25

Hydrocarbons
Hydrocarbons are the organic compounds containing carbon and
hydrogen only, e.g. alkane, alkene and alkynes.

Classification of Hydrocarbons
Hydrocarbons

Open chain compounds Cyclic compounds

(Aliphatic compounds)

Saturated Unsaturated Aromatic Alicylic

hydrocarbon hydrocarbon compounds compound
(Alkane) (e.g. cyclobutane)
[CnH2n + 2]
Alkene Alkyne
[CnH2n] [CnH2n – 2]
Benzenoids Non-benzenoids
(e.g. benzene, (Tropolone)
toluene etc.)

Alkanes
Alkanes are saturated, open chain hydrocarbons containing
carbon-carbon single bonds, e.g. methane (CH 4 ), ethane (C2H 6 ),
propane (C3H 8 ), etc.
These hydrocarbons are inert under normal conditions [i.e. do not react
with acids, bases and other reagents]. Hence, they were earlier known
as paraffins (Latin : parum-little; affins-affinity)
Alkanes exhibit chain isomerism and position isomerism.
362 Handbook of Chemistry

Structure
Alkanes possess only sigma bonds. In these molecules, carbon atom lies
at centre and hydrogen atoms lie at the corners of regular tetrahedron.
All H—C—H bond angles are 109.5°.

Methods of Preparation of Alkanes

(i) From hydrogenation of alkenes and alkynes
Pt/Pd/Ni
CH 2 ==CH 2 + H 2 ¾¾¾® CH3 ¾ CH3
Ethene Ethane
Pt/Pd/Ni
CH3 ¾ C ººC ¾ H + 2H ¾¾¾® CH3 ¾ CH 2 ¾ CH3
Propane

Ease of hydrogenation depends on the steric crowding across the

multiple bond. More is the steric crowding, the less is the
reactivity towards hydrogenation.
(ii) By sodalime Decarboxylation of sodium or potassium salts of
fatty acids [decarboxylation reaction] in presence of NaOH, CaO
gives alkane.
sÅ
CaO
RCOON a + NaOH ¾¾® R ¾ H + Na 2 CO3
D
This reaction is used for descending of series as the alkane
obtained has one carbon less than the parent compound. CaO is
more hygroscopic than NaOH and it keeps NaOH in dry state.
(iii) By Wurtz reaction
Dry ether
R ¾ X + 2 Na + X ¾ R ¾¾¾® R ¾ R + NaX
Alkyl halide
This reaction is used to increase the length of the carbon chain.
(iv) By reduction of alkyl halides
Zn ¾ Cu /Alcohol
R ¾ X + 2[H] ¾¾¾¾¾¾¾® R ¾ H + HX
Reducing agents like Zn/HCl, HI/Red P, H 2/Pd can also be used.
(v) By Kolbe’s electrolysis
- Å Electrolysis
2CH3COONa + 2H 2O ¾¾¾¾®
CH3 ¾ CH3 + 2NaOH + 2CO2 + H 2
Only alkanes with even number of carbon atoms can be formed.
Alkane and CO2 are liberated at anode while H 2 is liberated at
cathode.
 Hydrocarbons 363
(vi) Clemmensen’s reduction
H3C H H Zn ¾ Hg /HCl
C == O + 4[H] ¾¾¾¾¾® H3C ¾ CH3 + H 2O
H H H ethane
ethanal
(vii) From compounds containing oxygen Alcohols,
aldehydes, ketones, carboxylic acids and their derivatives give
alkane when treated with hot conc. HI and red P in a sealed
tube.
Red P
ROH + 2HI ¾¾¾® R ¾ H + H 2O + I2 ­
150°C
Red P
R ¾ C ==O + 4HI ¾¾¾® R ¾ CH 2 + H 2O + I2 ­
½ 150°C ½
H H
Red P
RCOOH + 6HI ¾¾¾® R ¾ CH3 + 2H 2O + 3I2 ­
150°C
(viii) Wolff-Kishner’s reduction
H3C
C ==O + H 2 N ¾ NH 2 ¾¾¾®
- H2O
H3C
H3C KOH/Glycol
C ==N ¾ NH 2 ¾¾¾¾¾¾¾® H3C ¾ CH 2 ¾ CH3
435- 473 K, - N2 Propane
H3C
(ix) From carbides
Al4C3 + 12H 2O ¾® 4Al(OH)3 + 3CH 4
Aluminium Steam Methane
carbide
and, Be2 C + 4H 2O ¾® 2Be(OH)2 + CH 4
Beryllium carbide Methane

