯⎯ →[H2C = CH2 ] ⎯⎯→CH3 –CH3
is
on warming with mercuric sulphate and dilute
(13.62) sulphuric acid at 333 K to form carbonyl
Pt/Pd/Ni
CH3 – C ≡ CH + H2 ⎯⎯⎯⎯→[CH3 – CH = CH2 ] compounds.
bl
Propyne Propene
pu ↓ H2
CH3 – CH2 – CH3
Propane
(13.63)
be T
(13.67)
tt E
C
no N
(13.64)
Reddish orange colour of the solution of
bromine in carbon tetrachloride is decolourised.
This is used as a test for unsaturation.
©
(13.68)
(iii) Addition of hydrogen halides
(v) Polymerisation
Two molecules of hydrogen halides (HCl, HBr,
HI) add to alkynes to form gem dihalides (in (a) Linear polymerisation: Under suitable
which two halogens are attached to the same conditions, linear polymerisation of ethyne
carbon atom) takes place to produce polyacetylene or
H – C ≡ C – H + H – Br ⎯→ [CH2 = CH – Br] ⎯→ CHBr2 polyethyne which is a high molecular weight
Bromoethene | polyene containing repeating units of
CH3 (CH = CH – CH = CH ) and can be represented
1,1-Dibromoethane as —( CH = CH – CH = CH )— n Under special
(13.65) conditions, this polymer conducts electricity.
388 CHEMISTRY
d
derivatives of benzene, dyes, drugs and large Some examples of arenes are given
number of other organic compounds. This is below:
he
the best route for entering from aliphatic to
aromatic compounds as discussed below:
is
Benzene Toluene Naphthalene
bl
pu (13.69)
Problem 13.14
How will you convert ethanoic acid into Biphenyl
be T
benzene?
13.5.1 Nomenclature and Isomerism
re
Solution
The nomenclature and isomerism of aromatic
o R
d
of benzene structure later as:
FRIEDRICH
“I was sitting writing at my text book,but the work did not progress; my thoughts
AUGUST KEKULÉ
he
were elsewhere.I turned my chair to the fire, and dozed. Again the atoms were
(7th September
gambolling before my eyes. This time the smaller groups kept modestly in the
1829–13th July
background. My mental eye, rendered more acute by repeated visions of this kind, 1896)
could now distinguish larger structures of manifold conformations; long
is
rows,sometimes more closely fitted together; all twisting and turning in snake like motion. But look! What
was that? One of the snakes had seized hold of it’s own tail, and the form whirled mockingly before my eyes.
As if by a flash of lightning I woke;.... I spent the rest of the night working out the consequences of the
bl
hypothesis. Let us learn to dream, gentlemen, and then perhaps we shall learn the truth but let us beware of
making our dreams public before they have been approved by the waking mind.”( 1890).
One hundred years later, on the occasion of Kekulé’s centenary celebrations a group of compounds having
pu
polybenzenoid structures have been named as Kekulenes.
be T
d
concept of oscillating nature of double bonds
in benzene as given below.
he
The unhybridised p orbital of carbon atoms
are close enough to form a π bond by lateral
overlap. There are two equal possibilities of
forming three π bonds by overlap of p orbitals
is
of C1 –C2, C3 – C4, C5 – C6 or C2 – C3, C4 – C5,
Even with this modification, Kekulé
C6 – C1 respectively as shown in the following
structure of benzene fails to explain unusual
bl
figures.
stability and preference to substitution
reactions than addition reactions, which could
later on be explained by resonance.
pu
Resonance and stability of benzene
According to Valence Bond Theory, the concept
be T
between all the carbon atoms in the ring has (i) Planarity
been determined by the X-ray diffraction to be (ii) Complete delocalisation of the π electrons
the same; there is equal probability for the p in the ring
orbital of each carbon atom to overlap with the
(iii) Presence of (4n + 2) π electrons in the ring
p orbitals of adjacent carbon atoms [Fig. 13.7
where n is an integer (n = 0, 1, 2, . . .).
