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Hydrocarbons

Question
CBSEENCH11007769

Discuss:
(a) Nitration of an alkane.
(b) Sulphonation of alkane.

Solution

(a) Nitration of alkane: The process which involves the replacement of hydrogen atom of alkanes by nitro group (-NO2) is known as nitration of an alkane. It can be carried out in two ways:
(i) Liquid phase nitration; In this method higher alkane is heated with fuming HNO3 at 413 K under pressure.
stack straight C subscript 6 straight H subscript 13 straight H with Hexane below space space plus space stack HONO subscript 2 with Fuming space nitric space acid below space rightwards arrow space stack straight C subscript 6 straight H subscript 13 NO subscript 2 with Nitro space hexane below space plus straight H subscript 2 straight O
(ii) Vapour phase nitration: Lower member of alkanes can be nitrated by vapour phase nitration i.e. by heating a gaseous mixture of hydrocarbon and nitric acid vapours at 673-773 K.
stack CH subscript 3 space minus space straight H with Methane below space plus space HO space minus space NO subscript 2 space rightwards arrow with 750 space straight K on top space stack CH subscript 3 NO subscript 2 with Nitromethane below space plus space straight H subscript 2 straight O
stack straight C subscript 2 straight H subscript 5 with Ethane below space minus straight H space plus space HO space minus space NO subscript 2 space rightwards arrow with 750 space straight K on top space stack straight C subscript 2 straight H subscript 5 space minus space NO subscript 2 with Nitroethane below space plus space straight H subscript 2 straight O
CH subscript 3 CH subscript 2 CH subscript 3 space plus space HONO subscript 2 space rightwards arrow with Heat on top

Mechanism of nitration:
The nitration of alkanes proceeds by the free radical mechanism.
HO space minus space NO subscript 2 space rightwards arrow from fission to Homolytic of space straight H space minus space straight O with. on top space plus space straight N with. on top straight O subscript 2
space straight R minus straight H space plus space straight O with. on top space minus straight H space rightwards arrow space space space straight R with. on top space plus space straight H subscript 2 straight O
space space space straight R with. on top space plus space stack NO subscript 2 space space rightwards arrow space space space space straight R space minus space NO subscript 2 with. on top

(b) Sulphonation of alkane: The process which involves the replacement of hydrogen atom of alkanes with a sulphonic acid group (-SO3H) is known as sulphonation of alkane.
It is carried out by heating higher alkanes (hexane or higher members) with fuming sulphuric acid.
stack straight C subscript 6 straight H subscript 13 straight H with Hexane below space plus space stack HOSO subscript 3 straight H with left parenthesis Fuming right parenthesis below space rightwards arrow from 673 space straight K to Heat of space straight C subscript 6 straight H subscript 13 SO subscript 3 straight H space plus space straight H subscript 2 straight O 

Mechanism of sulphonation:
The sulphonation of alkanes proceeds by the free radical mechanism.
HO minus SO subscript 3 straight H space rightwards arrow from fission to Homolytic of space straight H space minus space straight O with. on top space plus space straight S with. on top straight O subscript 3 straight H
space space space straight R minus straight H space plus space straight O with. on top straight H space rightwards arrow space space space straight R with. on top space plus space straight H subscript 2 straight O
space space space straight R with. on top space plus space stack SO subscript 3 straight H space rightwards arrow space space stack straight R minus SO subscript 3 straight H with Alkane space sulphonic space acid below with. on top