(x) Corey-House synthesis This method can be used to prepare

alkanes having odd number of carbon atoms.
Ether
RX + 2Li ¾¾® R ¾ Li + LiX
2R ¾ Li + CuI ¾¾® LiR2Cu
LiR2Cu + R¢ X ¾¾® R ¾ R¢ + R ¾ Cu + LiX
Alkane
364 Handbook of Chemistry

Physical Properties of Alkanes

(i) The first four members are colourless gas, next thirteen
members are colourless liquids and next higher members are
colourless solids.
(It can be explained on the basis of magnitude of attraction
forces.)
(ii) Boiling point of alkanes decreases on branching.
BP µ VAF (van der Waals’ forces)
VAF µ molecular mass or VAF µ SA (Surface area)
So, boiling point order can be given as
n-octane > iso-octane > 2, 2, 3, 3-tetramethyl butane
(iii) Alkanes with even number of carbon atoms have higher melting
points as compared to next higher or lower alkanes with odd
number of carbon atoms.
(iv) Alkanes being non-polar in nature, soluble in non-polar solvents
but insoluble in polar solvent such as water.

Chemical Properties of Alkanes

(i) Halogenation of alkanes
(a) Chlorination
hn hn Cl 2 /hn
CH 4 + Cl2 ¾® CH3Cl ¾¾® CH 2Cl2 ¾¾¾® CHCl3
- HCl Cl 2 - HCl
- HCl
Cl 2 /hn
¾¾¾¾® CCl4
- HCl
(b) Bromination of alkanes proceeds in the same way but not so
easily.
(c) Iodination
CH 4 + I2 º
CH3I + HI
Order of reactivity of halogens is
F2 > Cl2 > Br2 > I2
Order of reactivity of hydrogen of alkane is
3° > 2° > 1°
Mechanism of halogenation of alkanes proceed via free radical
formation, i.e. the attacking reagent is a halogen free radical ( X · ). It is
a chain reaction.
 Hydrocarbons 365
(ii) Combustion
( 3n + 1)
Cn H 2n + 2 + O2 ¾® nCO2 + ( n + 1) H 2O
2
Due to the evolution of a large amount of heat during combustion,
alkanes are used as fuels.
(iii) Controlled oxidation
Cu / 523 K / 100 atm
(i) 2CH 4 + O2 ¾¾¾¾¾¾¾® 2 CH3OH
9:1 methanol
Mo 2O3
(ii) CH 4 + O2 ¾¾¾® HCHO + H 2O
D
(CH3 COO) 2 Mn
(iii) 2CH3 ¾ CH3 + 3O2 ¾¾¾¾¾® 2CH3COOH + 2H 2O
D
Burn
(iv) CH 4 + O2 ¾¾® C + 2H 2O
limited carbon
black
(iv) Isomerisation
Anhy. AlCl3
CH3 (CH 2 )4CH3 ¾¾¾¾¾® CH3 ¾ CH¾ (CH 2 )2CH3
HCl
½
CH3
2-methylpentane

+ CH3 ¾ CH 2CH ¾ CH 2 CH3

½
CH3
3-methylpentane

(v) Aromatisation

CH3 Cr2O3 or V2O5

CH2 CH3 or Mo2O3

CH2 CH2 773 K

10–20 atm
CH2

(vi) Reaction with steam

Ni
CH 4 + H 2O ¾¾® CO + 3H 2
D
366 Handbook of Chemistry

(vii) Pyrolysis
Pt or Pd or Ni
C12H 26 ¾¾¾¾¾® C7H16 + C5H10 + Other products
(viii) Nitration
D
C6H13 ¾ H + HO ¾ NO2 ¾® C6H13NO2 + H 2O
Nitrohexane
(ix) Sulphonation
400°C
C6H13 ¾ H + HOSO3H (conc. ) ¾¾® C6H13 ¾ SO3H + H 2O
Hexane sulphonic acid

Reactions for Methane (CH4 )

O2
2CH3OH
Cu/523 K/100 atm
È Å NaOH
CH3COONa HCHO + H2O
CaO Mo2O3
H2 O 2O2
CH3MgCl CO2 + 2H2O
(Hydrolysis)
CH 4 (Combustion)
(Methane)
Al4C3 + H2O 1000°C
C + 2H2
(Pyrolysis)
Ni/300°C
CO + 3H2 Excess Cl2
(Reduction) CH3Cl + CH2Cl2 + CHCl3
+ CCl4 + 4HCl
Conc. HNO3
CH3NO2 + H2
(Methane cannot be prepared by Wurtz reaction, Kolbe’s electrolytic
process and by reduction of alkenes or alkynes).

