836

Nootan ISC Chemistry-XI

REVI" EXERCISES
13.8 Explain the formation of carbon-carbon double bond
in ethene. 13.12 Explain why
13.9 Write all the (1) alkanes and alkynes unable
possible isomers of CHg.
are to show
Ans. But-1-ene, geometrical isomerism;
2-methylpropene, cis-but-2-ene,
trans-but-2-ene, cyclobutanel (11) Cis-isomer is less stable as compared to trans-
13.10 Give the IUPAC name of the following alkenes isomer
(1) cis and trans isomers do not change into one
CH3 another under ordinary conditions;
() CH-CH-C-CH2-CH (iv) compounds of the type aaC = Cab are unable to
exhibit geometrical isomerism.
CH5 13.13 How would you prepare ethene from
(i) CH2=CH-CH=CH2 (i) ethyl iodide (i) ethylene dibromide and
(ii) ethanol?
CH CH3 CH3 13.14 The reductive of alkene
ozonolysis an
gives a
(ii) CH3- H- =CH- H-CH mixture of acetone and formaldehyde. VWhat is the
structural formula of the alkene?
(iv) (CH3)2 C=C(CH32
CH3
Ans. (i) 3-ethyl-3-methylpent-1-ene Ans.
C=CH
(ii) Buta-1, 3-diene (iii)
2,3,5-trimethylhex-3-ene CH
(iv) 2, 3-dimethylbut-2-enel 13.15 How would you identify the position of double bond
13.11 Which of the in a given unknown butene by
following can show geometrical reductive ozonolysis?
isomerism? 13.16 What happens when
i) Propene ) isopropyl bromide is heated with alcoholic KOH;
ii) Pe 2-ene reacts with HBr;
(ii) But-1-ene
(ii) ethene is treated with chlorine water;
(ii) But-2-ene (iv) 2-methyl propene is heated with acidic
iv) Pent-2-ene KMnO4;
Ans. (iil) and (iv)] (v) 2-methylpent-2-ene is subjected to reductive
ozonolysis?
13.4 ALKYNES
Alkynes are unsaturated hydrocarbons containing one
or more triple bonds. Alkynes containing one triple bond
have the general formula
CHg--c-H Propane ane + yne = Propyne
C,Hl2n-2
13.4.1 Nomenclature of Alkynes CH=-CH,-CH Butane - ane +yne =But-1-yne
In the trivial system, alkynes (because triple bond
are usually referred by is present on the first carbon atom)
their specific names, Por example, CH-C-C-CH3 Butane ane + yne But-2-yne
=

H-C=C-H CH3-C=C-H CH-C=C-CH3 (because triple bond is present on the second carbon
Acetylene Allylene Crotonylene atom)
In the IUPAC system, the name of an alkyne is Similarly,
derived by replacing the suffix-ane present in the name of
corresponding alkane by the suffix-yne. The numbering of
CH3 CH3
carbon atoms in the longest chain is done from the end 4
from which triple bond is nearer. The position of triple bond
CH-CH-C CH CH-C-C-C-CH2-CH3
is indicated by a suitable arabic numeral. The positions and
3-methylbut-1-yne
the names of the side chains are written according to the CH3
4, 4-dimethylhex-2-yne
rules already discussed in Unit 12. Following
examples
illustrate the procedure. CH3 CH3
6
H=_H,-=H3
4
H-C H Ethane -

ane + yne =
Ethyne CH-CH---CH-CH,
2, 5-dimethylhex-3-yne Penta-1, 4-diyne
Hydrocarbons 837

13.4.2 Structure of Alkynes 13.4.3 Isomerism in Alkynes

Alkynes are formed by stereoisomerism because
hybridisation
of carbon
sp Alkynes are unable to exhibit
atoms uvOIVea In triple bond formation. The sp hybrid their molecules are linear. They show only sue ur
are
orbltais are colinear and exist at an angle of 180. The isomerism. Following types of structural isomerism
triple bond existing between the two carbon atoms consists possible for alkymes.
of one CC o-and
1. Chain isomerism: Two alkynes having the
two C-C T-bonds. As an same
example, let
us aiscuss the structure of ethyne (acetylene) which is the molecular formula may differ in the size of the main chain
simplest alkyne. This gives rise to chain isomerism in alkynes. For example,
In ethyne
(H-C==C-H) both the carbon atoms are C5Hg
in a state of sp hybridisation. The half filled one 2s and one H-C=C-CH2-CH2-CH3 H-C=C--CH-CH3
2p orbitals of each carbon (in the excited state) mix up
Pent-1-yne
together and redistribute their energy. On account of this, CH3
each carbon acquires two hybrid orbitals of 3-methylbut-1-yne
equal energy
as shown below.
2. Position isomerism: Two alkynes having the same
c 1s 2s 2p 2p 2p c 1s2 25 2p 2p 2p molecular formula may possess triple bonds at different
positions. This gives rise to position isomerism in alkynes.
sp hybridisation sphybridisation For example,
CaHG
2-hybrid orbitals
of equal energy
2-hybrid orbitals
of equal energy
H-C=C-CH2-CHg CH3-C=C-CH3
But-1-yne But-2-yne
The hybrid orbitals of each carbon are collinear and 3. Functional isomerism: Alkynes show functional
lie at an angle of 180°. One sp hybrid orbital of one carbon isomerism with alkenes containing two double bonds. For
overlaps with sp hybrid orbital of the second carbon to example,
form a C-C o-bond. The remaining sp hybrid orbital of
each carbon atom overlaps with the filled 1s orbital of a CaHg: CH-C=C-CH3 CH2=CH-CH=CH2
But-2-yne Buta-1,3-diene
hydrogen atom to form a C-Ho-bond. All the o-bonds thus
formed (one C-C and two C-H o-bonds) are collinear. At
13.4.4 Preparation of Alkynes
this stage,each carbon is left with two unhybridised half
filled p-orbitals. These orbitals are mutually perpendicular Some general methods for the preparation of alkynes
with one another and also perpendicular to C--Co -bond. are as follows.
1. By dehydrohalogenation of 1, 2-dihalides
unhybridised half filled p-orbitals of one carbon
atom
The
orbitals of the Acetylene as well as higher alkynes can be prepared by
overlap sidewise with the corresponding
second carbon atom resulting in the formation of two C--C dehydrohalogenation of 1, 2-dihalides (vicinal dihalides).
thus formed are also
T-bonds (Fig. 13.11). The two T-bonds
mutually perpendicular
to one another. Thus, a carbon-
and two t-bonds Alc. KOH
carbon triple bond consisting
of one o-

The molecule is
R-C-C-H R-C=C-H +2HX
is formed between the two carbon atoms. Alkyne
equal to 180°.
linear and H-C-C bond angles
are
HX
Vicinal dihalide

For example,
1so
29 /2 BH
Hsp SPH
H-C-C-H +
2KOH
*******
1, 2-dibromoethane
S-Sp p-P (T) S-SSp
(Alcoholic)
bond
C
(o)H
bond H-C=C-H+ 2KBr +
2H,0
Hbond, P-P (7)
bond Acetylene

sp-sp (o) The use of KOH gives rise to side reactions. Therefore,
bond dehydrohalogenation is usually carried out with sodamide
in ethynhe.
Fig. 13.11
The o-and T-bonds
(NaNH2).
 838 Nootan ISC Chemistry-XI
For example, 5. By Kolbe's electrolytic method Acetylene can be

Br H prepared by the electrolysis of a concentrated aqueous

solution of the potassium salt of maleic acid or fumaric

acid.
CHg-C-C-H+2NaNH2 CHCOOK CHCOO
2KT
H Br
1, 2-dibromopropane CHCOOK CHCOOT
Potassium maleate

At anode:
CH-CCH+ 2NaBr + 2NH3 CHCOO CH
Propyne +2CO2 + 2e
2. By dehydrohalogenation of 1, 1-dihalides: When 1, CH
1-dihalides are treated with alcoholic KOH or sodamide,
CHCOO Acetylene
alkynes are obtained. For example, Atcathode
2H,0 + 2e 20H H2
HBr
CH-C- -H Alc KOH CH3-C=C-H +2HBr
13.4.5 Physical Properties of Alkynees
Propyne Some important physical properties of alkynes are as

HBr follows.
1, 1-dibromopropane 1. Physical state: The first three members i.e., ethyne,
3. By dehalogenation of tetrahalides : Tetrahalides propyne and 1-butyne are gases at room temperature;
containing halogen atoms on adjacent carbon atoms when 2-butyne and higher members upto C1 are liquids
whereas those having more than 11 carbon atoms are
heated with zinc dust in alcohol yield alkynes.
solids. Acetylene has a garlic odour due to the presence
For example,
of impurities of phosphine and arsine which are often
BrB Ethano
associated with it. Higher members are odourless. All
alkynes are colourless substances.
CH3-C-C-H + 2Zn
Heat
2. Melting and boiling points : The melting and boiling
Br Br points of alkynes are slightly higher than those of the
1, 1, 2, 2-tetrabromo corresponding alkenes and alkenes. This is because alkynes
propane
possess greater polarity as compared to alkenes and
CH-C=C-H + 2ZnBr2 alkenes. Moreover, alkynes have linear structure and their
propyne molecules can pack more closely as compared to those of
4. From acetylene: Acetylene can be used to prepare alkenes and alkanes. Thus, the magnitude of intermolecular
its higher homologues. This is done by treating the sodium forces is higher in alkynes. Consequently, alkynes possess
derivative of acetylene known as sodium acetylide with higher melting and boiling points.
alkyl halides. The melting and boiling points of alkynes increase
Sodium acetylide is prepared by treating acetylene regularly with increase in the molecular mass. The
with sodamide in ether or with metallic sodium in liquid branched chain alkynes possess lower melting points than
ammonia. Sodium acetylide thus prepared is then treated the corresponding straight chain isomers.
with a suitable alkyl halide to give the required higher 3. Solubility : Alkyne molecules are slightly polar.
homologue of acetylene. Therefore they are slightly soluble in water. They are more
For example, soluble in non-polar or slightly polar solvents such as
benzene, carbon tetrachloride, etc.
H-C=CNa + CH,CHBr CoH5-0-C2Hs
4. Density: Alkynes possess low density and are lighter
Sodium acetylide Ethylbromide than water.
H-C=C-CH2-CH3 + NaBr
But-1-yne 13.4.6 Chemical Properties of Alkynes
Due to the presence of a triple bond, alkynes are quite
H-C=CNa + CH,CH,CH.CH Br 2Hs-0-C2Hs reactive and undergo addition and oxidation reactions
Butyl bromide
readily. Their chemical behaviour is much similar to that
H-C=C-CHCHCH,CH3+ NaBr of alkenes. Some important chenmical properties of alkynes
Hex-1-yne are described ahead.
 839
tudrocarbons
and metal
These reactions catalysed by Ilight
are
1. Addition Reactions colour of
bromine
halides. In case of bromine, the brown
Alhough the trmple bond present in alkynes consists of used as a test
or
the reaction may be
a bonds, alkynes are less reactive than alkenes towards gets discharged and
geoeme
nts (the attacking reagents having a unsaturation as we have seen in case o aikeic