(c)]. This can be represented in the form of two
doughtnuts (rings) of electron clouds [Fig. 13.7 This is often referred to as Hückel Rule.
(d)], one above and one below the plane of the Some examples of aromatic compounds are
hexagonal ring as shown below: given below:
d
he
is
(electron cloud)
bl
Fig. 13.7 (c) Fig. 13.7 (d)
The six π electrons are thus delocalised and
pu
can move freely about the six carbon nuclei,
instead of any two as shown in Fig. 13.6 (a) or
(b). The delocalised π electron cloud is attracted
be T
cyclohexatriene.
X-Ray diffraction data reveals that benzene
C
(iii) Reduction of phenol: Phenol is reduced (ii) Halogenation: Arenes react with halogens
to benzene by passing its vapours over in the presence of a Lewis acid like anhydrous
heated zinc dust FeCl3, FeBr3 or AlCl3 to yield haloarenes.
(13.71) Chlorobenzene
d
13.5.5 Properties (13.73)
(iii) Sulphonation: The replacement of a
he
Physical properties
Aromatic hydrocarbons are non- polar hydrogen atom by a sulphonic acid group in
molecules and are usually colourless liquids a ring is called sulphonation. It is carried out
or solids with a characteristic aroma. You are by heating benzene with fuming sulphuric acid
also familiar with naphthalene balls which are (oleum).
is
used in toilets and for preservation of clothes
because of unique smell of the compound and
the moth repellent property. Aromatic
bl
hydrocarbons are immiscible with water but
are readily miscible with organic solvents. They
burn with sooty flame.
pu
Chemical properties (13.74)
Arenes are characterised by electrophilic
be T
+
is an electrophile (E )
(i) Nitration: A nitro group is introduced into (13.75)
no N
(13.76)
(13.77)
d
In the case of nitration, the electrophile,
he
+
nitronium ion, N O2 is produced by transfer
of a proton (from sulphuric acid) to nitric acid
in the following manner:
(13.78) Step I
is
If excess of electrophilic reagent is used,
further substitution reaction may take place
bl
in which other hydrogen atoms of benzene ring Step II
may also be successively replaced by the
electrophile. For example, benzene on
treatment with excess of chlorine in the
pu
presence of anhydrous AlCl 3 can be
chlorinated to hexachlorobenzene (C6Cl6)
Protonated Nitronium
nitric acid ion
be T
d
to further substitution, three possible
disubstituted products are not formed in equal
amounts. Two types of behaviour are observed.
he
Either ortho and para products or meta
product is predominantly formed. It has also
been observed that this behaviour depends on
the nature of the substituent already present
is
in the benzene ring and not on the nature of
the entering group. This is known as directive
Addition reactions influence of substituents. Reasons for ortho/
bl
Under vigorous conditions, i.e., at high para or meta directive nature of groups are
temperature and/ or pressure in the presence discussed below:
of nickel catalyst, hydrogenation of benzene
pu Ortho and para directing groups: The
gives cyclohexane. groups which direct the incoming group to
ortho and para positions are called ortho and
para directing groups. As an example, let us
be T
following structures:
(13.80)
Under ultra-violet light, three chlorine
tt E
Benzene hexachloride,
©
(BHC)
(13.81) It is clear from the above resonating structures
Combustion: When heated in air, benzene that the electron density is more on
burns with sooty flame producing CO2 and o – and p – positions. Hence, the substitution
H2O takes place mainly at these positions. However,
it may be noted that –I effect of – OH group
15 also operates due to which the electron density
C6 H 6 + O2 → 6CO2 + 3H2O (13.82)
2 on ortho and para positions of the benzene ring
General combustion reaction for any is slightly reduced. But the overall electron
hydrocarbon may be given by the following density increases at these positions of the ring
HYDROCARBONS 395
due to resonance. Therefore, –OH group are also called ‘deactivating groups’. The
activates the benzene ring for the attack by electron density on o – and p – position is
an electrophile. Other examples of activating comparatively less than that at meta position.
groups are –NH2, –NHR, –NHCOCH3, –OCH3, Hence, the electrophile attacks on
–CH3, –C2H5, etc. comparatively electron rich meta position
In the case of aryl halides, halogens are resulting in meta substitution.
moderately deactivating. Because of their
13.6 CARCINOGENICITY AND TOXICITY
strong – I effect, overall electron density on
benzene ring decreases. It makes further Benzene and polynuclear hydrocarbons
d
substitution difficult. However, due to containing more than two benzene rings
resonance the electron density on o – and p – fused together are toxic and said to possess
he
positions is greater than that at the m-position. cancer producing (carcinogenic) property.