Reactions for Ethane (C 2H 6 )

2Na O2
2CH3Br 2CO2 + 3H2O
Dry ether (Combustion)
(Wurtz reaction)
C2H5MgCl 800°C
H 2O C 2H6 C 2 H 4 + H2
(Pyrolysis)
(Ethane) Cl2
C2H5 COONa C2H5Cl + HCl
NaOH/CaO
H 2O Conc. HNO3
CH3 COONa 450°C
Electrolysis C2H5NO2 + H2O

Pt or Pd or Ni Oxidation
CH2 CH2 C2H5OH
H2
 Hydrocarbons 367
Conformations of Alkanes
Alkanes have C—C sigma ( s) bonds and rotation about C—C single
bond is allowed. This rotation results in different spatial
arrangements of atoms in space which can change into one another,
such spatial arrangements are called conformations or conformers or
rotamers.
Conformations of ethane
(i) Sawhorse projections
H H

H H H H
H
H
H
H H H
eclipsed staggered
(ii) Newman projections
H
H H

H H

H
H H H H
H
H
eclipsed staggered

Intermediate conformation between eclipsed and staggered are

known as skew (gauche) conformations.
Eclipsed form is least stable but staggered form is most stable due to
greater distance between the bond pairs or lesser torsional strain.
The energy difference between the two extreme forms is of the order of
12.5 kJ mol -1.

Alkenes
These are unsaturated non-cyclic hydrocarbons which have
sp2-hybridisation with 120° bond angle.
Alkenes are also called olefins [oil forming] which indicates their high
reactive nature.
Alkenes have general formula Cn H 2n , where n = 2, 3, 4 …
e.g., C2H 4 (ethene), C3H 6 (propene), etc.
368 Handbook of Chemistry

Structure
Alkenes possess atleast one p bond and have triangular planar shape
with a bond angle of 120° between C—H bonds.

Isomerism in Alkenes
Alkene show both structural isomerism and geometrical isomerism.
Structural isomerism exhibited by alkenes are chain isomerism and
position isomerism.
Alkenes also exhibit stereoisomerism as geometrical (cis-trans)
isomerism. cis-form of alkene is found to be morepolar than trans-form
because dipolemoment of trans-form is almost zero.
H3C CH3 H3C H
C ==C C ==C
H H H CH3
(m = 0.33D) (m = 0)
[ cis- but-2-ene] [ trans- but-2-ene]

Methods of Preparation of Alkenes

(i) From alkynes
Pd/C R R¢
R ¾ C ººC ¾ R¢ + H 2 ¾¾® C ==C
H H
cis-alkene

(ii) From alkyl halide [dehydrohalogenation]

H H
½ ½ Alc. KOH H H
H ¾ C ¾ C ¾ H ¾¾¾¾® C ==C
½ ½ D
H H
H X [ b- elimination product]
[ X = Cl, Br, I]
(iii) From vicinal dihalides
CH 2Br ¾ CH 2Br + Zn ¾® CH 2 ==CH 2 + ZnBr2
CH3 ¾ CH ¾ CH 2 + Zn ¾® CH3 ¾ CH ==CH 2 + ZnBr2
½ ½
Br Br
(iv) From alcohols by acidic dehydrogenation
H H
½ ½ Conc. H2SO 4
H ¾ C ¾ C ¾ H ¾¾¾¾® CH 2 ==CH 2 + H 2
½ ½ D
ethene
H OH
ethanol
 Hydrocarbons 369
Physical Properties of Alkenes
Alkene as a class resemble alkanes in physical properties, except in
types of isomerism and difference in polar nature.
C1 to C3 are gases, the next fourteen are liquids and the higher
members are solids.
Alkenes show a regular increase in boiling point with increase in size.