: Addition
of halogen
deficteny of eiectrons). This is quite unexpected and against (ii) Addition of halogen acids
the arguements based on bond strengths. This is probably acids to alkynes takes place in two stages i t ae
due to the tact that the -electrons of the C C bond are the Markownikoff's rule. For example,
more firmiy held by the carbon nuclei as
compared to the H C
electrons of the C-C bond due to a difference in the
state of hybndisation. On the other hand, alkynes are mmore
CHCH HC HC=C-H
liabie to be attacked by nucleophilic reagents (the reagents Chloroethene
(Vinyl chloride)
having an excess of clectrons) as compared to alkenes.
In alkynes. addition occurs in two steps. In the first H C
step. one molecule of the attacking reagent is added to
HCI
the alkyne when its triple bond changes to a double bond. H-CC-H
In the second step. a second molecule of the reagent is
added when double bond changes to a single bond and a H CI
saturated compound is obtained. Some important addition 1,1-dichloroethane
(Ethylidene chloride)
reactions of alkynes are as follows.
(0) Addition of hydrogen: Alkynes add hydrogen in the Br H
presence of catalysts such as nickel. platinum or palladium.
HBr CH3-C=C-H
CH3-C=C-H
CH-CH
Ethyme Catalyst CH-CH
Ethene Caatalyst
CH3-CH3
Ethane
Propyne 2-bromopropene
Br H
The intermediate alkene formed in the reaction can be
obtained by using Lindlar's catalyst which is a mixture of HBT CH-C-C-H
palladtum and banum sulphate or palladium supported over
CaCO, and posoned partially by lead acetate or quinoline Br H
2, 2-dibromopropane
Lindlar's catalyst checks the hydrogenation of alkynes at
che alkene stage (iv) Addition of water (Hydration) Alkynes add a
molecule of water when treated with dilute sulphuric acid
Pd BaSO4
CH-CH H2 CH2=CH2 containing mercuric sulphate. The product is an aldehyde
( )Addition of halogens:Alkynes add on two molecules or a ketone. The intermediate compound formed in
of halogens forming first a dihaloalkane and then a the reaction is an unstable enol which immediately gets

tetrahaloalkane rearranged into a more stable keto form.

CI CI For example, when acetylene is treated with dilute
sulphuric acid containing mercurie sulphate at 348 K,
H-CC-H HC-C-H
1,2-dichioroethene unstable enol, vinyl alcohol is first formed which rearranges
Erhye
CI CI to the more stable ethanol.

O, H-C-C- H-C-C-H+H:0-H
HgSO4
Ethyne
Water Dil.
348 K
HSO4
CI CI (Acetylene)
1 2 2tetra hloroethane
Westron)
Br Br HOH HO

12 CH,-CC-H H C-H Rearrangement

CH-CCH
1,2-dibromopropene
H-C-C-H
Propyne Vinyl alcohol
Br Br (Unstable) H
Ethanal
CH C-C-H (Acetaldehyde)
Similarly, propyne undergoes hydration as shown
Br Br ahead.
1,1,2,2-tetrabromopropane
 840
Nootan ISC Chemistry-XI
oH R-C=0 group whereas ==C-H
part gets oxidised
CH-C=CH +H,0 HgSO4CH3-C CH
to

Dil.HSO4 -COOH group.

O For example,

Rearrangement, CH-C-CH3 H-C=C-H+40-

oAlk.KMnO4
298-303K HOOC-COOH
Acetone Ethyne Oxalic acid
(v) Addition of hypohalous acid: Alk.KMnO4
acids in two
steps and form dihalo
Alkynes add hypohalous CH-C=CH +30 298-303 K CH3C-COOH
For example, aldehydes or ketones. Propyne
O
Cl OH 2-ketopropanoic acid
H-C=C-H HOC
CI OH
H-C-C-H
CI
HOCI CH-C=C-CH+ 20
But-2-yne
Alk.KMnO4CH3
298-303K
O O
Buta-2, 3-dione
H-C-C-HH205
Cl OH
H-C-C-H In these reactions, purple colour of alkaline KMnO4
(Baeyer's reagent) is discharged in the same way as we
Cl have seen in case of alkenes.
(Unstable) 2, 2-dichloroethanal Therefore, they may be used
as a testfor alkynes (Baeyer's test).
(Dichloroacetaldehyde) (b) With hot and concentrated alkaline
vi Addition of
hydrogen cyanide : Alkynes add a KMn04
molecule of
hydrogen cyanide in the presence of catalyst solution, cleavage of the molecule at the site of triple bond
barium cyanide to form takes place. This results in the formation of
alkenyl cyanide. For example, acids and carbon dioxide. Under carboxylic
acetylene adds HCN to give vinyl cyanide which is largely these conditions,=R
used in the manufacture of part gets oxidised to RCOOH whereas=C-H
fibre orlon. synthetic rubber and synthetiC
Oxidised to CO and HO. For example,
part gets

CH=CH + HCN BalCN2 CH-CHCN CHg-C=C-H + 40 Alk.KMn04

373-383K
Vinyl cyanide Propyne
(Acrylonitrile) CH COOH +CO2
vii) Addition
of arsenic trichloride:
Acetylene adds on Ethanoic acid
arsenic trichloride in the
presence of anhydrous AlCl3, Alk.KMnO4,
Cu2Cl2 or HgCl2 to form CH-C=C-CH3 + 40
commonly known as Lewisite.
2-chlorovinyldichloroarsine, But-2-yne 373-383Kk
CH CHCI CH COOH
HgCl2 +
CH,COOH
+AsClg (ii) Oxidation with ozone (0zonolysis) : Unlike alkenes,
CH
CHAsCl2 alkynes react slowly with ozone to form ozonides. The
Lewisite ozonides upon decomposition with Zn and
Lewisite is a powerful poisonous gas and is four times diketones. HO formn
as active as the mustard gas.
For example,
2. Oxidation Reactions
Alkynes are quite susceptible to oxidation and yield H-C=C-H +03 H
a of products under different conditions. Some
variety C-H
important oxidation reactions of alkynes are as follows.
O -O
(i) Combustion: Alkynes burn with a luminous smoky Zn +H20 Ozonide
flame to form carbon dioxide and water. The reaction is
highly exothermic and a large amount of heat is produced.
H-C-C-H +H02
2CH=CH+ 50O2 4C02 + 2H0; O O
Glyoxal
AH° =
-1300 kJ mol
(ii) Oxidation with KMn04 : The products obtained
depend upon the concentration of the solution and
CH-C=C-CH3 +Og
But-2-yne
cCH3
CH3-C -C-CH
temperature. Zn +H2C
O-0
(a) With cold and dilute neutral or alkaline CH3-C-C-CH3 + H202
KMnO4, alkynes give 1, 2-diketones. Under these
conditions,=C-R part of alkyne gets oxidised to O
Buta-2,3-dione
 841
Hydrocarbons
The diketones formed in the above reactions get
CH3
oxidised acids by the action of H2O2
into simpler carboxylic Red hot
which is also formed in the reaction. Therefore,the final 3CH-C= CH
iron tube
products obtained on ozonolysis of alkynes are carboxylic Propyne H3C CH3
acids containing lesser number of carbon atoms.
Mesitylene
COOH
oxidised by H202
H-C-C-H of
(formed in the reaction) 4. Acidic Character of Alkynes (Formation
COOH
Oxalic acid alkynides) and
oxidised by H202 atoms present in acetylene
The hydrogen
CH3 C-CH3(formed in the reaction) terminal alkynes (1-alkynes) containing
==C-H group are
be removed as protons
weakly acidic in character and can
CHCOOH +CHCOOH and other reagents.
(H ions) by the action of strong bases
character of 1-alkynes
Some reactions showing the acidic
3. Polymerisation Reactions are as follows.
Alkynes undergo polymerisation under suitable (i) Reaction with NaNH2: 1-alkynes are treated
When
sodium in liquid
conditions and form different products under different with strong bases like sodamide (or
conditions. Some examples are given below. ammonia), sodium derivatives called acetylides or alkynides
(a) Polymerisation of acetylene Some important are obtained.
polymerisation reactions of acetylene are as follows. R-C=CNa +2NH3
R-C=C-H+NaNH2
i) When acetylene is passed through a red hot iron
Sodium alkynide
tube, benzene is obtained.
CH For example,
HC CH H-C=C-H+ NaNH2 H-C=CNa + NH3
HC
....
HC Red hot Sodamide Monosodium
Iron tube acetylide
CH
HC HC HC
CH CH H-C=C-H+2NaNH2 ÑaC=CNa +2NH3
Benzene Disodium acetylide
Three molecule
of acetylene (Kekule structure)
Acetylides react with alkyl halide to give higher
dissolved in
(ii) Under suitable conditions, acetylene alkynes. For example,
tetrahydrofuran polymerises into cyclooctatetraene. H-C=CÑa + CH3Br H-C =C-CH3 + NaBr
CH=CHH
Propyne
CH CH
ammonical CuCI: and
4CH=CH
Ni(CN)2 (ii) Reaction with
1-alkynes react with ammoniacl solution
Acetylene
of cuprous
Tetrahydrofuran, H CH
high pressure chloride to form corresponding copper alkynides.
CH=CH R-C =C-H +[Cu(NH3)21Cl
Cycloocta-1, 3,
5, 7-tetraene