Hence, they are also o – and p – directing Such polynuclear hydrocarbons are formed
groups. on incomplete combustion of organic
materials like tobacco, coal and petroleum.
Meta directing group: The groups which
They enter into human body and undergo
is
direct the incoming group to meta position are
various biochemical reactions and finally
called meta directing groups. Some examples
damage DNA and cause cancer. Some of
of meta directing groups are –NO2, –CN, –CHO,
the carcinogenic hydrocarbons are given
bl
–COR, –COOH, –COOR, –SO3H, etc.
below (see box).
Let us take the example of nitro group. Nitro
group reduces the electron density in the
pu
benzene ring due to its strong– I effect.
Nitrobenzene is a resonance hybrid of the
following structures.
be T
re
o R
tt E
C
no N
©
SUMMARY
Hydrocarbons are the compounds of carbon and hydrogen only. Hydrocarbons are mainly
obtained from coal and petroleum, which are the major sources of energy.
Petrochemicals are the prominent starting materials used for the manufacture of a
large number of commercially important products. LPG (liquefied petroleum gas) and
CNG (compressed natural gas), the main sources of energy for domestic fuels and the
automobile industry, are obtained from petroleum. Hydrocarbons are classified as open
chain saturated (alkanes) and unsaturated (alkenes and alkynes), cyclic (alicyclic)
d
and aromatic, according to their structure.
The important reactions of alkanes are free radical substitution, combustion,
he
oxidation and aromatization. Alkenes and alkynes undergo addition reactions, which
are mainly electrophilic additions. Aromatic hydrocarbons, despite having unsaturation,
undergo mainly electrophilic substitution reactions. These undergo addition reactions
only under special conditions.
is
Alkanes show conformational isomerism due to free rotation along the C–C sigma
bonds. Out of staggered and the eclipsed conformations of ethane, staggered conformation
is more stable as hydrogen atoms are farthest apart. Alkenes exhibit geometrical
(cis-trans) isomerism due to restricted rotation around the carbon–carbon double bond.
bl
Benzene and benzenoid compounds show aromatic character. Aromaticity, the
property of being aromatic is possessed by compounds having specific electronic structure
characterised by Hückel (4n+2)π electron rule. The nature of groups or substituents
pu
attached to benzene ring is responsible for activation or deactivation of the benzene ring
towards further electrophilic substitution and also for orientation of the incoming group.
Some of the polynuclear hydrocarbons having fused benzene ring system have
be T
carcinogenic property.
re
o R
EXERCISES
13.1 How do you account for the formation of ethane during chlorination of methane ?
tt E
d
(i) Butane (ii) Pentene
(iii) Hexyne (iv) Toluene
he
13.9 Draw the cis and trans structures of hex-2-ene. Which isomer will have
higher b.p. and why?
13.10 Why is benzene extra ordinarily stable though it contains three double
bonds?
13.11 What are the necessary conditions for any system to be aromatic?
is
13.12 Explain why the following systems are not aromatic?
bl
(i) (ii) (iii)
atoms and give the number of H atoms bonded to each one of these.
13.15 What effect does branching of an alkane chain has on its boiling point?
re
13.16 Addition of HBr to propene yields 2-bromopropane, while in the presence
o R
13.20 How would you convert the following compounds into benzene?
(i) Ethyne (ii) Ethene (iii) Hexane
13.21 Write structures of all the alkenes which on hydrogenation give
2-methylbutane.
©