Chemical Properties of Alkenes

(i) Addition of halogens
CCl 4
CH 2 ==CH 2 + Br ¾ Br ¾¾® CH 2 ¾ CH 2
ethene ½ ½
Br Br
1,2 -dibromoethane

CH3 ¾ CH ==CH 2 + Cl ¾ Cl ¾® CH3 ¾ CH ¾ CH 2

propene ½ ½
Cl Cl
1,2 -dichloropropane

(ii) Addition of hydrogen halides HCl, HBr, HI add up to

alkenes to form alkyl halides as per their reactivity order
HI > HBr > HCl
Addition reaction of HBr to unsymmetrical alkenes
(Markownikoff ’s rule) According to Markownikoff's rule,
the negative part of the addendum (adding molecule) gets
attached to that carbon atom which possesses lesser number of
hydrogen atom.
H Br
½ ½
H ¾ C ¾ C ==C ¾ H + HBr ¾® H3C ¾ C ¾ CH3
½ ½ ½ ½
H H H H
prop-1-ene 2- bromopropane
Anti-Markownikoff addition or peroxide effect or
Kharash effect In the presence of organic peroxide, addition
of only HBr molecule on unsymmetrical alkene takes place
contrary to the Markownikoff’s rule.
CH3 ¾ CH ==CH 2 + HBr ¾¾¾¾¾® CH3CH 2 CH 2 Br
prop-1ene (C6H5 CO) 2 O 2 1- bromopropane
370 Handbook of Chemistry

(iii) Addition of sulphuric acid

CH3 ¾ CH ==CH 2 + HOSO2OH —® CH3CH(OSO3 H ) CH3
[cold and conc.] propyl hydrogen sulphate
(iv) Addition of water
H3C
H+
CH3 ¾ C== CH 2 + H 2O ¾® C— CH3
½ H3C ½
CH3 OH
2-methylpropene 2-methylpropan-2-ol

(v) Oxymercuration-demercuration This reaction is an

example of hydration of alkene according to Markownikoff’s rule.
(CH3 COO) 2 Hg
(CH3 )3 ¾ CH==CH 2 ¾¾¾¾¾®
3,3-dimethylbut-1-ene THF, H2O

NaBH4
(CH3 )3 C ¾ CH ¾ CH 2Hg OOCCH3 ¾¾® (CH3 )3C ¾ CH ¾ CH3
½ NaOH ½
OOCCH3 OH
3,3-dimethylbutan 2-ol

It is an anti-addition reaction.
It is better than catalytic hydration by dil. H 2SO4, as it avoids
rearrangement.
(vi) Hydroboration oxidation
OH-
6( R ¾ CH ==CH 2 ) + B2H 6 —® 2( R ¾ CH 2 CH 2 )3 B ¾¾¾¾®
+6H2O 2
trialkyl borane

6RCH 2CH 2 OH + 2H3 BO3

primary alcohol
This reaction involved syn-addition of reagent.
(vii) Oxidation Alkenes decolourise cold dilute aqueous solution
of potassium permanganate (Baeyer’s reagent). It is used as a
test for unsaturation.
Dil. KMnO 4
CH 2==CH 2 + H 2O + [O] ¾¾¾¾® CH 2 ¾ CH 2
273 K ½ ½
OH OH
ethane -1,2- diol
or glycol
 Hydrocarbons 371
Acidic KMnO4 or acidic K 2Cr2O7 oxidise alkenes to ketones
and/or acids depending upon the nature of alkene and the
experimental conditions.
KMnO 4 /H+
(CH3 )2C==CH 2 ¾¾¾¾® (CH3 )2CO + CO2 + H 2O
2-methyl propene propan-2-one

KMnO 4 /H+
CH3 ¾ CH ==CH ¾ CH3 ¾¾¾¾® 2CH3COOH
but-2-ene ethanoic acid
(viii) Ozonolysis
H3C Zn/ H 2O
H3C
C ==CH 2 + O3 — ¾® C ==O + HCHO + H 2O2
H3C H3C
Zn + H 2O2 ¾® ZnO + H 2O
(ix) Polymerisation
High temperature/pressure
n(CH 2 ==CH 2 ) ¾¾¾¾¾¾¾¾¾¾¾® ¾ [CH 2 ¾ CH 2 ¾ ]n
catalyst
polythene