(ii) When is passed into cuprous chloride

acetylene R-C=CCu + NH4Cl+ NH3
ammonium chloride, a mixture of vinyl
Copper alkynide
solution containing
is obtained. For example,
acetylene and divinyl acetylene
*****

CH-CH + CH=CH
uCl+NH4C CH2-CH-C=CH
H-C=C-H +
2[Cu(NH3)21Cl
Vinyl acetylene CuC=CCu + 2NH4CI+2NH3
** * . Copper acetylide
(Red precipitate)
CuCl+NH4Cl
CH2=CH-C=CH + CH=CH It is to be noted that in these reactions, acetylenic
hydrogen atoms are replaced by Cu () ions.
CH2-CH-C=C-CH=CH2
Divinyl acetylene (ii) Reaction with ammonical AgN03 Acetylenic
of propyne When propyne is passed hydrogens of 1-alkynes can also be replaced by Ag (I) ions
(b) Polymerisation 3, 5-trimethyl
through a red hot iron tube, mesitylene (1, by treating them with ammoniacl solution of silver nitrate.
benzene) is obtained.
 842 Nootan ISC Chemistry-XI

C=C-H [Ag(NH3)2 1NO3

8-
R-C=C-zHH/ + Na NH2)
R-C=CAg
Silver alkynide
+ NH4NO3+ NH3
Weakened
C-H bond
For example,
R - C = CNa + NH3
H-C=C-H 2Ag(NH3)2 1NO3
It is worthwhile to mention here that the acidic
AgC=CAg +2NH4NO3 +2NH character of hydrocarbons decreases in the following order.
Silver acetylide HC=CH> CH2=CH2 > CH3 -CH3.
(White precipitate) Although acetylene is most acidic among the
nese reactions clearly indicate that 1-alkynes are hydrocarbons mentioned above, it is far less acidic
aciaic in nature. Alkenes, alkenes and other alkynes (e.g.. than organic acids such as ethanoic acid (acetic acid).
Acetylene is about 10 times less acidic than acetic acid.
2-alkynes) do not give these reactions. Therefore 1-alkynes Alkenes and alkanes are even much less acidic. This is why
can easily be distinguished from 2 -alkynes, alkenes and alkenes and alkanes practically do not show any acidic
alkanes by the above reactions particularly those with
character.
ammonical CuCl or AgNO3
For example, 13.4.7 Acetylene (Ethyne), CH=CH
CHg-CH2-C=CH + [Ag(NH3)2]NO3
Acetylene is the first member of the alkyne series and
But-1-yne is of significant industrial importance. It is present in traces
White precipitate in coal gas and the gases obtained by the decomposition of
complex organic matter.
CH3-C=C-CH3 Ag(NH3)2]NO3
But-2-yne A Preparation
No reaction 1. Laboratory method: Acetylene can conveniently
be prepared in the laboratory by the action of water on
Explanation of acidic character of 1-alkynes The
calcium carbide.
acidic character of 1-alkynes can easily be explained on the
basis of their molecular structure. We have already studied CaC2 +2H0 Ca(OH)2 + CH=CH
Calcium carbide Acetylene
that the carbon atoms indulged in triple bond formation in
an alkyne exist in a state of sp hybridisation. An sp hybrid The apparatus used is shown in Fig. 13.12. Calcium
carbide is taken over a layer of sand in a flask fitted with
orbital possesses about 50% s-character. The s-character
a dropping funnel and a
in an sp hybrid orbital is much more as compared to that delivery tube. Since acetylene
forms an explosive mixture with air, the air of the flask is
present in an sp (33%) or sp (25%) hybrid orbital. An displaced with oil gas. Water is dropped from the dropping
electron in an s orbital is more tightly held than in ap orbital funnel drop by drop. The evolved acetylene gas is usually
because the s electrons are closer to the nucleus. The same contaminated with small amounts of phosphine, arsine,
logic applies to the status of electrons in a hybrid orbital. ammonia, hydrogen sulphide etc. In order to remove these
An electron present in a hybrid orbital having a greater impurities, the evolved gas is passed through an acidified
s-character will be more tightly held than the electron solution of copper sulphate. The pure gas thus obtained is
present in the hybrid orbital with lesser s-character. Since collected by the downward displacement of water.
an sp hybrid orbital possesses much more s-character as Water
compared to sp and sp" hybrid orbitals, the electrons in
an sp hybrid orbital are held more strongly by the nucleus
than in sp and sp orbitals. Hlence, the electron density Acetylene
on the carbon atom involved in triple bond formation
increases because the bond pair of CH bond lies closer
to carbon atom. Consequently, the acetylenic hydrogen CaC2
develops a substantial positive charge and shows acidic -Water
character. The C-H bond gets weakened and facilitates Sand-
the release of positively charged hydrogen in the form
Acidified solution
of H+ ion or proton when attacked by a strong base like of CuSO4
NaNH2 as shown below.
Fig. 13.12 Laboratory preparation of acetylene.
Hydrocarbons 843
2. By heating
iodoform with silver powder Pure Cage
acetylene can be prepared by heating iodoform with silver Acetylene
powder.

CH136AgI3 CH
- CH=CH + 6Agl
*********************************

3. By heating
tetrabromoethane with zinc dust
When 1, 1, 2, 2-tetrabromoethane is heated with zinc dust,
acetylene is obtained. Calcium
carbide
CHBT2 CH Gas
Iron tank
2Zn +2ZnBr2 holder
CHBr
1,1,2,2-tetrabromo
CH
Acetylene
ethane
WATER

4. By Kolbe's electrolytic method When an electric

current is passed through an aqueous solution of sodium
or potassium fumarate acetylene is obtained at the anode.
Fig. 13.13 Manufacture of acetylene using
CHCOOK CHCOO2 calcium carbide.
+2K
From methane: Acetylene can also be
CHCOOK CHCOO (ii)
manufactured by the controlled partial oxidation of
CHCOO- CH methane at high temperature
At anode. +2CO2 +2e 1773 K
2CH=CH + 2CO +10H2
CHCOO CH 6CH4+O2
20H+ H2 (iii) From natural gas : Natural gas which consists
At cathode: 2H20 + 2e of mainly methane is also used for the manufacture
of
in electric
5. Synthesis : Berthelot synthesised acetylene by acetylene. Natural gas is heated at 1773 K an arc

electric between carbon electrodes in an when acetylene is obtained

striking an arc

atmosphere of hydrogen. Electric arc CH=CH +3H2

2CH4
Electric arc
> CH =CH
2C + H2
BPhysical Properties
6. Manufacture : On commercial scale, acetylene
can

methods. (1) Acetylene is a colourless gas with garlic like

be prepared by any of the following odour. The odour is due to the presence of
can be obtained
(i) From calcium carbide : Acetylene Pure acetylene has pleasant ethereal
impurities.
on large scale by the
action of water on calcium carbide. odour.
Ca(OH)2 +CHCH (ii) It is almost insoluble in water but readily soluble
CaC2 + 2H20 in acetone.
is prepared
Calcium carbide required for the process (ii) It is lighter than air.
limestone and coke in an electric furnace. (iv) It is somewhat poisonous in nature and produce
by heating
Heat general anaesthesia when inhaled.
CaCO3 CaO CO2 (v) Liquid acetylene boils at 191 K.
Quicklime
Limestone
Heat CaC2 + CO
C Chemical Properties
CaO 3C almost all the reactions of
Acetylene gives general
in a cage fitted in agas holder alkynes described earlier (see § 13.4.6). A brief summary
Calcium carbide is taken
stored in a n iron tank (Fig. 13.13). of its chemical properties is given on the next page.
which floats in the water
with water to produce acetylene
Calcium carbide reacts 13.4.8 Uses of Alkynes
the gas holder. As m o r e and more
which gets collected in
holder rises and the cage goes (i) Acetylene is used for illumination in hawker's
of the gas collects, the gas
the generation of lamps, light houses, etc.
out of contact
with water. This stops
is withdrawn from the gas holder, ii) Acetylene is used for making oxy-acetylene flame
acetylene. When the gas
reaction between calcium carbide which has a temperature of about 3000 K and is
it comes down and the
and acetylene is again produced. used for cutting and welding of iron and steel.
and w a t e r again starts
844 Nootan ISC Chemistry-XI
H2
catalyst CH3-CH3
Ethane

CHCl2-CHCl2
1,1,2,2-tetrachloroethane
(Westron)
HCI
CH3-CHCl2
Ethylidene chloride
CH3CHO
H20 Acetaldehyde
HgSO4/Dil. H2S04
348 K

HOC CHCl,CHO
Dichloroacetaldehyde
HCN CH=CH.CN
Vinyl cyanide
AsCl3
CHCI=CHAsCl2
HgCl2 Lewisite

O2
> CO2 +
H20
O
HOOC-COOH
Alk. KMnO4 Oxalic acid
298-303K

CH=CH CH COOH + CO
Alk. KMn04 Acetic acid
373-383 K

H- -C-H Zn+H CHO-CHO + H2O2

Glyoxal
O-0 Oxidation
Red hot
>CgH6 HOOC-COOH
Iron tube Oxalic acid
Benzene

Ni(CN)2
CgHs
Tetrahydrofuran Cyclooctatetraene
High pressure
CuCl+NHCI
CH2=CH-C=C-CH=CH
Divinyl acetylene
NaNH2 H-C=CN NaNH2
NaC=C Na
Mono sodium Disodium acetylide
acetylide
Cu(NHg)2Cl
CuC=C Cu
Copper acetylide (Red ppt.)
Ag(NH3)2NO3 Ag C=Ag"C
Silver acetylide (White ppt.)
(1i) Acetylene is used for the artificial ripening of (v) Acetylene is used as a starting material for the
fruits and vegetables. preparation of plastics, synthetic rubbers and
(iv) Acetylene is used as a starting material for the synthetic fibre orlon.
manufacture of acetaldehyde, acetic acid, ethyl (vi) Acetylene is also used for making Lewisite which
alcohol, etc. is a war gas and was used in second world war.
 8
Huirocarbons

REVI W
XERCISES

(ii Chloroform
13.17 Give the lUPAC names ofthe following alkynes
(ii) 1, 2-dibromoethane?

Ct 13.23. How would you

obtain following compounds
tre

CH CC-CH-CH acetylene
( Acetaldehyde
CH
(ii Ethylene
(i) CH-C=C-CH-CH-CHCH (iin) Lewisite
show acidi
CH CH 13.24 Which of the following alkynes
charater?
(ii) CH-CH-CHC=CC-CH,
()Propyne
ii) But-1-yne
CH
(ii) But-2-yne
CH Ans. and in
(iv) Pent-2-yne
13.25 What happens when
iv) CHC--CHCH-C=CH
i) acetylene is treated with hypochlorous acid;
2
Ans. i) 4-methylhex- 2-yne (i 4-methy lhept
vne
ii) acetylene is passed in a dilute solution of H,SO
1
iin) 2, 2. 6-trimethy lhept 3 yne (IVmethyIhexa
containing HgsO,;
5-dienel (11) Baeyer's reagent reacts with acetylene;
13.18 What the states of hybridisation of carbon atoms
are
iron tube?
Ans (iv) Propyne is passed through a red hot
forming a triple bond? 13.26 Name the monomers which constitute the following
13.19 Why is acetylene molecule linear?
by But-2-yne and polymers.
13.20 What type of isomerism is shown
But-1, 3-diene? i) Teflon
isomers with molecular tormula (ii) Vinyl acetylene
13.21 Write the possible
Ans. (i CF,=CF i CH=CH
CHs trom
(ii) Oron
in CH=CHCN
13.22 How would you prepare acetylene
(i) CaC2

13.5 PETROLEUM:AN INDUSTRIAL SOURCE OF HYDROCARBONS

oleum oil) is a dark (offshore area). Efforts are being made to explore new oil
Petroleum (Latin: Petra =rock; =

tound in certain regions at fields and to increase the production of the oil.
coloured, viscous, oily liquid
beneath the surface of the earth. It is also Petroleum is perhaps the biggest and the cheapest
various depths
oil. source of hydrocarbons. Petroleum sources are now-a
called crude oil, mineral oil o r rock
days used derive large number of organic chemicals
Petroleum is usually found beneath the rocky strata of
to a

over salted water (brine) known as Petrochemicals. They are produced either from
the earth's crust where it floats
natural gas, a mixture natural gas or from the various fractions obtained during
and is covered by an atmosphere of
of mainly gaseous alkenes. Huge deposits of petroleum the refining of the crude oil. According to a rough estimate,
the world. The United States of more than half a million of organic compounds can be
occur in many parts of
America is the biggest oil producing country. Other major synthesised from hydrocarbons derived from natural
oil producing countries are Russia, Saudi Arabia, Iran, gas, gasoline and naphtha. Petrochemicals are of great
Iraq, Kuwait, Canada, Indonesia, Mexico, Venezuela etc. As importance in industry.

ompared to the world production of oil, India is a poor In the forthcoming discussion, we shall briefly study
oil producing country. At present, the main oil producing the mining and refining of petroleum. We shall also study
Ceptres in India are Assam, Gujarat and Mumbai High some important topics related to petroleum.

Nt included In the latest 1SC Syllabus.

 846 Nootan ISC Chemistry-XI

13.5.1 Composition and Origin of occurrence but it always contains a very high percentage
of methane. Methane can be present to an extent of even
Petroleum
95% in it.
Although petroleum is oily in nature, its chemical Earlier, natural gas was considered a hazard in
composition is entirely different from that of the vegetable petroleum industry as it formed explosive mixtures
and animal oils. A brief discussion of the composition and with air. Therefore, it was usually taken away from the
the theories of origin of petroleum are given below source and burnt. But, now-a-days, it is liquefied at room
temperature under a pressure of 3-5 atmospheres and is
A Composition of Petroleum used as a domestic fuel under the name LPG (Liquefied
petroleum gas). It mainly consists of a liquid mixture of
The exact composition of petroleum varies with the
place of occurrence. However, it is essentially a mixture propane, butanes and pentanes.
of hydrocarbons. The important constituents of
petroleum B Origin of Petroleum in Nature
are as follows.
Many theories have been proposed to explain the
(i) Alkanes Petroleum consists of alkanes right from
origin of petroleum in nature. Some of these theories are
methane upto higher members containing as many as
given below.
forty carbon atoms (i,e., C1-C40). Most of the alkanes
1. Carbide theory: According to this theory the
present in petroleum are straight-chain but a few may be
petroleum present beneath the layers of earth crust is of
branched chain also. Petroleum rich in alkanes is termed as
inorganic origin and is formed by the action of steam on
paraffinic oil.
metallic carbides present in the hot interior of the earth.
(ii) Cycloalkanes The cycloalkenes usually present
The theory assumes that the molten metals in the
in petroleum are methylcyclopentane, cyclohexane and
hot interior of the earth combined with coal and formed
methylcyclohexane. They are also termed as naphthenes. carbides.
The oil rich in naphthenes is known as asphaltic oil.
(ii) Aromatic hydrocarbons: The aromatichydrocarbons
4Al + 3C Al4C3
usually present in petroleum are benzene, toluene, xylenes, Ca 2C CaC2
cumene and naphthalene.
The carbides thus formed reacted with steam under
(iv) Organic compounds containing sulphur, nitrogen and high pressure and temperature to form saturated and
oxygen Besides hydrocarbons, petroleum also contains unsaturated hydrocarbons.
certain organic compounds having sulphur, nitrogen and
Al4C3 + 12H,0 4Al(OH)3 +3CH4
oxygen. Methane
The sulphur containing compounds that are present
in petroleum are usually mercaptans (RSH), thioethers
CaC2 +2HOO Ca(OH)2 + C2H2
Acetylene
(R-S-R) and thiophene (CH4S). The unpleasant smell
of crude petroleum is due to the presence of these sulphur The unsaturated hydrocarbons formed as above
compounds. The nitrogen containing compounds usually underwent a series of reactions such as hydrogenation,
present in petroleum are pyridine, quinoline, pyrrole polymerisation, cyclisation etc., in the presence of metal
and their derivatives. The oxygen containing compounds
catalysts under high temperature and pressure to form a
number of hydrocarbons.
usually present are alcohols, phenols and resins.
Besides the above mentioned compounds, Hydrogenation
CH=CH +H2 > CH2=CH2
petroleum also contains chlorophyll and haemin derivatives.
Ethylene
Natural Gas
CH2=CH2 + H2 Hydrogenation
Petroleum occurs in nature in association with a CH-CH3
mixture of gases called the natural gas. It is usually found Ethane

above petroleum deposists in nature but may also be CH

dissolved in natural petroleum. CH CH
The natural gas is a mixture of several low molecular 3CH=CH Polymerisation
mass alkenes such as methane, ethane, propane, butane CH
CH
etc., along with small amounts of hydrogen, nitrogen,
carbon dioxide, hydrogen sulphide and water vapours. CH
Benzene
The composition of natural gas varies with the source of
 849
Hydrocarbons
In india, O1l refineries are located at Kovali. Mumbai, like silica, zinc oxide, titanium dioxide,
hvdrocarbons
ferric Oxe1s
1s
into lower hydrocarbons
Cochin, Chennai, Visakhapatnam, Haldia, Ddrdunl, alumina The conversion
etc. octane
number

Guwahati, Digboi and Mathura. and the resulting product has

about 70%
of about 65-70.
13.5.3 Cracking, Reforming and Vapour-phase cracking
This method is
generally

Synthetic Petrol (17) kerosene oil

o r gas oil. The process
used for the cracking of of 3.5
pressure
about 600-800°C under
a
The 1S carried out at
refining of crude oil
(petroleum) gives several The cracking is
facilitated by the use

to 10.5 atmospheres.
products as we have seen earlier. Among these, petrol, of a suitable catalyst.
kerosene and diesel are the most important. The modern It is used
useful industrial process.
civilisationleans heavily on these Cracking is a very
products for its energy from residual oil or heavy
requirement. Their demand is increasing day-by-day and for the preparation of gasoline The
useful fraction of petroleum.
is much more than what is produced by the above method. oil which is a much less
of oil gas from
used for the preparation
Therefore, techniques have been developed to convert less process is also Alkenes like ethene,
kerosene and petrol gas from gasoline.
useful products of petroleum refining into gasoline and
other more useful products. The two important techniques propene and butene
a r e also
manufactured by cracking.

used for this purpose are cracking and reforming.