é ù
High temperature/pressure ê ú
n(CH3 ¾ CH ==CH 2 ) ¾¾¾¾¾¾¾¾¾® ê ¾ CH ¾ CH 2 ¾ ú
catalyst ê ½ ú
ê CH ú
ë 3 ûn
(x) Reaction with sulphur monochloride
CH 2 CH 2CH 2Cl
2½½ + S2Cl2 ¾® S +S
CH 2 CH CH Cl 2 2
mustard gas
(war gas)

(xii) Diels-Alder reaction (via conjugated dienes)

CH2
CH CH2
+
CH CH2
CH2
conjugated dienophile cyclohexene
diene
372 Handbook of Chemistry

Dienes having alternate single (–) and double bonds ( == ) are

called conjugated alkenes. These give Diels (-) Alder reaction.

+ ||

(xiii) Substitution reactions These occur at very high

temperature at allylic position.
500°C
CH3CH ==CH 2 + Cl2 ——® ClCH 2 ¾ CH ==CH 2 + HCl
propene D
allyl choride
(3-chloroprop-1-ene)

Reactions for Ethene [Ethylene] (C 2H4 )

2O2
2CO2 + 2H2O
(Combustion)

Ni/H2
CH3—CH3

800°C Br2 CH2—CH2

C 2 H6
(Pyrolysis)
Br Br
H2SO4 1,2-dibromoethane
C2H5OH
170°C
(Dehydration) HBr
Alc. KOH C2H4 CH3CH2Br
C2H5Cl ( Ethylene) (i) H2SO4
(Dehydrohalogenation)
CH3CH2OH
(ii) H2O
CH2—Br
+ Zn CH3CH2HSO4
H2SO4
CH2—Br (Dehalogenation)
H2O+ O
C2H2 +H2 CH2—CH2
Pd/BaSO4 dil. KMnO4
(Partial hydrogenation) 273K OH OH
(i) O3
2HCHO + H2O2
(ii) Zn/H2O

Alkynes
These are unsaturated hydrocarbons with general formula Cn H 2n - 2
e.g. C2H 2 (ethyne), C3H 4 (propyne).

Structure
H ¾ C ººC ¾ H contains 3 s and 2p-bonds and bond length is 120 pm. In
acetylene, H—C—C bond angle is 180°. In alkynes, position of triple
bond is determined by ozone (O3 ). In alkynes show position chain
functional and ring chain isomerism.
 Hydrocarbons 373
Methods of Preparation of Alkynes
(i) From calcium carbide
CaCO3 ¾® CaO + CO2
D
CaO + C ¾® CaC2 + CO
CaC2 + 2H 2O ¾® Ca(OH)2 + C2H 2
(ii) From vicinal dihalides
KOH H H
H 2C ¾ CH 2 ¾¾¾¾® C ==C
Alcohol
½ ½ - KBr H Br
Br Br - H 2O
NaNH2 - NaBr, - NH3

HC ººCH
(iii) From tetrahalides
CH3 OH
Br2CH ¾ CHBr2 + 2Zn ¾¾¾® H ¾ C ººC ¾ H + 2ZnBr2
D
Physical Properties of Alkynes
(i) The first two members are gases, next eight members (C5 ¾ C12 )
are liquids and higher members are solids.
(ii) They are all colourless and odourless with the exception of
acetylene which has slightly garlic odour due to the presence of
PH3 and H 2 S as impurities.
(iii) Alkynes are insoluble in water but soluble in organic solvents
like ethers, carbon tetrachloride and benzene.
(iv) Melting point, boiling point and density increase with increase
in molar mass.

Chemical Properties of Alkynes

Alkynes also exhibit electrophilic addition reaction but less reactive
than alkenes because the dissociation of p-electron cloud requires more
energy. Alkynes show electrophilic as well as nucleophilic addition
reactions.
(i) Acidic character of alkyne
1
HCººCH + Na ¾® HC ººC–Na + + H 2
Monosodium 2
acetylide
– – 1
H ¾ CººCNa + + Na ¾® Na + ¾ C ººCNa + + H2
Disodium acetylide 2
–
CH3 ¾ CººC ¾ H + NaNH 2 ¾® CH3 ¾ C ººCNa + + NH3
Sodium propynide
374 Handbook of Chemistry