B Reforming acyclic and
A Cracking Reforming is the process of converting
aromatic hydrocarbons
the decomposition of higher yclic alkenes into corresponding suitable conditions of
c n g may be defined as in the presence ofa catalyst
under
hydrocarbons into lower hydrocarbons at high temperature. also known as aromatisation.
molecules temperature. The process is
racking actually involves the breaking of larger In this process, a straight chain alkane
or a cycloalkane
into smaller molecules. When a higher alkane is heated is heated to about
containing six to eight carbon
atoms
carbon-
Strongiy in the absence of air, the cleavage of 400°C in the presence of palladium, platinum
or nickel

bonds takes place resulting in the formation of

a
carbon the best catalyst
which act as catalysts. Platinum is perhaps
mixture of lower hydrocarbons. For example, when decane of platinum, the
for the process. Due to the wide use
C1oH22) is heated to 500°C, mixture of octane and ethene process is also referred to as platforming.
Some examples
may be obtained. follows.
of reforming (platforming) are as

CH (CH2)g CH3 500 CH (CH,)CH +CH2=CH2

Decane EtheneOctane
CH3
CH2 CH3
In fact, it is difficult to predict the nature of products
obtained on cracking of a higher hydrocarbon
because
Pt

400°C
O +4H2

cracking is a very complicated process. Apart

from the CH2 CH2 Benzene

possibilities of the chain fission at arbitrary points, the CH2

process is also accompanied by many other processes such as Hexane

carbonisation, dehydrogenation, alkylation, polymerisation CH3

etc. In the cracking of
decane mentioned above, there are
fair chances of getting heptane, hexane, pentane,
butane, CH3
hexene also. Similarly, two
CH2
etc.,
propane, butene, pentene,
modes of cracking of
hexadecane (C16H34) can be shown CH3 Pt +4H2
as given below.
s00CCH3-(CH2)6-CH3+GgH16 CH2 CH2 400°C
Toluene

CH3-(CH2)14CH
Octane Octene CH2
Heptane
Hexadecane
sO0cCH3-(CH2)4-CH3+Cot20 Aromatic hydrocarbons like benzene, toluene,
Hexane Decene
xylene, etc., formed on account of reforming are used to
and improve the quality of gasoline. They are also used for the
Thus, thermal cracking is a complicated process
it complex mixtures of manufacture of other organic chemicals.
difficult to control. Moreover, gives
products. carried Synthetic Petrol
is generally
Therefore, now-a-days, cracking lower With the advancement of civilization, the consumption
of a catalyst at temperatures.
out in the presence of
cracking. Usually, silica and petrol and other petroleum products is increasing day-
This is known as catalytic
Cracking is usually carried by-day and our existing oil fields are unable to meet the
alumina are used as catalysts.
two ways.
increasing demand of the society. Therefore it has become
out in the following
lliuid-ohase cracking: This method is generally uSed essential to explore methods to synthesis petrol and other
in the laboratory. Chemists accentod
for the cracking of heavy oil or residual oll. Ihe Cracking petroleum products
t earried outat a high temperature (475-530C) and high this challenge and developed methods to synthesis fuels
Dresure (7 to 70 atmospheres) in the presence of catalysts (mixture of hydrocarbons) resembling those obtained
 850
Nootan lISC Chemistry-XI
rom petroleum. The fuel synthesised from coal is termed
ds
In Bergius process, the coal is finely powdered
Synthetic petrol. The important methods to prepare and mixed with heavy oil (produced in the process)
synthetic petrol are as follows. and a suitable catalyst to form a paste. The coal paste
e r g u s process: Coal is amixture of high molecular is preheated and taken to a converter. Here the paste is
a s complex organic compounds deficient in hydrogen. heated to 450°C and hydrogen gas is bubbled through it
Therefore saturation of coal with hydrogen under suitable at 250 atmosphere pressure. The vapour oDtalned from
Conditions followed by cracking yields a mixture of converter on condensation yields synthetic petroleum.
hydrocarbonswhich resembles petroleum. This forms the This upon fractional distillation produces synthetic petrol,
basis of the manufacture of synthetic petrol by Bergius middle oil and heavy oil. The middle oil fraction is further
process. cracked to give more of synthetic petrol. The flow diagram
of the process is given in Fig. 13.16.

Coal
Synthetic
Powder
Petrol
Catalyst
**************

Heavy oil
Middle
Coal Converter Oil
Paste 450°C -*****--*|

H2
(250atm.)
Heavy Oil

Still

Fig. 13.16 Manufacture of synthetic petrol by Bergius process.

2. Fischer-Tropsch process In this process, steam is mixture of
passed over red hot coke when a mixture of CO and H2 a piston in a cylinder and then ignited by an electric spark
(water gas) is obtained.
C+ H20 CO +H2
Water gas
The water gas thus obtained is mixed with excess of
hvdrogen and the mixture is passed over a cobalt catalyst at after
200°C under a pressure of 5-10
atmospheres. The product
obtained on condensation resembles artificial petroleunm compression ratio, greater is the efficiency of the engine.
and consists of a mixture of liquid hydrocarbons.
n(CO+ H2)+ (n +1)H2 CH2n+2 + nHg0
Water gas
The artificial petroleum is subjected to fractional
distillation when synthetic petrol is obtained.
13.5.4 Quality of Gasoline : Octane
Number
The quality of gasoline depends upon how smoothly
can it burn without producing any unpleasant sound
called knocking in an internal combustion engine and is
expressed in terms of a number called Octane number
A fuel which produces mininum knocking is considered
as a good quality fuel. In the forthcoming discussion, we
shall learn briefly the factors which decide the quality of
gasoline.
A Knocking
Gasoline is used as a fuel in scooters, motor cars,
aeroplanes etc., which are equipped with internal
combustion engines. In an internal combustion engine, a
gasoline vapour and air is first compressed by
with the help of a spark plug. The controlled combustion
of the fuel provides sufficient energy to the piston which
forces the vehicle to move. The
efficiency of the engine
depends upon the compression ratio (the ratio of the
original volume of the fuel-air mixture to that obtained
compression) of the fuel before ignition. Higher the
When the compression ratio exceeds the limit, the
of the fuel takes place before the
ignition
piston head reaches the
end of its stroke. This causes the fuel to burn
suddenly and
irregularly resulting in jerks against the piston and giving
rise to a sharp metallic sound known as knocking. The
knocking involves a loss of energy and decreases the power
of the engine. It may also cause
damage to the cylinder and
piston.
The maximum compression ratio that can be
obtained
without knocking in an engine with a fuel depends
given
upon the structure of hydrocarbons present in the fuel. The
ragnt cnan alkenes have practically no tendency to check
knocking. Therefore, straight chain alkenes give maximu
knocking and are regarded as poor fuels. Cycloalkenes ana
olefins possess a higher resistance to knocking as compared to
straight chain alkenes. Branched chain alkenes and aromatic
hydrocarbons possess the greatest resistance to knocking and
are regarded as superior fuels.
BOctane Number
The quality of a fuel is usually expressed in terms of
a number known as Octane number. An arbitrary scale of
Hydrocarbons
octane number has been set
up using n-heptane and iso-
octane (2, 2, 4-trimethylpentane) as
reference
n-heptane, being a straight chain alkane, givescompounds.
maximum
knocking and is regarded as a very poor
quality fuel. It is
arbitrarily assigned an octane number equal to zero. On the
other hand, iso-octane (2, 2,
branched chain hydrocarbon, 4-trimethylpentane), being a
shows a very high resistance
toknocking and is regarded as an ideal fuel. It has been
assigned octane number equal to 100.
CH3-CH2-CH2-CH2-CH2-CH3
n-heptanne
Octane number=0
CH3 CH3
CH3-C-CH2-CH-CH3
CH3
isO-octane
(2,2,4-trimethylpentane)
Octane number = 100
All other fuels are graded between octane numbers 0
and 100 by comparing with similarly working mixture of
iso-octane and n-heptane. Octane number of a fuel may be
defined as follows.
The octane number of a fuel is the percentage
by volume of iso-octane in a mixture of iso-octane
and n-heptane which possesses the same knocking
performance in the experimental engine as the fuel
under examination.
For example, a motorfuel is said to have an octane
number 70 when it is as good as a mixture containing
70% iso-octane and 30% n-heptane. It should be clearly
understood that octane number 70 of a fuel does not
mean that the given fuel contains 70% iso-octane and
30% n-heptane. It simply means that a fuel with octane
number 70 will work in an engine in the same way as a
mixture containing 70% iso-octane and 30% n-heptane
does. Similarly, a fuel with octane number 60 gives the
same knocking performance as that given by a mixture
containing 60% iso-octane and 40% n-heptane.
The quality of a motor fuel is decided by its octane
number. The antiknock property of the fuel increases with
an increase in the octane number. Therefore, higher the
Octane number better is the fuel.
C Octane Number and Structure of
Hydrocarbons
The octane number of a fuel is closely related to the
structure of its constituent hydrocarbons. As mentioned
earlier, different types of hydrocarbons possess antiknock
properties to different extents and therefore they possess
different octane numbers as described below.
chain alkanes
i) Straight possess
antiknock properties. Therefore, their octane
minimum E Quality of Diesel: Cetane Number
numbers are very low. The value decreases with
the increase in the length of the chain.
851
octane numbers
(1) Cycloalkenes possess higher
than the corresponding straight
chain alkanes.
(i) The branching of the chain
increases the octane
a branched
chain
number of a fuel. Therefore, number as
alkane possesses a higher octane
chain alkane having the
compared to a straight
same molecular formula.
and
(iv) The unsaturated hydrocarbons (alkenes
numbers than the
alkynes) have higher octane
corresponding straight chain alkenes.
(v) Aromatic hydrocarbons usually possess very high
values of octane number.
Commercial gasolines usually have octane numbers
81, 74 and 65 for the premium, regular and third grade
gasolines. Usually branched chain alkanes, alkenes and
aromatic hydrocarbons are added to straight run gasoline
to raise its octane number.
D Gasoline Additives (Antiknock Compounds)
Since knocking involves a loss of energy and causes
damage to the cylinder and piston of the engine, it is
undesirable and should be checked as far as possible.
Knocking tendency of a fuel can be decreased by the addition
of certain additives known as antiknock compounds. An
antiknock compound decreases the knocking tendency ofa
fuel and thus improves its octane number.
The commonly used antiknock compound is tetraethyl
lead (TEL), Pb (C2Hs)4. It is added to an extent of 0.01% to
the gasoline. Gasoline containing tetraethyl lead is called
leaded gasoline or ethyl gasoline.
The combustion of gasoline in engines produces
many gases such as carbon monoxide, carbon dioxide,
nitrogen dioxide and unburnt hydrocarbons. In case
of leaded gasoline, certain volatile compounds of lead
are also formed. The emission of these gases into the
atmosphere causes a great deal of pollution and poisoning.
The compounds of lead emitted into the atmosphere are
poisonous and pose serious health problems. With the
increasing use of automobiles, the pollution and poisoning
problem is getting more and more serious day-by-day. The
scientific community is trying hard to control and check
the pollution and poisoning problems. In order to control
pollution, following measures are being taken.
) Certain devices are being used to oxidise the
unburnt hydrocarbons and carbon monoxide. Devices
have also been suggested to decompose the oxides of
nitrogen formed during the combustion of gasoline.
(i) The frequent addition of tetraethyl lead to
gasoline is also being avoided. Efforts are being made
to improve the
quality of gasoline by adding aromatic
hydrocarbons and branched chain allkanes to straight
run gasoline instead of tetraethy lead.
Diesel oil is extensively used as a fuel in
heavy vehicles.
Itsquality is expressed in terms of Cetane number. It is
defined as follows.
 852 Nootan ISC Chemistry-XI
Cetane number of a fuel is the percentage of cetane CH
(n-hexadecane) in a mixture of cetane and a-methyl
Tnaphthalene that will have the same ignition characteristics
as the fuel under examination.
CH-(CH2)14-CH
Cetane ignites rapidly and is assigned cetane number Cetane (Hexadecane)
1-methylnaphthalene
equal to 100, whereas ca-methyl naphthalene ignites slowly Cetane number 100
(1-methylnaphthalene)
and is assigned a cetane number equal to zero. Cetane number = 0

REVI XERCISES
13.27 Write the name, compositions and uses of the 13.31 Out of n-heptane and 2-methylhexane which has a

fractions obtained on fractional distillation of higher octane number and why?

petroleum. 13.32 What is the composition of natural gas?
13.28 Why is it not possible to predict the exact nature of
13.33 How did petroleum come into existence in nature?
products obtained on thermal cracking ?
13.29 Why is an octane number equal to 100 has been 13.34 What do you understand by knocking?
assigned to iso-octane? 13.35 How is octane number of a fuel related to its
13.30 What are the pollution problems associated with the structure?
useof leaded gasoline in automobiles?

13.6 AROMATIC HYDROCARBONS (ARENES) : SOME IMPORTANT CONCEPTS

The unsaturated hydrocarbons containing one or more
bensene rings are called aromatic hydrocarbons. They are
also known as arenes. All arenes are cyclic compounds.
They may be monocyclic, bicyclic or polycyclic. The general
formula of monocyclic arenes like benzene (CgH) is
CnH2n - 6 while that of bicyc-lic arenes like naphthalene
(C1oHg) is CH2n - 12. In general, an arene with m rings
has the formula C, H2n -6m. The structures of some simple
arenes are given below.
H H
H H H H
H H H corresponding to the molecular formula CgH, will possess
H H
Benzene(C6H6) Naphthalene(C1otlg)
(Monocyclic) (Bicyclic)
H H
most of the chemical reactions, arenes behave like saturated
compounds and do not show much chemical reactivity. This
unique behaviour of arenes can be explained on the basis
of their structures. The structure of benzene is discussed
below
13.6.1 Structure of Benzene
The elucidation of the correct structure of benzene
remained a big problem in organic chemistry. The molecular
H
formula of the compound is found to be CoH6. Although the
molecular formula recommends it to be highly unsaturated,
it is a very stable compound and behaves very differently
from alkenes and alkynes. It cannot be represented by an
open chain structure because any open chain structure
double and triple bonds and will be unable to explain the
properties of benzene.
Hence, benzene must have a ring structure. Several
ring structures for benzene were proposed from time to
time, Sonme ofthese are as follows

Kekule (18o5) Dewar (1867) Claus (1867) Baeyer (1892)

H H Howeve, the liSt acceptabie ring structure for

benzene was proposed by a German chemist August
H H H
Kekule in 1865. The structure proposed by Kekule was
Anthracene(C14H1o0
(Tricyclic) widely accepted although it had some drawbacks. The
From the above structures, it appears that arenes are defects in Kekule's structure were later on rectified on the
highly unsaturated and highly reactive but it is not so. In basis of molecular orbital theory and concept of resonance.
 853
Hydrocarbons
basis of modern X-ray
of benzene could be possible on the
A Kekule's Structure of Benzene molecular orbital theory
diffraction techniques and benzene and
its
Kekule suggested that the benzene molecule is diffraction studies of
made The X-ray contains a regular
up of hexagonal ring of six carbon atoms joined alternately suggest that benzene
derivatives carbon-carbon bond
distance equal
by double and single bonds. Each carbon atom is attached
hexagonal ring with a at
to a nyarogen atom with a single bond, Thus. Kekule's to 139 pm, This bond distance is intermediare
carboon-
bond (154 pm) and
a
structure of benzene can be represented as of a carbon-carbon single and H-C-C
All C-C-C
carbon double bond (134 pm). be
bond angles are equal to
120°. These facts can easily
The
Molecular orbital theory.
explained on the basis of of benzene
molecular orbital explanation of the
structure

or is as follows.
It is assumed that each carbon
in benzene issp
(In this bond line representation, each
H C 2s and two 2p orbitals of
it is understood that each corner
Contains a carbon atom attached
hybridised. The half filled one
and redistribute
carbon (in the excited state) mix up together
to a hydrogen atomn) hybridisation, each
H their energy. On account of this sp-
evidences carbon acquires three sp hybrid orbitals lying
found in favour
in plane a
everal experimental were
orbitals,
of Kekule's structure and the structure was able to explain at an
angle of 120°. Out of the three sps hybrid
most of the properties of benzene. However, it failed to carbon overlap with the
two sp hybrid orbitals of each
certain facts about benzene. The main drawbacks
explain its neighbouring carbon atoms while
of Kekule's structure are as follows. sp hybrid orbitals oforbital
) The normal bond length of carbon-carbon single the third sp° hybrid overlaps with the half filled 1s
results in the formation of
bond is 154 pm while that of double bond is 134 pm. Since orbital of a hydrogen atom. This
a coplanar ring containing 6 C-C o
and 6 C-H o bonds
Kekule's structure possesses three carbon-carbon single
bonds and three double bonds, the benzene ring should not as shown in Fig. 13.17.
be a regular hexagon as proposed by Kekule. This is against
the observed facts. All C-C bonds in benzene are found
to be of equal length. The observed C-C bond length in
1s
Sp2
benzene is 139 pmn.
(i) The Kekule's structure of benzene possesses three sp-sp2
double bonds. This implies that benzene should be at least
three times as reactive as ethene which contains only
one

facts. Benzene is
double bond. This is against the observed
found to be very stable. Unlike alkenes, it does not undergO
addition reactions easily.
(ii) The Kekule's structure of benzene allows
the
disubstituted Hp 9pH
formation of two types of 1, 2-(ortho) 1s 1s
derivatives. Thus, we can have two types of 1, Sp2/

2-dichlorobenzenes as shown below.

CI
CI
Cl Cl
sp sp2

This is also against the observed facts. Actually, only

one type of ortho
disubstituted derivatives are known. 1s
H
1S
H
Kekule tried to explain the last drawback by suggesting
that the double bonds in benzene ring were continuously H

back and forth between the neighbouring carbon

oscillating
atoms as shown below. sp2-sp2
(o) bond

H-c 120 sp5H

()
Since the position of the double bonds are not fixed, bond
derivative.
we shall get only one type of ortho disubstituted
/120
B Orbital Structure of Benzene
Although Kekule could not explain the above H H
mentioned first and second drawbacks in his model of Fig. 13.17 Overlapping of hybrid orbitals of carbon to from
correctness of his structure
benzene, the proot of the basic 6 C-C and 6 C-H G-bonds in benzene.
 856 Nootan ISC Chemistry-XI
In the above reaction, m-nitrophenol is obtained onh
CH3 CH3 to an extent of about 1%. Thus, the products of the reaction
CH3 and p-nitrophenol.
are primarily o-nitrophenol
benzoic acid is subjected
On the other hand, when to

acid (85%)
m-nitrobenzoic
CH3 nitration, the major product is
The o-and p-nitrobenzoic acids are obtained only in smal
1,2-dimethylbenzene 1,3-dimethylbenzene
(0-xylene) (m-xylene) amounts.
COOH COOH

CH3 CHCH3 Conc. H2S04

+ HNO3
Benzoic acid NO2
m-nitrobenzoic acid
Ethylbenzene (85%)
CH3 From the above, it may be concluded that -OH
1,4-dimethylbenzene group when present on the ring directs the incoming
(p-xylene)
group towards ortho and para positions, whereas
In case of naphthalene, even mono-substituted -COOH group present on the benzene ring directs the
derivative show isomerism as in 1-methyl
can
and
naphthalene incoming group towards meta position.
2-methyl naphthalene. These isomers are shown below. On the bais of directive influence, the substituent
H3 groups can be classified into following two categories.
CH3 (i) Ortho and para directing groups The
substituent groups which direct the incoming group to
enter the ring prinmarily on ortho and para positions
1-methylnaphthalene 2-methylnaphthalene are called ortho and para directing groups.
(a-methylnaphthalene) (B-methylnaphthalene) Some important 0-and p-directing groups are
13.6.4 Directive Influence of
Substituents -NH2-NHR,-NR2,-OH,-OR-CoOR,-R,-:
When a monosubstituted derivative of benzene (halogen), etc.
(or some other arene) is subjected to further substitution, (ii) Meta directing groups : The substituent groups
the position occupied by the incoming substituent which direct the incoming
group on group to enter the ring primarily
the ring primarily depends on the nature of the substituent on the meta
position are called m-directing groups.
already present on the ring. In other words, a substituent Some important
m-directing
already present on the benzene ring decides primarily the groups are-NO2, -C=N,
position to be taken by the incoming substituent group on the
-SOgH, --CHO,-COOH, etc.
ring. This tendency of the substituent already present on Activating and
Deactivating Influence of
the ring is called its directive influence. Substituents
For example, when phenol is subjected to nitration, A substituent
group already present on the benzene
the product obtained is a mixture of mainly o-and ring not only determines the
position occupied by the
p-nitrophenols. incoming group on the ring but also activates or deactivates
OH the ring towards the second
OH substitution. Thus, the groupP
already present on the ring decides the rate of reaction
NO2 involving further substitution.
O +HNO3
Conc. H2S04
The substituents which enhance
the rate of secona
Phenol (Conc.) substitution with respect to benzene are called
substituents, while those which decrease theactivating8
0-nitrophenol
58%
rate of
OH second substitution with
respect to benzene are called
deactivating substituents. In general, o-and p-directing
substituents are activating
substituents, whereas
m-directing substituents are deactivating substituents.
However, groupX -Cl, B r orI) is an exception.
NO2 Inspite of being o-and p-directing, it is a deactivating
substituent. The activating and
p-nitrophenol are listed in Table 13.2.
deactivating substituents
41%
Hydrocarbons
Table 13.2
Activating and
Activating Substituents Deactivating Substituents From the above
857

o-and p-directing Deactivating Substituents an o-and

p-directing
resonance structures, it is clear that
group increases the electron density
-NH2,-NHR,-NR2, m-directing: in the
ring and thus makes the
monosubstituted derivative
more
-OH
-NO2,-CN,-CHO, susceptible to the further
electrophilic attack. Thus,
-COR, -COOH, an o-and p-directing group
-OR,-NHCOR, -COR, above resonance activates the ring. From the
-R,Ar (aryl group) -COOR,-CONH2 structures it is also clear that the
electron
density is relatively greater at ortho and
-SOgH Therefore, the incoming electrophile attacks onpositions.
para
O-and p-directing: P-positions and occupies these positions o -and