These reactions are not shown by alkenes, alkanes and

non-terminal alkynes, hence used for distinction between alkane,
alkene and alkyne. Acetylenic hydrogens are acidic in nature due to
50% s-character in sp-hybridised orbitals.
Acidity of alkynes is lesser than water.
Acidic behaviour order
(a) HC ººCH > CH 2 ==CH 2 > CH3 ¾ CH3
sp
sp 2 sp3
(b) HC ººCH > CH3 ¾ C ººCH > > CH3 ¾ CººC ¾ CH3
(ii) Electrophilic addition reactions
H H Z
H + ½ Å ½ ½
¾ C ººC ¾ + HZ ¾® ¾ C == C ¾ + ··Z - ¾® ¾ C == C ¾
vinyl cation

The addition product formed depends upon the stability of vinylic

cation. Addition on unsymmetrical alkynes takes place according to
Markownikoff ’s rule.
Few addition reactions are as follows :
(a) Addition of dihydrogen
Pt/Pd/Ni
H3CCººC ¾ H + H 2 ¾¾¾® [CH3 ¾ CH ==CH 2 ]
propyne propene

H2
—® CH3CH 2CH3
propane
(b) Addition of halogens
HC ººCH + Cl ¾ Cl ¾® [ClHC==CHCl]
1,2-dichloropropene

Cl 2

Cl Cl
½ ½
HC ¾ CH
½ ½
Cl Cl
1, 1, 2, 2-tetrachloroethane
or westron

-HCl
CH ==CCl2
|
Cl
westrosol(1, 1, 2- trichloroethene )
 Hydrocarbons 375
(c) Addition of hydrogen halides
Br
½
HBr HBr
CH3 ¾ C ººCH ¾® CH3 ¾ C== CH 2 ¾® CH3 ¾ C ¾ CH3
½ ½
Br Br
2- bromopropene 2,2-dibromopropane

(d) Addition of water

Hg 2+ /H+
CH3 ¾ C ººCH + HOH ¾¾¾® CH3 ¾ C==CH 2
propyne 333 K ½
O¾H
isomerisation

CH3 ¾ C ¾ CH3
½½
O
propanone

(iii) Cyclic polymerisation

CH
CH CH Red hot iron
CH CH tube
873 K
CH

(iv) Reaction with AsCl 3 (arsenic trichloride)

Anhy. AlCl3
CH + Cl ¾ ¾¾¾¾ ¾® CHCl
||| | ||
CH AsCl2 CHAsCl2
Lewisite
(poisonous gas)
(v) Oxidation
CH Alk. KMnO 4 COOH
½½½ + 4 [O] ¾¾¾¾® ½
CH COOH
Oxalic acid
CH Acidic
½½½ + 3[O] + H 2O ¾¾¾® 2HCOOH
CH KMnO 4 Formic acid

CH K 2Cr2O7
½½½ + H 2O + [O] ¾¾¾® CH3COOH
CH Acetic acid
376 Handbook of Chemistry

(vi) Ozonolysis
CCl 4
CH ººCH + O3 ¾¾¾® CHO ¾ CHO ¾® 2HCOOH
Zn /H2O glyoxal formic acid
Higher alkynes give diketones which are further oxidised to
carboxylic acid.
(vii) Linear polymerisation
Cu 2Cl 2
2HC ººCH ¾¾¾® CH 2 ==CH ¾ C ººCH
NH 4Cl
HC ºº CH
¾¾¾® CH 2 ==CH ¾ C ººC ¾ CH ==CH 2
divinyl acetylene

Reactions for Acetylene (C 2H 2 )

O2
2CO2 + 3H2O
(Combustion)
6 Ag NH4OH, AgNO3
2CHCl3 Ag—C C—Ag
2H2O white
O3 CHO
CaC2
Zn/H2O
CHO
CH2—Br 2KOH CH CH Ni/H2
(Acetylene) CH3—CH3
CH2—Br
2Br2
CH—CHBr2
CHCl2 Zn
D Br2
CHCl2
HCN
Berthelot synthesis
CH2 CHCN
2C + H2
- +
sis Hg2+
CHCOOK e lectroly
Kolbe's CH2 CHOOCH3
- + CH3COOH
CHCOOK

Benzene
The parent member of the family of aromatic hydrocarbons is
benzene (molecular formula: C6H 6 ). It has hexagonal ring of six
carbon atoms with three double bonds at alternate positions. It is
resonance stabilised and the structure may be represented as given
ahead.
 Hydrocarbons 377
Structure of Benzene
On the basis of Kekule, structure of benzene has cyclic arrangement of
six carbon atoms with alternate single and double bonds and one
hydrogen atom attached to each carbon atom.