- -CI, -Br,-| 0- and on the ring. Thus,

p-disubstituted derivatives are obtained.
Explanation of Directive
and
2. m-directing groups: In
of Substituents Activating Influencekey atom is usually attached m-directingto an
groups, the
The directive atom by a
multiple bond. Such a substituent electronegative
influence and the exerts an
deactivating effects of the substituent activating or electron-withdrawing
is because the
influence on the ring
system. This
explained on the basis of charge groups can be electronegative atom pulls the electron
1. 0-and distribution as given below. pair the multiple bond resulting in a decrease in
of
p-directing
groups (except alkyl groups: The o-and electron density at the the
p-directing
of electrons on their groups) possess one or more lone pair atom withdraws electrons from the
key atom. Therefore, the key
the ring). For key atoms (atoms directly attached to to several resonance structures. ring. This gives rise
example, the monosubstituted Thus, the structure of
derivative (carrying a
group) can be m-directing
-NH2 -H represented as a resonance hybrid of several
(One lone pair
of electrons)
(Two lone pairs
--R canonical forms. For
nitrobenzene are as follows.
example, the resonance structures of

of electrons)
(Two lone pairs
of electrons)
The lone pair of electrons
interacts with the 0
system of the ring and gives rise to several T-electron N
resonance
structures. Thus, the structure of a
benzene (carrying an o-and monosubstituted
p-directing group) can be
represented as a resonance hybrid of several canonical
forms. For example, the resonance structures of
aniline are as follows.
phenol and
:ÖH +ÖH +OH
O

Resonance
OH OH hybrid
From these resonance structures, it is clear that a
,

- Resonance
m-directing group withdraws electrons from the ring
and decreases the electron density in the ring. Due to a
decrease in the electron density, the benzene ring becomes
NH2 H2 NH2 hybrid
less susceptible to the further electrophilic attack.
Thus, a
m-directing group deactivates the ring. Moreover, due
to the presence of a m-directing group at the benzene
ring,
the electron density decreases at ortho and
para positions
NH2 of the ring. Consequently meta positions become centres
NH2 NH2
of relatively higher electron density. Hence, the incoming
electrophile prefers to attack at the meta position and
-
occupies this position on the ring. Thus, a meta disubstituted
Resonance derivative is obtained.
hybrid
 858 Nootan 1SC Chemistry-XI

13.7 BENZENE
Benzene is the simplest and the most
arene lt is regarded as the parent hydrocarbon of aromatic
important 3CH=CH 673 K CH6
compounds. It was discovered by Faraday in 1825.
Acetylene

13.7.1 Preparation of Benzene B Manufacture

On commercial scale, benzene is prepared by the
ALaboratoryMethods following methods.
In the laboratory, benzene can be prepared by the 1. From coal tar: The light oil fraction obtained by the
tollowing methods. fractional distillation of coal tar upto 443 K is mainly a
1.From sodium benzoate Benzene can conveniently mixture of benzene, toluene and xylene. It also contains
be prepared in the laboratory by heating sodium benzoate and some
some compounds such as pyridine
basic acidic
with soda lime.
cresols.
COONa compounds such as phenol and
The light oil is first washed with conc. HoSO to
remove the basic compounds and then with dilute NaOH
NaOH Hear
CaO [O+ +Na,CO3 solution to remove acidic compounds. It is then washed with
LT
Sodium benzoate Benzene water and subjected to fractional distillation. The fraction
A mixture of sodium benzoate and soda lime is taken passing upto 383 K is collected. It is called 90% benzol. It
in a round bottomed flask fitted with a condenser and a consists mainly of benzene, toluene and thiophene. It is
receiver. On heating the reaction mixture, benzene distills refactionated and the fraction distilling over at 353-354
Over and collects in the receiver. It may be further purified K is collected. It is then cooled in a freezing mixture to
by redistillation. almost pure benzene. Benzene thus
get the crystals of
2. From phenol When phenol is distilled with zine obtained may further be purified by treating it with cold
dust, benzene is obtained.
and concentrated sulphuric acid.
OH
2. From coal gas: Coal gas obtained by high temperature
coking of coal is an important industrial source of benzene.
O Zn
Distillation
+ZnO Coal gas is passed through towers in which high boiling
creosote oil is sprayed from the top (Fig. 13.20). Benzene
Pheno Benzene
3. From benzene sulphonic acid: When benzene
sulphonic acid is boiled with concentrated HCl at 423 K, it
and
toluene present in the coal gas get dissolved in the
creosote oil. The solution thus obtained is subjected to
undergoes hydrolysis to give benzene. steam distillation when a mixture of benzene and toluene
SO,H is obtained. Benzene is separated from this mixture by
fractional distillation.
403-423 K , O J +H2SO4
H,0 HCl
Creosote oil
Benzene Benzene
sulphonic acid
4. From benzene diazonium chloride:When benzene
diazoníum chloride is reduced by ethyl alcohol, benzene Residual gas
is obtained.
NC
-
Coal gas
CH CH0OH -

Benzene Benzene
Pump
diazonium chloride

+ CH CHO + N2 +HCI Creosote Oil + Dissolved

Benzene & Toluene
5. From acetylene (synthesis): Benzene can also be
obtained by passing acetylene under pressure through a Fig. 13.20 Recovery of benzene and toluene from coa
tube heated to 673 K. gas.
Hydrocarbons 859

molecule adds three

13.7.2 Physical Properties of Benzene (iii) Addition of ozone: Benzene
which upon
molecules of ozone to form benzene triozonide
1) Benzene 1S a
colourless mobile
characteristic odour. liquid having hydrolysis yields three molecules or
8yOxdl
(ii) It boils at 353.1 K and on
white crystalline solid which melts
cooling solidifies
278 K. at
to a
CH-CH-Q
(iii) It is insoluble in water but is miscible with alcohol CH CH40
and ether in all CHTQ CH-Ö
proportions. + 303
iv) It is a good solvent for fats, resins, sulphur, iodine HGCH CH Ozone CH
and a
large number of organic compounds.
(v) It burns with a luminous
sooty flame. Benzenetrizonide
(vi) Its vapours are toxic and
produce unconsciousness Benzene
when inhaled in (Kekule's structure)
large quantity.
13.7.3 Chemical Properties of Benzene CHO
Inspite of the presence of three double bonds in the Hydrolysis +3H202
ring, benzene is quite stable and behaves in a much different 3H20
way as compared to alkenes. The stability of benzene CHO
may be attributed to the delocalisation of r-electrons as
Glyoxal
discussed earlier. Some important chemical reactions of
benzene are as follows.
2. Substitution Reactions
1. Addition Reactions Substitution reactions are the most characteristic
The delocalised n-electrons in benzene possess extra and useful reactions of benzene. Benzene undergoes
stability and show chemical properties much different electrophilic substitution reactions readily. This is
from those of alkenes and alkynes. This is why it does not because benzene ring contains a delocalised r-molecular
undergo addition reactions frequently and easily. However, orbital containing six t-electrons and thus acts as a source
it may be forced to undergo addition reactions in more of electrons for the attacking electrophile. These reactions
drastic conditions (like higher temperature and pressure). involve the replacement of one or more hydrogen atoms of
Some important addition reactions of benzene are given the ring by electrophiles.

below. General mechanism of electrophilic

(i) Addition of hydrogen: Benzene reacts with hydrogen substitution: Due to the presence of six delocalised
in the presence of a catalyst such as finely divided nickel or Tt-electrons, benzene ring behaves as a source of
platinum at 473-573 K to give cyclohexane. electrons and invites electrophiles to attack on it.
When an electrophile (E) attacks on the benzene
Ni or Pt
O 3H2 473-573 K
ring, a o-complex is formed which is a resonance
stabilised carbocation.
Benzene Cyclohexane
(i) Addition of halogens: In the presence of ultraviolet
benzene reacts with chlorine (or
light (or sunlight),
bromine, but not iodine) to form benzenehexachloride
which is commonly known as BHC.
Cl Benzene Electrophile

Cl CI
HE
Benzene
+ 3Cl2
CI C -
Canonical forms of o-complex
(Resonance stabilised carbocation)
G-complex
(Resonance hybrid)
Benzenehexachloride (BHC)

BHC is used
sold under the name
as an insecticide and
o-complex thus formed eliminates a proton (H)
lindane. It is also referred to as 666 due to by the action of a base to yield the final
substitution
gammexane or
its molecular formula GgH6Cl6. product.
 860
Nootan 1SC Chemistry-XI

H Cl H Cl
B
[O] +H: B [o)a
d-complex Base Substitution product Benzene Electrophile

place
(i) Halogenation The
in the presence of Lewis
halogenation in benzene takes H-
C H C
acids like ferric
aluminium or
salts of the
corresponding halogen which act as catalysts
and are also referred to as
halogen carriers. o-Complex
For example, (Resonance hybrid)
CI
CI HC
FeCl3
+FeCl4 OJ +FeCl3 +HCl
+Cl
OJ + HCl G-complex Base Chlorobenzene Halogen carrier
(Substitution product) (Regenerated)
Benzene
Chlorobenzene (ii) Nitration The replacement of a hydrogen atom
in the benzene ring by a nitro
Br (-NO2) group is called
nitration. Nitration of benzene is carried out by
with a mixture of concentrated nitric acid and
treating it
+Br2 FeBt3 +HBr sulphuric acid at 333 K.
concentrated

Benzene
Bromobenzene NO2
Reaction with iodine is reversible due to the formation HSO4
of HI in the reaction. Therefore, iodination is + HNO3 +H20
carried out in 333 K
the presence of an Benzene
oxidising agent such as nitric acid. Nitrobenzene
Mechanism Concentrated sulphuric acid first
:
protonates concentrated nitric acid to generate the
electrophile NO2 (nitronium ion) which attacks on
HNO3 benzene ring to form a resonance stabilised
o+l OJ + HI
The o-complex then reacts with the base
the final substitution
o-complex.
HSO4 to form
lodobenzene product.
6HI + 2HNOg > 4H0 + 2NO +312
Fluorination is very vigorous in the case of arenes and HSO4 +H-0-N H-o-N
is rarely used to prepare fluoroarenes. O
Conc. sulphuric acid Conc. nitric acid
Protonated
Mechanism : The halogen carrier first attacks nitric acid
on the halogen molecule to form the HSO4
corresponding Base
electrophile. The electrophile thus produced attacks
on the benzene ring to form a resonance stabilised H--N H o +NO2
Nitronium ion
o-complex which reacts with the base to give the final H
substitution product. The mechanism can be written as
(Electrophile)
follows. NO2 H NO2

Cl-Cl+ FeClg CI FeCl4

Halogen Halogen Electrophile Base Benzene Electrophile
carrier H NO2 H. NO2

a-Complex
 861
NO2 NO2
+ HSO4
SO3
SO3
plex Base (o]++HSO4 +HSO4
[ o J + H2SO4
Nitrobenzene
Substitution product)
ii)Sulphonation : Sulphonation
cement of involves the
SO3 SOgH
a
hydrogen atom in the
SO3H) group. Benzene ring by asulphonic + H20
can be +H30
edting itwith
fuming sulphonated by
sulphuric acid containing sulphuric
Benzene sulphonic acid
acid
dissolved
(concentrated (Substitution product)
obtained is benzene sulphonic acid. sOa). The product be carried out by
Sulphonation of benzene can also

SOgH treating it with chlorosulphonic acid.

SO3H

H2SO4 O ++HO + HCl

+CISOgH
Benzene Containing SO3) Benzene sulphonic acid
Benzene Chlorosulphonic
Benzene sulphonic
acid
Mechanism : Sulphonation of benzene takes place acid
was
reaction : This reaction
through the following mechanism. Friedel-Crafts
(iv) and is
M. Crafts in 1877
molecule discovered by Charles Friedel and
) Concentrated sulphuric acid releases a
important organic synthesis.
reaction in
regarded as a very
of SO3 the replacement of a hydrogen
atom
The reaction involves
HSO H2SO4 2 H o +HSO4+ SO3 O

hybrid of the following

SO3 is a resonance
or acyl (R--C-) group in the
in benzene ringby an alkyl The
canonical forms. aluminium chloride as catalyst.
presence of anhydrous termed as
a n alkyl group
is
O O replacement of hydrogen by
whereas the replacement of H
Friedel-Crafts alkylation,
referred to as Friedel-Crafts acylation.
by a n acyl group is
==o O

-o (a) Friedel-Crafts alkylation:

When benzene is
halide in the presence of anhydrous
treated with a n alkyl
a n alkyl
benzene is obtained. For
aluminium chloride,

example,
=O CH3
SOg and
acts
as
be represented
AlCl3
(o
SOg can HCI
Therefore,
to
+CH3Cl
as an electrophile. benzene ring Toluene
attacks on
electrophile
(ii) The C2H5
form a a-complex.
H SO3
sOg
H +CaH5Cl
AlCla ( o ] + HCI
Ethylbenzene
SO SO3 Friedel-Crafts alkylation takes
H Mechanism: The
sOg mechanism.
the following
H place through
CH CH2Cl + AICl3 CH CH2 +AlCl4
Ethyl carbocation Base
Aluminium chloride
o-Complex

(Resonance stabilised)

Ethyl chloride (Lewis acid) (Electrophile)

(An alkyl halide)
to
base HSO4
the
with
reacts product.
substitution
o-complex
final
The the
ui) form
and
proton
aa
lrse
 Nootan 1SC Chemistry-XI
862
Oxidation Reactions
CHCH3 H CHCH3.
Since benzene is a stable compound, it is not readily
oxidation
of its important
+CHCH2 Oxidised. Following are some

reactions.

Benzene Electrophile (i) Combustion Benzene burns with a smoky flameto

H CH,CH CHCH3 give carbon dioxide and water

2GH6 + 150 > 12C02 + 6H,0

oxidation When mixture of benzene
a
o-complex (ii) Catalytic
vanadium pentoxide at 723-
(Resonance stabilised) vapour and air is passed over
773 K, maleic anhydride is obtained.
CH,CH
CH2CH3 H CHCOOH

+AICl4 + AlCl + HCl C6H6 2 VO5

723-773 K CHCOH
+2C02 + H20
Maleic acid
-Complex Base Ethyl benzene Catalyst
(Substitution product) regenerated
(b) Friedel-Crafts acylation: When benzene is
-H0
treated with a carboxylic acid halide (acyl halide) in the CHCO
presence of anhydrous aluminium chloride, an acyl halide
is obtained. For example, CHCO
COCH3 Maleic anhydride

13.7.4 Uses of Benzene

+CHCOCl AlCl3 + HCl
(1) Benzene is used as a solvent for fats, resins,
Ethanoyl chloride Acetylbenzene rubbers, paints etc.
(Acetyl chloride) (Acetophenone)
Mechanism: The Friedel-Crafts acylation takes (ii) It is used in the manufacture of styrene,
place as follows. gammaxene, nitrobenzene, chlorobenzene,
phenol, nylon, detergents, insecticides etc.
(ii) It is used in dry cleaning of woollen clothes.
CH-CLci+ AlCl3 CH3-C +AlCl4
Acetyl chloride Aluminium Acetylinium ion Base iv) Mixed with petrol, it is used as a motor fuel
chloride (Electrophile) under the name benzol.
(Lewis acid)
O 13.7.5 Tests for Benzene
) It forms nitrobenzene when warmed with conc.
H C-CH3
HNO and conc. H2SO4. Nitrobenzene thus formed has a
+CHg-C characteristic bitter almond odour.
Take 1 c.c. of the given compound and add to it
Benzene Electrophile 1 c.c. of the mixture containing equal volumes of
conc. HNO3 and conc. H2SO4. Warm the contents
(to about 50°C) and pour into 5 c.c. of cold water contained
H C-CH3 H -CH H -CH3 in a beaker. A bitter almond odour indicates the
presence
of benzene.
(ii) It forms pale yellow m-dinitrobenzene when
G-complex boiled with conc. H2SO4
(Resonance stabilised)
Take 1 c.c. of the given compound and add to it
O=C-CH3 2 c.c. each of conc. HNO3 and conc. H2S04. Heat to
CH3 boiling
and then pour into 20 c.c. of cold water contained in a
+AlCl | 0 +AlCl3 + HCI beaker. Appearance of a pale yellow solid due to formation
of m-dinitrobenzene confirms the presence of benzene.
o-complex Base Acetophenone Catalyst
(Substitution product) regenerated
 13.8 CAR

The
ARCI N OGENECI
HYDROCARBONS T Y AND OXICITY
TOXICITY
863

or isolate hydrocarbons containing

benzene rings
OF BENZENE AND POLYNUCL
drocarbons.
re
more
In
fused
two or
more fused
are called Polynuclear
benzene rings are polynuclear
togetherhydrocarbons,
Some exa mples of fused CH3
fused in ortho two or 8
follows:
polynuclear hydrocarbonspositions.
are as C
CH3
1,2-benzanthracene 9,10-dimethyl-1,2-
benzanthracene

Naphthalene Anthracene Pyrene

1,2,5,6-dibenzanthracene
1,2-benzpyrene

Phenanthrene
Coal-tar IS the main source of polynuclear
hydrocarbons. Naphthalene
the is
constituent (6-10%) of coal-tar. It islargest single
obtained
HgC
cooling the middle oil fraction. (b.p. 443-503 K) byof 3-methylcholanthrene
coal tar. Anthracene is obtained from
green oil fraction Such polynuclear hydrocarbons are formed on
(b.p. 543-633 K) of coal-tar to an extent of about 1%.
incomplete combustion of organic materials like tobacco,
Benzene and polynuclear hydrocarbons containing coal and petroleum. They enter into human body and cause
more than two benzene rings fused together are
cancer by damaging DNA through various biochemical
carcinogenic, i.e., cancer producing in nature. Some of the
notable ones are reactions.
No general rule is available to predict the
1,2-benzanthracene; of hydrocarbons or their
carcinogenic activity
1,2-benzpyrene; derivatives. However, the number and position of certain
9,10-dimethyl-1,2-benzanthracene; have been
groups such as-CH3,-OH,-CN,-OCH3
1,2,5,6-dibenzanthracene;
found to influence the carcinogenic activity.
3-methylcholanthrene, etc.

REVI XERCISES
fact that C-C bond
13.41 How would you account for the
Give twoexamples. benzene is intermediate to that of C-C
arenes? length in
13.36 What are
structure of benzene. and C-C bonds?
13.37 Discuss
the orbital stable compound does not satisfy Huckel's
benzene behave
as a 13.42 Which of the following
does
13.38 Why contains
three double bonds? rule?
What
although it structure of benzene.
(a) Benzene
Explain the
r e s o n a n c e

13.39 r e s o n a n c e
hybrid? (b) 1, 3-cyclobutadiene
understand by aromatic
do you
isomers of the following (c) Naphthalene
the possible Ans. 1, 3-cyclobutadienel
13.40 WVrite (d) Furan
Compounds.
13.43 Why are naphthalene and anthracene regarded as
(i) C7Hs aromatic compounds?
(ii) C6H4 (OH)2
(iii) CoH4 (CH3)2