Aromaticity
Aromatic compound should possess the following characteristics :
(i) Planarity.
(ii) Complete delocalisation of the p electrons in the ring.
(iii) Presence of ( 4n + 2)p electrons in the ring where n is an integer
( n = 0, 1, 2, K ). This is often referred to as Huckel rule.

Methods of Preparation
(i) Cyclic polymerisation of ethyne Refer to text on page 371.
(ii) Decarboxylation of aromatic acids
ÈÅ
COONa

CaO
+ NaOH + Na2CO3
D

OH

Zn
(iii) + ZnO
D

Physical Properties of Benzene

Aromatic hydrocarbons are non-polar molecules and are usually
colourless liquids or solids with a characteristic aroma.
Aromatic hydrocarbons are immiscible with water but readily miscible
with organic solvents.
Aromatic compounds burn with sooty flame.

Chemical Reactions of Benzene

Benzene gives electrophilic substitution reactions.
According to experimental evidences, electrophilic substitution reaction
involve following three steps :
(a) Generation of electrophile
(b) Formation of carbocation intermediate
(c) Removal of proton from the carbocation intermediate.
378 Handbook of Chemistry

Common electrophilic substitution reactions are as follows :

(i) Nitration
NO2

323–333 K
+ Conc. HNO3 + Conc. H2SO4 + H2 O

nitrobenzene

(ii) Halogenation
Cl

Anhy. AlCl3
+ Cl2 + HCl

chlorobenzene

(iii) Sulphonation
SO3H

+ H2SO4 + H 2O
D
(fuming sulphuric
acid) benzene sulphonic acid

(iv) Friedel-Crafts alkylation reaction

CH3

Anhy. AlCl3
+ CH3Cl + HCl

toluene

When Friedel-Craft alkylation is carried out with CH3Cl the

product obtained is C6H5CH3 . In case the alkylation is carried out
with higher alkyl halide, e.g. n-propyl chloride, then the
+
electrophile n-propyl carbocation (CH3 ¾ CH 2 ¾ CH 2 ) which is a
primary carbocation rearranges to form more stable secondary
carbocation (iso-propyl carbocation) and the main product formed
will be iso-propyl benzene.
 Hydrocarbons 379
(v) Friedel-Crafts acylation reaction
COCH3

Anhy. AlCl3
+ CH3COCl D
or
(CH3CO)2O acetophenone

(vi) With Cl2 In excess of chlorine, benzene yields hexachlorobenzene

[C6Cl 6 ].
Cl
Cl Cl
Anhy. AlCl3
+ 6Cl2
Dark, cold
Cl Cl
Cl
hexachlorobenzene

Benzene also undergoes addition reactions e.g.,

Ni
(i) + 3H2 D

cyclohexane

Cl
Cl Cl
UV
(ii) + 3Cl2
500 K
Cl Cl
Cl
benzene hexachloride
(BHC or Gammexane or lindane)

Combustion 2C6H 6 + 15O2 ¾® 12CO2 + 6H 2O

380 Handbook of Chemistry

Reactions for Benzene

CO2 + H2O NO2
n
io
st

2
O
.
b u conc
om HNO 3 onc. (Nitrobenzene)
Red hot Fe C O4 c
3CH CH H 2S
– + NaOH Cl
C6H5COONa
CaO
Zn,D Cl2
C6H5OH
H3PO2 Anhy. AlCl3 (Chlorobenzene)
C6H5N2+Cl–
Ni–Al alloy Benzene
SO3H
C6H5Cl NaOH H2 S
O4
(Benzene
sulphonic
C y. A C y . A
An

H 3 l H 3 lC

acid)
h

C Cl 3 CO l 3
l

CH3
An
UV,Cl2
5 00K

(Toluene)
Cl

COCH3
H2

Cl

Cl Cl (Acetophenone)

Cl Cl
(Cyclohexane)
Cl
(BHC)
Directive Influence of Substituents
on Benzene Ring
The first substituent on benzene ring directs the next incoming group.
A A

d- d- E+ (electrophile) d+ d+
[Always attack the positions
of high electron density]
d+ d+
o and p-directing m-directing
e.g. —NH2,—OH,—OR,—R e.g. —F, —Cl, —C N
 Hydrocarbons 381
Carcinogenicity and Toxicity
Benzene and polynuclear hydrocarbons containing more than two
benzene rings fused together are toxic and said to possess cancer
producing (carcinogenic) property. e.g.

H3C

1-2-benzanthracene 3-methylcholanthrene

Petroleum
It is a dark coloured oily liquid with offensive odour, found at various
depths in many region below the earth’s surface. It is also called rock
oil, mineral oil or crude oil. It is covered by an atmosphere of a
gaseous mixture known as natural gas.
It contains mainly alkanes, cycloalkanes, aromatic hydrocarbons,
sulphur, nitrogen and oxygen compounds.
When subjected to fractional distillation, it gives different fractions at
different temperatures.
S.No. Fraction Boiling range Composition Uses

1. Uncondensed gases Room C1 - C 4 Fuel gases,

temperature refrigerants,
production of carbon
black, hydrogen.
2. Crude naphtha 30–150° C 5 - C10
(Its refractionation
gives
(i) Petroleum ether 30 - 70° C5 - C6 Solvent
(ii) Gasoline 70 - 120° C6 - C8 Fuel, petrol gas
(iii) Benzene 120 - 150° C 8 - C10 Solvent, drycleaning
derivative
3. Kerosene 150–250° C11 - C16 Fuel, illuminants, oil
gas
382 Handbook of Chemistry

S.No. Fraction Boiling range Composition Uses

4. Heavy oil 250–400° C15 - C18 Fuel for diesel
(Its refractionation engines
gives
(i) Gas oil
(ii) Fuel oil
(iii) Diesel oil
5. Residual oil Above 400°C C17 - C 40
(Its vacuum
distillation gives
(i) Lubricating oil C17 - C20 Lubrication
(ii) Paraffin wax C20 - C 30 Candles, boot polish
(iii) Vaseline C20 - C 30 Toilets, lubrication
(iv) Pitch C 30 - C 40 Paints, road
surfacing
6. Petroleum coke As fuel

LPG (Liquified Petroleum gas)

It is a mixture of butane and iso-butane with a small amount of propane.
A strong foul smelling substance, called ethyl mercaptan (C2H5SH) is
added to LPG cylinders, to help in the detection of gas leakage.
CNG (Compressed Natural Gas)
It consists mainly of methane (95%), which is a relatively unreactive
hydrocarbon and makes its nearly complete combustion possible.
Artificial Methods for Manufacturing Petrol
From higher alkanes, petrol or gasoline is obtained by cracking or
pyrolysis.
From coal, petrol can be synthesised by following two processes :
(i) Bergius process
FeO3
Coal + H 2 ¾¾¾¾® Mixture of hydrocarbons or crude oil.
450 -500°C
250 atm
The yield of gasoline by this method may be as high as 60%.
(ii) Fischer- Tropsch process
1200°C Co/Ni
C + H 2O ¾¾® CO + H 2 ¾¾¾¾® mixture of hydrocarbons.
steam 1424 3 200°C
water gas 5 -10 atm
The best catalyst for this process is a mixture of Co, thoria,
magnesia and kieselguhr.
 Hydrocarbons 383
The overall yield in this process is slightly higher than Bergius
process.
Octane Number
The quality of petrol is expressed in terms of octane number which is
defined as the percentage of iso-octane by volume in a mixture of
iso-octane and n-heptane which has the same antiknock properties as
the fuel under test.
The octane number is 100 for iso-octane (2,2,4-trimethylpentane)
Natural gas has octane number 130.
TEL (tetraethyl lead) is used as antiknocking compound.
Octane number is increased by isomerisation, alkylation or
aromatisation.
Cetane Number
Quality of diesel oils is measured in terms of cetane number which is
defined as the percentage of cetane (hexadecane) by volume in a
mixture of cetane and a-methyl naphthalene which has the same
ignition property as fuel oil under similar experimental conditions.
It is 100 for cetane and 0 for a-methyl naphthalene.